CN119816577A

CN119816577A - Process for preparing a reaction product comprising a quaternary ammonium salt

Info

Publication number: CN119816577A
Application number: CN202380057615.5A
Authority: CN
Inventors: P·R·斯蒂文森; K·K·塞勒姆; D·帕马; N·蒲鲁斯特; P·W·派克; T·D·麦卡利斯特
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2022-08-05
Filing date: 2023-08-04
Publication date: 2025-04-11
Also published as: CA3264135A1; WO2024030591A1; EP4565669A1

Abstract

A process for preparing a reaction product is disclosed, the process comprising reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound, and reacting the quaternizable compound with a quaternizing agent to form the reaction product, wherein the reaction product comprises a quaternary ammonium salt. Compositions comprising such reaction products and methods of using such compositions are also disclosed.

Description

Process for preparing a reaction product comprising a quaternary ammonium salt

The disclosed technology relates to a process for preparing a reaction product comprising a quaternary ammonium salt. Also disclosed are compositions comprising such reaction products, methods of using such compositions, uses of such compositions in fuel compositions and/or lubricating compositions, and methods of using such fuel compositions and/or lubricating compositions.

Deposit formation in diesel fuel injector nozzles is often problematic, resulting in incomplete diesel combustion, and thus power loss and/or misfire. Conventionally, polyisobutylene succinimide detergents have been used to inhibit injector fouling, but these materials have shown poor efficacy in modern engines. One class of compounds based on quaternized polyisobutylene succinimides has been shown to provide improved detergency performance in both conventional and modern diesel engines.

It has been found that quaternary ammonium salts prepared from hydrocarbyl-substituted acylating agents result in quaternary ammonium salts that provide reverse-emulsifying properties when blended into fuels. It has now been found that the use of a free radical functionalized PIBSA product (as defined and described herein) to produce a reaction product comprising a quaternary ammonium salt can provide an alternative (and possibly superior) quaternary ammonium salt for use as a deposit control additive in fuels.

The presently disclosed subject matter provides a process for preparing a reaction product comprising reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound, and reacting the quaternizable compound with a quaternizing agent to form the reaction product, wherein the reaction product comprises a quaternary ammonium salt.

The following embodiments of the present subject matter are contemplated:

1. A method for preparing a reaction product comprising reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound, and reacting the quaternizable compound with a quaternizing agent to form the reaction product, wherein the reaction product comprises a quaternary ammonium salt.

2. The method of embodiment 1, wherein the nitrogen-containing compound has (a) a nitrogen atom capable of reacting with the free-radically functionalized PIBSA product to form an imide, and (b) at least one quaternizable amino group.

3. The method of embodiment 1 or embodiment 2, wherein the quaternizing agent is suitable for converting the quaternizable amino groups to quaternary nitrogen groups.

4. The method of any of embodiments 1-3, wherein the quaternizing agent comprises at least one of an alkyl sulfonate, a dialkyl sulfate, an alkyl halide, a sultone, an alkyl phosphate, a borate, an alkyl nitrite, an alkyl nitrate, a dialkyl carbonate, an alkyl alkanoate, a hydrocarbyl-substituted carbonate, or a hydrocarbyl epoxide.

5. The method of any of embodiments 1 through 4, wherein the quaternizing agent comprises a hydrocarbyl epoxide in combination with an acid.

6. The method of any of embodiments 1-5, wherein the free-radically functionalized PIBSA product is the product of a method comprising reacting polyisobutylene with a free-radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150 ℃ to 225 ℃ to produce the product, wherein the polyisobutylene is brought to the reaction temperature prior to the addition of the free-radical initiator, and wherein the ethylenically unsaturated acylating agent is added at any time prior to or during the addition of the free-radical initiator.

7. The method of embodiment 6, wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the method.

8. The method of embodiment 6, wherein the ethylenically unsaturated acylating agent is combined with the free radical initiator for addition to the polyisobutylene after the polyisobutylene has reached the reaction temperature.

9. The method of any of embodiments 6-8, wherein the free radical functionalized PIBSA product comprises less than 15 weight percent of a material comprising two or more polyisobutylene units connected by one or more acylating agent units.

10. The method of any of embodiments 6 to 9, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

11. The method according to any one of embodiments 6 to 10, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

12. The method of embodiment 11, wherein the organic peroxide initiator comprises dipentaerythritol (diglutaroyl), dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di (t-butyl) peroxide, t-butyl hydroperoxide, 3, 4-dimethyl-3, 4-diphenyl-hexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxypivalate, t-butyl peroxy-3, 5-trimethyl-hexanoate, bis (2, 4-dichlorobenzoyl) peroxide, bis (2-methylbenzoyl) peroxide, or bis (4-t-butylcyclohexyl) peroxydicarbonate.

13. The method of any of embodiments 6-12, wherein the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, or methylenemalonic anhydride.

14. The method of any one of embodiments 6 to 13, wherein the free radical functionalized PIBSA product comprises at least one compound of the following general formula I:

Wherein each R ¹ independently represents- (CH ₂)–(C(CH₂))–(CH₃); H, or none, wherein when R ¹ is absent, the dashed double bond represents a double bond, and when R ¹ is present, the dashed double bond represents a single bond, each m independently is an integer from 1 to 52, and each n independently is 0,1, or 2.

15. The method according to any one of embodiments 6 to 14, wherein the free radical functionalized PIBSA product comprises at least 30mol% of the at least one compound of formula I.

16. The method of any of embodiments 6-15, wherein the free-radical functionalized PIBSA product comprises less than 40 weight percent unreacted polyisobutylene.

17. A composition comprising the reaction product of the method according to any one of embodiments 1 to 16.

18. A fuel composition comprising a fuel and the composition of embodiment 17.

19. A lubricating composition comprising an oil of lubricating viscosity and the composition of embodiment 17.

20. A method of improving the dehydration performance of a fuel composition, the method comprising incorporating the composition of embodiment 17 into the fuel composition.

21. A method of reducing and/or preventing injector deposits in an engine, the method comprising supplying the fuel composition of embodiment 18 to a fuel injector of the engine and operating the engine.

22. A method of lubricating a crankcase of an engine, the method comprising supplying the lubricating composition of embodiment 19 to the engine and operating the engine.

23. Use of the fuel composition of embodiment 18 for reducing and/or preventing internal deposits in an engine operated with the fuel composition.

24. The use of the lubricating composition of embodiment 19 for lubricating the crankcase of an engine.

Various features and embodiments of the subject matter are described below by way of non-limiting illustration.

Unless otherwise indicated, the amounts of each chemical component described herein do not include any solvents or diluents which may typically be present in a commercial substance, i.e., on an active chemical basis. Unless otherwise indicated, each chemical or composition referred to herein should be construed as a commercial grade material that may contain isomers, byproducts, derivatives, and other such materials that are generally understood to be present in the commercial grade.

As used herein, the term "hydrocarbyl" refers to a group having a carbon atom directly attached to the remainder of the molecule, wherein the group includes at least a carbon atom and a hydrogen atom. If the hydrocarbyl group contains more than one carbon atom, the carbons do not have to be attached to each other. For example, at least two carbons may be attached via a suitable element or group. In various embodiments, the term "hydrocarbyl" refers to a group having a carbon atom directly attached to the remainder of the molecule, wherein the group consists of carbon, hydrogen, optionally one or more heteroatoms, provided that the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. The heteroatoms may be attached to at least two carbons in the hydrocarbyl group and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen, oxygen, phosphorus, and silicon. When the hydrocarbyl group contains heteroatoms, optionally, no more than two heteroatoms will be present per ten carbon atoms in the hydrocarbyl group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for example, halogen, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy.

Examples of hydrocarbyl groups in the context of this technology therefore include (i) hydrocarbyl groups selected from aliphatic (e.g., alkyl or alkenyl), cycloaliphatic (e.g., cycloalkyl, cycloalkenyl, cyclodienyl) and aromatic groups, (ii) substituted hydrocarbyl groups selected from the group defined in (i) substituted with no more than two non-hydrocarbon substituents selected from the group consisting of halogen, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy, and/or (iii) heteroatom-containing hydrocarbyl groups selected from the group defined in (i) containing one or more heteroatoms in the ring or chain, provided that no more than two heteroatoms are present per ten carbon atoms in the group, selected from the group consisting of sulfur, nitrogen, oxygen, phosphorus and silicon. The heteroatom-containing hydrocarbon group may be substituted with no more than two non-hydrocarbon substituents and/or one or more hydrocarbon substituents. In certain embodiments, the term "hydrocarbyl" refers to a group having a carbon atom directly attached to the remainder of the molecule, wherein the group consists of a carbon atom and a hydrogen atom.

It is known that some of the materials described herein may interact in the final formulation such that the components of the final formulation may be different from those originally added. For example, metal ions (e.g., metal ions of a detergent) may migrate to other acidic or anionic sites of other molecules. The products formed thereby, including those formed when the subject compositions are employed in their intended use, may not be readily described. However, all such modifications and reaction products are included within the scope of the present subject matter, which includes compositions prepared by mixing the components described herein.

As used herein, the indefinite article "a" or "an" is intended to mean one or more than one/one or more than one. As used herein, the phrase "at least one" means one or more than one/one or more than one of the following terms. Thus, "a"/"an" and "at least one" are used interchangeably. For example, "at least one of A, B or C" means that in alternative embodiments, only one of A, B or C may be included, and any mixture of two or more of A, B and C may be included.

As used herein, the term "substantially free" means that a component does not include any intentional addition of material that is "substantially free" of the component. For example, the component may include a material of the component that is "substantially free" of material that does not exceed impurity levels, which may be the result of incomplete chemical reactions and/or unintended/undesired (but may be unavoidable) reaction products.

As used herein, the transitional term "comprising" synonymous with "comprising," "containing," or "characterized by" is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each use of "comprising" herein, the term is intended to also encompass, as alternative embodiments, the phrases "consisting essentially of, and" consisting of, wherein "consisting of excludes any elements or steps not specified, and" consisting essentially of, allows for the inclusion of additional, unrecited elements or steps that do not materially affect the essential or essential and novel characteristics of the composition or method under consideration.

Reaction products comprising quaternary ammonium salts

A process for preparing a reaction product is provided, the process comprising reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound, and reacting the quaternizable compound with a quaternizing agent to form the reaction product, wherein the reaction product comprises a quaternary ammonium salt. The preparation of reaction products comprising quaternary ammonium salts generally results in mixtures of compounds comprising quaternary ammonium salts, and such mixtures may be difficult to define except for the process steps used to prepare the reaction products.

In certain embodiments, the quaternary ammonium salt consists essentially of an imide quaternary ammonium salt. In certain embodiments, the quaternary ammonium salt consists of an imide quaternary ammonium salt. In certain embodiments, the quaternary ammonium salt is substantially free of amide quaternary ammonium salts. In certain embodiments, the reaction product is substantially free of amide quaternary ammonium salts.

Embodiments of the present technology described herein may provide for the use of reaction products comprising quaternary ammonium salts for at least one of antiwear properties, friction modification (such as for improving fuel economy), detergent properties (such as deposit control and/or varnish control), or dispersancy (such as soot control, sludge control, and/or corrosion control).

Free radical functionalized PIBSA products

Acylated polyisobutenes, such as polyisobutene succinic anhydride/acid ("PIBSA"), are useful as chemical intermediates in the preparation of a wide variety of chemical compositions, such as reaction products comprising quaternary ammonium salts as described herein. As used herein, the terms "polyisobutylene succinic anhydride," "polyisobutylene succinic acid," "polyisobutylene succinic anhydride/acid," and/or "PIBSA" mean any molecule (or composition comprising such molecules) that comprises a polyisobutylene moiety bonded (directly or indirectly) to a succinic anhydride/acid unit.

In certain embodiments, the free-radically functionalized polyisobutylene succinic anhydride/acid ("PIBSA") product is the product of a process comprising reacting polyisobutylene with a free-radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150 ℃ to 225 ℃ to produce a product, wherein the polyisobutylene is brought to the reaction temperature prior to the addition of the free-radical initiator, and wherein the ethylenically unsaturated acylating agent is added at any time prior to or during the addition of the free-radical initiator. Thus, as used herein, the term "free radical functionalized PIBSA product" refers to the product of this reaction, optionally including the following embodiments. Thus, the free radical functionalized PIBSA product may include other products of such reactions in addition to the intended and/or desired PIBSA product, as will be appreciated by one of ordinary skill in the art.

In certain embodiments, the ethylenically unsaturated acylating agent may be combined with the polyisobutylene at the beginning of the process. In certain embodiments, the ethylenically unsaturated acylating agent may be combined with a free radical initiator for addition to the polyisobutylene after the polyisobutylene has reached the reaction temperature. In certain embodiments, a method for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein the polyisobutylene is brought to the reaction temperature prior to adding the free-radical initiator and the ethylenically unsaturated acylating agent.

As used herein, the term "high vinylidene polyisobutylene" means a compound comprising at least 55 (such as at least 60, at least 65, at least 70, at least 75, or at least 80) weight percent alpha-methyl-vinylidene polyisobutylene. In certain embodiments, the high vinylidene polyisobutylene may comprise 55 to 80 wt% (such as 55 to 75 wt%, 55 to 70 wt%, 55 to 65 wt%, 55 to 60 wt%, 60 to 80 wt%, 60 to 75 wt%, 60 to 70 wt%, 60 to 65 wt%, 65 to 80 wt%, 65 to 75 wt%, 65 to 70 wt%, 70 to 80 wt%, 70 to 70 wt%, 70 to 75 wt%, or 75 to 80 wt%) of the alpha-methyl-vinylidene polyisobutylene. High vinylidene polyisobutenes are well known, are known to be highly reactive relative to other polyisobutenes, and are used as chemical intermediates in many chemical synthesis processes.

In certain embodiments, a method for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent added in two or more times at a temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product.

In certain embodiments, a method for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent added in two or more additions at a reaction temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein each of the two or more additions comprises at least 5 wt.% of the total amount of free-radical initiator to be reacted with the polyisobutylene and/or at least 5 wt.% of the total amount of ethylenically unsaturated acylating agent.

In certain embodiments, a method for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent added in two or more additions at a reaction temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein each of the two or more additions is separated in time by at least twice the half-life of the free-radical initiator.

In certain embodiments, a method for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent added in two or more additions at a reaction temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein each of the two or more additions comprises at least 5wt% of the total amount of free-radical initiator to be reacted with the polyisobutylene and/or at least 5wt% of the total amount of ethylenically unsaturated acylating agent, and wherein each of the two or more additions is separated in time by at least twice the half-life of the free-radical initiator.

In certain embodiments, a process for preparing a free-radically functionalized PIBSA product may include reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent at a temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein the polyisobutylene is brought to a reaction temperature in a continuous reactor prior to beginning continuous addition of the free-radical initiator to the polyisobutylene in the continuous reactor, and wherein the ethylenically unsaturated acylating agent is added to the continuous reactor in such a way that (i) as a mixture with the polyisobutylene, (ii) as a mixture with the free-radical initiator, and/or (iii) continuously and separately from the polyisobutylene or the free-radical initiator.

The above-described methods for preparing free-radical functionalized PIBSA products generally provide lighter colored products (e.g., free of black specks/resin without filtration), the ability to obtain functionality greater than 2, reduced energy consumption, reduced equipment maintenance, and/or reduced reaction time, as will become apparent in the specific embodiments and examples below, as compared to known methods for preparing PIBSA. These and/or other features of the free radical functionalized PIBSA products are believed to contribute to the benefits of the reaction products comprising the quaternary ammonium salts described herein.

In certain embodiments, the reaction temperatures utilized in the methods described herein for preparing the free radical functionalized PIBSA products are 155 ℃ to 225 ℃, 160 ℃ to 225 ℃, 165 ℃ to 225 ℃, 166 ℃ to 225 ℃, 167 ℃ to 225 ℃, 168 ℃ to 225 ℃, 169 ℃ to 225 ℃, 170 ℃ to 225 ℃, 171 ℃ to 225 ℃, 172 ℃ to 225 ℃, 173 ℃ to 225 ℃, 174 ℃ to 225 ℃, 175 ℃ to 225 ℃, 225 ℃ to 225 °, 150 ℃ to 220 ℃, 155 ℃ to 220 ℃,160 ℃ to 220 ℃, 165 ℃ to 220 ℃, 166 ℃ to 220 ℃, 167 ℃ to 220 ℃, 168 ℃ to 220 ℃, 169 ℃ to 220 ℃, 170 ℃ to 220 ℃, 171 ℃ to 220 ℃, 172 ℃ to 220 ℃, 173 ℃ to 220 ℃, 174 ℃ to 220 ℃, 175 ℃ to 220 ℃, 150 ℃ to 215 ℃, 155 ℃ to 215 ℃,160 ℃ to 215 ℃, 165 to 215 ℃, 166 to 215 ℃, 167 to 215 ℃, 168 to 215 ℃, 169 to 215 ℃, 170 to 215 ℃, 171 to 215 ℃, 172 to 215 ℃, 173 to 215 ℃, 174 to 215 ℃, 175 to 215 ℃, 150 to 210 ℃, 155 to 210 ℃,160 to 210 ℃, 165 to 210 ℃, 166 to 210 ℃, 167 to 210 ℃, 168 to 210 ℃, 169 to 210 ℃, 170 to 210 ℃, 171 to 210 ℃, 172 to 210 ℃, 173 to 210 ℃, 174 to 210 ℃, 175 to 210 ℃, 150 to 205 ℃, 155 to 205 ℃,160 to 205 ℃, 165 to 205 ℃, 166 to 205 ℃, 167 to 205 ℃, 168 to 205 ℃, 169 to 205 ℃, 170 to 205 ℃, 205 to 205 ℃, 171 to 205 ℃, 172 to 205 ℃, 173 to 205 ℃, 174 to 205 ℃, 175 to 205 ℃, 150 to 200 ℃, 155 to 200 ℃,160 to 200 ℃, 165 to 200 ℃, 166 to 200 ℃, 167 to 200 ℃, 168 to 200 ℃, 169 to 200 ℃, 170 to 200 ℃, 171 to 200 ℃, 172 to 200 ℃, 173 to 200 ℃, 174 ℃ to 200 ℃, 175 ℃ to 200 ℃, 150 ℃ to 195 ℃, 155 ℃ to 195 ℃,160 ℃ to 195 ℃, 165 ℃ to 195 ℃, 166 ℃ to 195 ℃, 167 ℃ to 195 ℃, 168 ℃ to 195 ℃, 169 ℃ to 195 ℃, 170 ℃ to 195 ℃, 171 ℃ to 195 ℃, 172 ℃ to 195 ℃, 173 ℃ to 195 ℃, 174 ℃ to 195 ℃, 175 ℃ to 195 ℃, 150 ℃ to 190 ℃, 155 ℃ to 190 ℃, 160 ℃ to 190 ℃, 165 ℃ to 190 ℃, 166 ℃ to 190 ℃, 167 ℃ to 190 ℃, 168 ℃ to 190 ℃, 169 ℃ to 190 ℃, 170 ℃ to 190 ℃, 171 ℃ to 190 ℃, 172 ℃ to 190 ℃, 173 ℃ to 190 ℃, 174 ℃ to 190 ℃, 175 ℃ to 190 ℃, 150 ℃ to 185 ℃, 155 ℃ to 185 ℃, 160 ℃ to 185 ℃, 165 ℃ to 185 ℃, 166 ℃ to 185 ℃, 167 ℃ to 185 ℃, 168 ℃ to 185 ℃, 169 ℃ to 185 ℃, 170 ℃ to 185 ℃, 171 ℃ to 185 ℃, 172 ℃ to 185 ℃, 173 ℃ to 185 ℃, 174 ℃ to 185 ℃, 175 ℃ to 185 ℃, 150 ℃ to 180 ℃, 155 ℃ to 180 ℃, 160 ℃ to 180 ℃, 165 ℃ to 180 ℃, 166 ℃ to 180 ℃, 167 ℃ to 180 ℃, 168 ℃ to 180 ℃, 169 ℃ to 180 ℃, 170 ℃ to 180 ℃, 171 ℃ to 180 ℃, 172 ℃ to 180 ℃, 173 ℃ to 180 ℃, 174 ℃ to 180 ℃, 175 ℃ to 180 ℃, 150 ℃ to 175 ℃, 155 ℃ to 175 ℃, 160 ℃ to 175 ℃, 165 ℃ to 175 ℃, 166 ℃ to 175 ℃, 167 ℃ to 175 ℃, 168 ℃ to 175 ℃, 169 ℃ to 175 ℃, 170 ℃ to 175 ℃, 171 ℃ to 175 ℃, 172 to 175 ℃, 173 to 175 ℃, 174 to 175 ℃, 150 to 174 ℃, 155 to 174 ℃, 160 to 174 ℃, 165 to 174 ℃, 166 to 174 ℃, 167 to 174 ℃, 168 to 174 ℃, 169 to 174 ℃, 170 to 174 ℃, 171 to 174 ℃, 172 to 174 ℃, 173 to 174 ℃, 150 to 173 ℃, 155 to 173 ℃, 160 ℃ to 173 ℃, 165 ℃ to 173 ℃, 166 ℃ to 173 ℃, 167 ℃ to 173 ℃, 168 ℃ to 173 ℃, 169 ℃ to 173 ℃, 170 ℃ to 173 ℃, 171 ℃ to 173 ℃, 172 ℃ to 173 ℃, 150 ℃ to 172 ℃, 155 ℃ to 172 ℃, 160 ℃ to 172 ℃, 165 ℃ to 172 ℃, 166 ℃ to 172 ℃, 167 ℃ to 172 ℃, 168 ℃ to 172 ℃, 169 ℃ to 172 ℃, 170 ℃ to 172 ℃, 171 ℃ to 172 ℃, 150 ℃ to 171 ℃, 155 ℃ to 171 ℃, 160 ℃ to 171 ℃, 165 ℃ to 171 ℃, 166 ℃ to 171 ℃, 167 ℃ to 171 ℃, 168 ℃ to 171 ℃, 169 ℃ to 171 ℃, 170 ℃ to 171 ℃, 150 ℃ to 170 ℃, 155 ℃ to 170 ℃, 160 ℃ to 170 ℃, 165 ℃ to 170 ℃, 166 ℃ to 170 ℃, 167 ℃ to 170 ℃, 168 ℃ to 170 ℃ or 169 ℃ to 170 ℃.

In certain embodiments, the total amount of free radical initiator added during the methods described herein for preparing the free radical functionalized PIBSA products can be from 0.01 equivalent to 1 equivalent (such as from 0.01 equivalent to 0.9 equivalent, from 0.01 equivalent to 0.8 equivalent, from 0.01 equivalent to 0.7 equivalent, from 0.01 equivalent to 0.6 equivalent, from 0.01 equivalent to 0.5 equivalent, from 0.01 equivalent to 0.45 equivalent, from 0.01 equivalent to 0.4 equivalent, from 0.01 equivalent to 0.35 equivalent, from 0.01 equivalent to 0.3 equivalent, from 0.01 equivalent to 0.25 equivalent, based on the amount of polyisobutylene being reacted, 0.01 to 0.2, 0.01 to 0.19, 0.01 to 0.18, 0.01 to 0.17, 0.01 to 0.16, 0.01 to 0.15, 0.01 to 0.14, 0.01 to 0.13, 0.01 to 0.12, 0.01 to 0.11, 0.01 to 0.1, 0.02 to 0.9, 0.02 to 0.8, 0.02 to 0.7, 0.02 to 0.6, 0.02 to 0.5, 0.02 to 0.45, 0.02 to 0.4, 0.02 to 0.35, 0.02 to 0.3, 0.02 to 0.25, 0.02 to 0.2, 0.02 to 0.19, 0.02 to 0.18, 0.02 to 0.17, 0.02 to 0.16, 0.02 to 0.15, 0.02 to 0.14, 0.02 to 0.13, 0.02 to 0.12, 0.02 to 0.11, 0.02 to 0.1, 0.03 to 0.9, 0.03 to 0.8, 0.03 to 0.7, 0.03 to 0.6, 0.03 to 0.5, 0.03 to 0.45, 0.03 to 0.4, 0.03 to 0.35, 0.03 to 0.3, 0.03 to 0.25, 0.03 to 0.2, 0.03 to 0.19, 0.03 to 0.18, 0.03 to 0.17, 0.03 to 0.16, 0.03 to 0.15, 0.03 to 0.14, 0.03 to 0.13, 0.03 to 0.12, 0.03 to 0.11, 0.03 to 0.1, 0.04 to 0.9, 0.04 to 0.8, 0.04 to 0.7, 0.04 to 0.6, 0.04 to 0.5, 0.04 to 0.45, 0.04 to 0.4, 0.04 to 0.35, 0.04 to 0.3, 0.04 to 0.25, 0.04 to 0.2, 0.04 to 0.19, 0.04 to 0.18, 0.04 to 0.17, 0.04 to 0.16, 0.04 to 0.15, 0.04 to 0.14, 0.04 to 0.13, 0.04 to 0.12, 0.04 to 0.11, 0.04 to 0.1, 0.05 to 0.9, 0.05 to 0.8, 0.05 to 0.7, 0.05 to 0.6, 0.05 to 0.5, 0.05 to 0.45, 0.05 to 0.4, 0.05 to 0.35, 0.05 to 0.3, 0.05 to 0.25, 0.05 to 0.2, 0.05 to 0.19, 0.05 to 0.18, 0.05 to 0.17, 0.05 to 0.16, 0.05 to 0.15, 0.05 to 0.14, 0.05 to 0.13, 0.05 to 0.12, 0.05 to 0.11, 0.05 to 0.1, 0.06 to 0.9, 0.06 to 0.8, 0.06 to 0.7, 0.06 to 0.6, 0.06 to 0.5, 0.06 to 0.45, 0.06 to 0.4, 0.06 to 0.35, 0.06 to 0.3, 0.06 to 0.25, 0.06 to 0.2, 0.06 to 0.19, 0.06 to 0.18, 0.06 to 0.17, 0.06 to 0.16, 0.06 to 0.15, 0.06 to 0.14, 0.06 to 0.13, 0.06 to 0.12, 0.06 to 0.11, 0.06 to 0.1, 0.07 to 0.9, 0.07 to 0.8, 0.07 to 0.7, 0.07 to 0.6, 0.07 to 0.5, 0.07 to 0.45, 0.07 to 0.4, 0.07 to 0.35, 0.07 to 0.3, 0.07 to 0.25, 0.07 to 0.2, 0.07 to 0.19, 0.07 to 0.18, 0.07 to 0.17, 0.07 to 0.16, 0.07 to 0.15, 0.07 to 0.14, 0.07 to 0.13, 0.07 to 0.12, 0.07 to 0.11 equivalent, 0.07 to 0.1 equivalent, 0.08 to 0.9 equivalent, 0.08 to 0.8 equivalent, 0.08 to 0.7 equivalent, 0.08 to 0.6 equivalent, 0.08 to 0.5 equivalent, 0.08 to 0.45 equivalent, 0.08 to 0.4 equivalent, 0.08 to 0.35 equivalent, 0.08 to 0.3 equivalent, 0.08 to 0.25 equivalent, 0.08 to 0.2 equivalent, 0.08 to 0.19 equivalent, 0.08 to 0.18 equivalent, 0.08 to 0.17, 0.08 to 0.16, 0.08 to 0.15, 0.08 to 0.14, 0.08 to 0.13, 0.08 to 0.12, 0.08 to 0.11, 0.08 to 0.1, 0.09 to 0.9, 0.09 to 0.8, 0.09 to 0.7, 0.09 to 0.6, 0.09 to 0.5, 0.09 to 0.45, 0.09 to 0.4, 0.09 to 0.35 equivalent, 0.09 to 0.3 equivalent, 0.09 to 0.25 equivalent, 0.09 to 0.2 equivalent, 0.09 to 0.19 equivalent, 0.09 to 0.18 equivalent, 0.09 to 0.17 equivalent, 0.09 to 0.16 equivalent, 0.09 to 0.15 equivalent, 0.09 to 0.14 equivalent, 0.09 to 0.13 equivalent, 0.09 to 0.12 equivalent, 0.09 to 0.11 equivalent, 0.09 to 0.1 equivalent, 0.1 to 0.9 equivalent, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.45, 0.1 to 0.4, 0.1 to 0.35, 0.1 to 0.3, 0.1 to 0.25, 0.1 to 0.2, 0.1 to 0.19, 0.1 to 0.18, 0.1 to 0.17, 0.1 to 0.16, 0.1 to 0.15, 0.1 to 0.14, 0.1 to 0.13, 0.1 to 0.12, or 0.1 to 0.11 equivalents).

In certain embodiments, the total amount of ethylenically unsaturated acylating agent added during the methods described herein for preparing the free-radically functionalized PIBSA products can be from 0.5 to 3 equivalents (such as from 0.5 to 2.9 equivalents, from 0.5 to 2.8 equivalents, from 0.5 to 2.7 equivalents, from 0.5 to 2.6 equivalents, from 0.5 to 2.5 equivalents, from 0.5 to 2.4 equivalents, from 0.5 to 2.3 equivalents, from 0.5 to 2.5 equivalents, from 0.5 to 2.2 equivalents, based on the amount of polyisobutylene reacted, 0.5 to 2.1, 0.5 to 2, 0.5 to 1.9, 0.5 to 1.8, 0.5 to 1.7, 0.5 to 1.6, 0.5 to 1.5, 0.5 to 1.4, 0.5 to 1.3, 0.5 to 1.2, 0.5 to 1.1, 0.5 to 1, 0.6 to 3, 0.6 to 2.9, 0.6 to 2.8, 0.6 to 2.7, 0.6 to 2.6, 0.6 to 2.5, 0.6 to 2.4, 0.6 to 2.3, 0.6 to 2.2, 0.6 to 2.1, 0.6 to 2, 0.6 to 1.9, 0.6 to 1.8, 0.6 to 1.7, 0.6 to 1.6, 0.6 to 1.5, 0.6 to 1.4, 0.6 to 1.3, 0.6 to 1.2, 0.6 to 1.1, 0.6 to 1, 0.7 to 3, 0.7 to 2.9, 0.7 to 2.8, 0.7 to 2.7, 0.7 to 2.6, 0.7 to 2.5, 0.7 to 2.4, 0.7 to 2.3, 0.7 to 2.2, 0.7 to 2.1, 0.7 to 2, 0.7 to 1.9, 0.7 to 1.8, 0.7 to 1.7, 0.7 to 1.6, 0.7 to 1.5, 0.7 to 1.4, 0.7 to 1.3, 0.7 to 1.2, 0.7 to 1.1, 0.7 to 1.7, 0.7 to 1, 0.8 to 3, 0.8 to 2.9, 0.8 to 2.8, 0.8 to 2.7, 0.8 to 2.6, 0.8 to 2.5, 0.8 to 2.4, 0.8 to 2.3, 0.8 to 2.1, 0.8 to 2.2, 0.8 to 2, 0.8 to 1.9, 0.8 to 1.8, 0.8 to 1.7, 0.8 to 1.6, 0.8 to 1.5, 0.8 to 1.4, 0.8 to 1.3, 0.8 to 1.2, 0.8 to 1.1, 0.8 to 1, 0.9 to 3, 0.9 to 2.9, 0.9 to 2.8, 0.9 to 2.7, 0.9 to 2.6, 0.9 to 2.5, 0.9 to 2.4, 0.9 to 2.3, 0.9 to 2.2, 0.9 to 2.1, 0.9 to 2, 0.9 to 1.9, 0.9 to 1.8, 0.9 to 1.7, 0.9 to 1.6, 0.9 to 1.5, 0.9 to 1.4, 0.9 to 1.3, 0.9 to 1.2, 0.9 to 1.1, 1 to 3, 1 to 2.9, 1 to 2.8, 1 to 2.7, 1 to 2.6, 1 to 2.5, 1 to 2.4, 1 to 2.3, 1 to 2.2, 1 to 2.1, 1 to 2.7, 1 to 1.9, 1 to 1.8, 1 to 1.7, 1 to 1.6, 1 to 1.5, 1 to 1.4, 1 to 1.3, 1 to 1.2, 1 to 1.1, 1.1 to 3, 1.1 to 2.9, 1.1 to 2.8, 1.1 to 2.7, 1.1 to 2.6, 1.1 to 2.5, 1.1 to 2.4, 1.1 to 2.3, 1.1 to 2.2, 1.1 to 2.1, 1.1 to 2, 1.1 to 1.9, 1.1 to 1.8, 1.1 to 1.7, 1.1 to 1.6, 1.1 to 1.5, 1.1 to 1.4, 1.1 to 1.3, 1.1 to 1.2, 1.2 to 3, 1.2 to 2.9, 1.2 to 2.8, 1.2 to 2.7, 1.2 to 2.6, 1.2 to 2.5, 1.2 to 2.4, 1.2 to 2.3, 1.2 to 2.2, 1.2 to 2.1, 1.2 to 2, 1.2 to 1.9, 1.2 to 1.8, 1.2 to 1.7, 1.2 to 1.6, 1.2 to 1.5, 1.2 to 1.4, 1.2 to 1.3, 1.3 to 3, 1.3 to 2.9, 1.3 to 2.8, 1.3 to 2.7, 1.3 to 2.6, 1.3 to 2.5, 1.3 to 2.4, 1.3 to 2.3, 1.3 to 2.2, 1.3 to 2.1, 1.3 to 2, 1.3 to 1.9, 1.3 to 1.8, 1.3 to 1.7, 1.3 to 1.6, 1.3 to 1.5, 1.3 to 1.4, 1.4 to 3, 1.4 to 2.9, 1.4 to 2.8, 1.4 to 2.7, 1.4 to 2.6, 1.4 to 2.5, 1.4 to 2.4, 1.4 to 2.3, 1.4 to 2.2, 1.4 to 2.1, 1.4 to 2.4, 1.4 to 1.9, 1.4 to 1.8, 1.4 to 1.7, 1.4 to 1.6, 1.4 to 1.5, 1.5 to 3, 1.5 to 2.9, 1.5 to 2.8, 1.5 to 2.7, 1.5 to 2.6, 1.5 to 2.5, 1.5 to 2.4, 1.5 to 2.3, 1.5 to 2.2, 1.5 to 2.1, 1.5 to 2, 1.5 to 1.9, 1.5 to 1.8, 1.5 to 1.7, 1.5 to 1.6, 1.6 to 3, 1.6 to 2.9, 1.6 to 2.8, 1.6 to 2.7, 1.6 to 2.6, 1.6 to 2.5, 1.6 to 2.4, 1.6 to 2.3, 1.6 to 2.2, 1.6 to 2.1, 1.1 to 2.1, 1.6 to 2.6, 1.6 to 1.9, 1.6 to 1.8, 1.6 to 1.7, 1.7 to 3, 1.7 to 2.9, 1.7 to 2.8, 1.7 to 2.7, 1.7 to 2.6, 1.7 to 2.5, 1.7 to 2.4, 1.7 to 2.3, 1.7 to 2.2, 1.7 to 2.1, 1.7 to 2.7, 1.7 to 2, 1.7 to 1.9, 1.7 to 1.8, 1.8 to 3, 1.8 to 2.9, 1.8 to 2.8, 1.8 to 2.7, 1.8 to 2.6, 1.8 to 2.5, 1.8 to 2.4, 1.8 to 2.3, 1.8 to 2.2, 1.8 to 2.1, 1.8 to 2, 1.8 to 1.9, 1.9 to 2.9, 1.9 to 2.8, 1.9 to 2.7, 1.9 to 2.6, 1.9 to 2.5, 1.9 to 2.4, 1.9 to 2.3, 1.9 to 2.2 equivalents, 1.9 to 2.1 equivalents, 1.9 to 2 equivalents, 2 to 3 equivalents, 2 to 2.9 equivalents, 2 to 2.8 equivalents, 2 to 2.7 equivalents, 2 to 2.6 equivalents, 2 to 2.5 equivalents, 2 to 2.4 equivalents, 2 to 2.3 equivalents, 2 to 2.2 equivalents, 2 to 2.1 equivalents, 2.1 to 3 equivalents, 2.1 to 2.9 equivalents, 2.1 to 2.8 equivalents, 2.1 to 2.7 equivalents, 2.1 to 2.6 equivalents, 2.1 to 2.5 equivalents, 2.1 to 2.4, 2.1 to 2.3, 2.1 to 2.2, 2.2 to 3, 2.2 to 2.9, 2.2 to 2.8, 2.2 to 2.7, 2.2 to 2.6, 2.2 to 2.5, 2.2 to 2.4, 2.2 to 2.3, 2.3 to 3, 2.3 to 2.9, 2.3 to 2.8, 2.3 to 2.7, 2.3 to 2.6, 2.3 to 2.5, 2.3 to 2.4, 2.4 to 3 equivalents, 2.4 to 2.9 equivalents, 2.4 to 2.8 equivalents, 2.4 to 2.7 equivalents, 2.4 to 2.6 equivalents, 2.4 to 2.5 equivalents, 2.5 to 3 equivalents, 2.5 to 2.9 equivalents, 2.5 to 2.8 equivalents, 2.5 to 2.7 equivalents or 2.5 to 2.6 equivalents).

In certain embodiments, the free radical functionalized PIBSA product comprises less than 15 wt% (such as less than 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5wt%, 4.5 wt%, 4 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1wt%, 0.9 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.9 wt% 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, or 0.1 wt%) of a material comprising two or more polyisobutylene units connected by one or more acylating agent units. in certain embodiments, the free radical functionalized PIBSA product is substantially free of materials comprising two or more polyisobutylene units connected by one or more acylating agent units. In certain embodiments, the free radical functionalized PIBSA product comprises from 0 wt% (such as greater than 0 wt%) to 15 wt% (such as 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8wt%, 7 wt%, 6 wt%, 5wt%, 4.5wt%, 4wt%, 3.5wt%, 3wt%, 2.5wt%, 2wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 3wt%, 2wt%, 1.5wt%, 1.8 wt% 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt% or 0.1 wt% of a material comprising two or more polyisobutylene units connected by one or more acylating agent units. in certain embodiments, the free radical functionalized PIBSA product comprises from 0 wt% to 15 wt% (such as from 0 wt% to 14 wt%, from 0 wt% to 13 wt%, from 0 wt% to 12 wt%, from 0 wt% to 11 wt%, from 0 wt% to 10 wt%, from 0 wt% to 9 wt%, from 0 wt% to 8 wt%, from 0 wt% to 7 wt%, from 0 wt% to 6 wt%, from 0 wt% to 5 wt%, from 0 wt% to 4.5 wt%, from 0 wt% to 4 wt%, from 0 wt% to 3.5 wt%, from 0 wt% to 3 wt%, from 0 wt% to 2.5 wt%, from 0 wt% to 2 wt%, and, 0 wt% to 1.9 wt%, 0 wt% to 1.8 wt%, 0 wt% to 1.7 wt%, 0 wt% to 1.6 wt%, 0 wt% to 1.5 wt%, 0 wt% to 1.4 wt%, 0 wt% to 1.3 wt%, 0 wt% to 1.2 wt%, 0 wt% to 1.1 wt%, 0 wt% to 1wt%, 0 wt% to 0.9 wt%, 0 wt% to 0.8 wt%, 0 wt% to 0.7 wt%, 0 wt% to 0.6 wt%, 0 wt% to 0.5 wt%, 0 wt% to 0.4 wt%, 0 wt% to 0.3 wt%, and, 0 wt% to 0.2wt%, 0 wt% to 0.1 wt%, more than 0 wt% to 15 wt%, more than 0 wt% to 14 wt%, more than 0 wt% to 13 wt%, more than 0 wt% to 12 wt%, more than 0 wt% to 11 wt%, more than 0 wt% to 10 wt%, more than 0 wt% to 9 wt%, more than 0 wt% to 8 wt%, more than 0 wt% to 7 wt%, more than 0 wt% to 6 wt%, more than 0 wt% to 5 wt%, more than 0 wt% to 4.5 wt%, more than 0 wt% to 4 wt%, more than 0 wt% to 3.5 wt%, From greater than 0 wt% to 3 wt%, from greater than 0 wt% to 2.5 wt%, from greater than 0 wt% to 2 wt%, from greater than 0 wt% to 1.9 wt%, from greater than 0 wt% to 1.8 wt%, from greater than 0 wt% to 1.7 wt%, from greater than 0 wt% to 1.6 wt%, from greater than 0 wt% to 1.5 wt%, from greater than 0 wt% to 1.4 wt%, from greater than 0 wt% to 1.3 wt%, from greater than 0 wt% to 1.2 wt%, from greater than 0 wt% to 1.1 wt%, from greater than 0 wt% to 1.9 wt%, from greater than 0 wt% to 0.8 wt%, From greater than 0wt% to 0.7 wt%, from greater than 0wt% to 0.6 wt%, from greater than 0wt% to 0.5 wt%, from greater than 0wt% to 0.4 wt%, from greater than 0wt% to 0.3 wt%, from greater than 0wt% to 0.2 wt%, from greater than 0wt% to 0.1 wt%, from 0.1 wt% to 15wt%, from 0.1 wt% to 14 wt%, from 0.1 wt% to 13 wt%, from 0.1 wt% to 12 wt%, from 0.1 wt% to 11 wt%, from 0.1 wt% to 10wt%, from 0.1 wt% to 9wt%, from 0.1 wt% to 8wt%, from 0.1 wt% to 7wt% 0.1 to 6 wt%, 0.1 to 5 wt%, 0.1 to 4.5 wt%, 0.1 to 4 wt%, 0.1 to 3.5 wt%, 0.1 to 3 wt%, 0.1 to 2.5 wt%, 0.1 to 2 wt%, 0.1 to 1.9 wt%, 0.1 to 1.8 wt%, 0.1 to 1.7 wt%, 0.1 to 1.6 wt%, 0.1 to 1.5 wt%, 0.1 to 1.4 wt%, 0.1 to 1.3 wt%, 0.1 to 1.2 wt%, and, 0.1 to 1.1 wt%, 0.1 to 1wt%, 0.1 to 0.9 wt%, 0.1 to 0.8 wt%, 0.1 to 0.7 wt%, 0.1 to 0.6 wt%, 0.1 to 0.5 wt%, 0.1 to 0.4 wt%, 0.1 to 0.3 wt%, 0.1 to 0.2 wt%, 0.2 to 15 wt%, 0.2 to 14 wt%, 0.2 to 13 wt%, 0.2 to 12 wt%, 0.2 to 11 wt%, 0.2 to 10 wt%, 0.2 to 9 wt%, 0.2 to 8 wt%, 0.2 to 7 wt%, 0.2 to 6 wt%, 0.2 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, 0.2 to 3.5 wt%, 0.2 to 3 wt%, 0.2 to 2.5 wt%, 0.2 to 2 wt%, 0.2 to 1.9 wt%, 0.2 to 1.8 wt%, 0.2 to 1.7 wt%, 0.2 to 1.6 wt% 0.2 to 1.5 wt%, 0.2 to 1.4 wt%, 0.2 to 1.3 wt%, 0.2 to 1.2 wt%, 0.2 to 1.1 wt%, 0.2 to 1 wt%, 0.2 to 0.9 wt%, 0.2 to 0.8 wt%, 0.2 to 0.7 wt%, 0.2 to 0.6 wt%, 0.2 to 0.5wt%, 0.2 to 0.4 wt%, 0.2 to 0.3 wt%, 0.3 to 15 wt%, 0.3 to 14 wt%, 0.3 to 13 wt%, 0.3 to 12 wt%, 0.3 to 11 wt%, 0.3 to 10 wt%, 0.3 to 9 wt%, 0.3 to 8 wt%, 0.3 to 7 wt%, 0.3 to 6 wt%, 0.3 to 5 wt%, 0.3 to 4.5 wt%, 0.3 to 4 wt%, 0.3 to 3.5 wt%, 0.3 to 3 wt%, 0.3 to 2.5 wt%, 0.3 to 2 wt%, 0.3 to 1.9 wt%, and, 0.3 to 1.8 wt%, 0.3 to 1.7 wt%, 0.3 to 1.6 wt%, 0.3 to 1.5 wt%, 0.3 to 1.4 wt%, 0.3 to 1.3 wt%, 0.3 to 1.2 wt%, 0.3 to 1.1 wt%, 0.3 to 1 wt%, 0.3 to 0.9 wt%, 0.3 to 0.8 wt%, 0.3 to 0.7 wt%, 0.3 to 0.6 wt%, 0.3 to 0.5 wt%, 0.3 to 0.4 wt%, and, 0.4 to 15 wt%, 0.4 to 14 wt%, 0.4 to 13 wt%, 0.4 to 12 wt%, 0.4 to 11 wt%, 0.4 to 10 wt%, 0.4 to 9 wt%, 0.4 to 8 wt%, 0.4 to 7 wt%, 0.4 to 6 wt%, 0.4 to 5 wt%, 0.4 to 4.5 wt%, 0.4 to 4 wt%, 0.4 to 3.5 wt%, 0.4 to 3 wt%, 0.4 to 2.5 wt%, 0.4 to 2 wt%, 0.4 to 1.9 wt%, 0.4 to 1.8 wt%, 0.4 to 1.7 wt%, 0.4 to 1.6 wt%, 0.4 to 1.5 wt%, 0.4 to 1.4 wt%, 0.4 to 1.3 wt%, 0.4 to 1.2 wt%, 0.4 to 1.1 wt%, 0.4 to 1 wt%, 0.4 to 0.9 wt%, 0.4 to 0.8 wt%, 0.4 to 0.7 wt%, 0.4 to 0.6 wt%, 0.4 to 0.5 wt%, 0.5 to 15 wt%, 0.5 to 14 wt%, 0.5 to 13 wt%, 0.5 to 12 wt%, 0.5 to 11 wt%, 0.5 to 10wt%, 0.5 to 9 wt%, 0.5 to 8 wt%, 0.5 to 7 wt%, 0.5 to 6 wt%, 0.5 to 5 wt%, 0.5 to 4.5 wt%, 0.5 to 4 wt%, 0.5 to 3.5 wt%, 0.5 to 3 wt%, and, 0.5 to 2.5 wt%, 0.5 to 2 wt%, 0.5 to 1.9 wt%, 0.5 to 1.8 wt%, 0.5 to 1.7 wt%, 0.5 to 1.6 wt%, 0.5 to 1.5 wt%, 0.5 to 1.4 wt%, 0.5 to 1.3 wt%, 0.5 to 1.2 wt%, 0.5 to 1.1 wt%, 0.5 to 1 wt%, 0.5 to 0.9 wt%, 0.5 to 0.8 wt%, 0.5 to 0.7 wt%, 0.5 to 0.6 wt%, 0.6 to 15 wt%, 0.6 to 14 wt%, 0.6 to 13 wt%, 0.6 to 12 wt%, 0.6 to 11 wt%, 0.6 to 10wt%, 0.6 to 9 wt%, 0.6 to 8 wt%, 0.6 to 7 wt%, 0.6 to 6 wt%, 0.6 to 5 wt%, 0.6 to 4.5 wt%, 0.6 to 4 wt%, 0.6 to 3.5 wt%, 0.6 to 3 wt%, and, 0.6 to 2.5 wt%, 0.6 to 2 wt%, 0.6 to 1.9 wt%, 0.6 to 1.8 wt%, 0.6 to 1.7 wt%, 0.6 to 1.6 wt%, 0.6 to 1.5 wt%, 0.6 to 1.4 wt%, 0.6 to 1.3 wt%, 0.6 to 1.2 wt%, 0.6 to 1.1 wt%, 0.6 to 1 wt%, 0.6 to 0.9 wt%, 0.6 to 0.8 wt%, 0.6 to 0.7 wt%, and, 0.7 to 15 wt%, 0.7 to 14 wt%, 0.7 to 13 wt%, 0.7 to 12 wt%, 0.7 to 11 wt%, 0.7 to 10wt%, 0.7 to 9 wt%, 0.7 to 8 wt%, 0.7 to 7 wt%, 0.7 to 6 wt%, 0.7 to 5 wt%, 0.7 to 4.5 wt%, 0.7 to 4 wt%, 0.7 to 3.5 wt%, 0.7 to 3 wt%, 0.7 to 2.5 wt%, 0.7 to 2 wt%, 0.7 to 1.9 wt%, 0.7 to 1.8 wt%, 0.7 to 1.7 wt%, 0.7 to 1.6 wt%, 0.7 to 1.5 wt%, 0.7 to 1.4 wt%, 0.7 to 1.3 wt%, 0.7 to 1.2 wt%, 0.7 to 1.1 wt%, 0.7 to 1 wt%, 0.7 to 0.9 wt%, 0.7 to 0.8 wt%, 0.8 to 15 wt%, 0.8 to 14 wt%, 0.8 to 13 wt%, 0.8 to 12 wt%, 0.8 to 11 wt%, 0.8 to 10wt%, 0.8 to 9 wt%, 0.8 to 8 wt%, 0.8 to 7 wt%, 0.8 to 6 wt%, 0.8 to 5 wt%, 0.8 to 4.5 wt%, 0.8 to 4 wt%, 0.8 to 3.5 wt%, 0.8 to 3 wt%, 0.8 to 2.5 wt%, 0.8 to 2 wt%, 0.8 to 1.9 wt%, and, 0.8 to 1.8 wt%, 0.8 to 1.7 wt%, 0.8 to 1.6 wt%, 0.8 to 1.5 wt%, 0.8 to 1.4 wt%, 0.8 to 1.3 wt%, 0.8 to 1.2 wt%, 0.8 to 1.1 wt%, 0.8 to 1 wt%, 0.8 to 0.9 wt%, 0.9 to 15wt%, 0.9 to 14 wt%, 0.9 to 13 wt%, 0.9 to 12 wt%, 0.9 to 11 wt%, 0.9 to 10 wt%, 0.9 to 9 wt%, 0.9 to 8 wt%, 0.9 to 7 wt%, 0.9 to 6 wt%, 0.9 to 5 wt%, 0.9 to 4.5 wt%, 0.9 to 4 wt%, 0.9 to 3.5 wt%, 0.9 to 3 wt%, 0.9 to 2.5 wt%, 0.9 to 2 wt%, 0.9 to 1.9 wt%, 0.9 to 1.8 wt%, 0.9 to 1.7 wt%, 0.9 to 1.6 wt% 0.9 to 1.5 wt%, 0.9 to 1.4 wt%, 0.9 to 1.3 wt%, 0.9 to 1.2 wt%, 0.9 to 1.1 wt%, 0.9 to 1 wt%, 1 to 15 wt%, 1 to 14 wt%, 1 to 13 wt%, 1 to 12 wt%, 1 to 11 wt%, 1 to 10 wt%, 1 to 9 wt%, 1 to 8 wt%, 1 to 7 wt%, 1 to 6 wt%, 1 to 5wt%, 1 to 4.5 wt%, 1 to 4 wt%, 1 to 3.5 wt%, 1 to 3 wt%, 1 to 2.5 wt%, 1 to 2 wt%, 1 to 1.9 wt%, 1 to 1.8 wt%, 1 to 1.7 wt%, 1 to 1.6 wt%, 1 to 1.5 wt%, 1 to 1.4 wt%, 1 to 1.3 wt%, 1 to 1.2 wt%, 1 to 1.1 wt%, 1.1 to 15 wt%, 1.1 to 14 wt%, 1.1 to 13 wt%, 1.1 to 12 wt%, 1.1 to 11 wt%, 1.1 to 10 wt%, 1.1 to 9 wt%, 1.1 to 8 wt%, 1.1 to 7 wt%, 1.1 to 6 wt%, 1.1 to 5 wt%, 1.1 to 4.5 wt%, 1.1 to 4 wt%, 1.1 to 3.5 wt%, 1.1 to 3 wt%, 1.1 to 2.5 wt%, 1.1 to 2 wt%, 1.1 to 1.9 wt%, 1.1 to 1.8 wt%, and, 1.1 to 1.7 wt%, 1.1 to 1.6 wt%, 1.1 to 1.5 wt%, 1.1 to 1.4 wt%, 1.1 to 1.3 wt%, 1.1 to 1.2 wt%, 1.2 to 15 wt%, 1.2 to 14 wt%, 1.2 to 13 wt%, 1.2 to 12 wt%, 1.2 to 11 wt%, 1.2 to 10 wt%, 1.2 to 9 wt%, 1.2 to 8 wt%, 1.2 to 7 wt%, 1.2 to 6 wt%, and the like, 1.2 to 5 wt%, 1.2 to 4.5 wt%, 1.2 to 4 wt%, 1.2 to 3.5 wt%, 1.2 to 3 wt%, 1.2 to 2.5 wt%, 1.2 to 2 wt%, 1.2 to 1.9 wt%, 1.2 to 1.8 wt%, 1.2 to 1.7 wt%, 1.2 to 1.6 wt%, 1.2 to 1.5 wt%, 1.2 to 1.4 wt%, 1.2 to 1.3 wt%, 1.3 to 15 wt%, 1.3 to 14 wt%, 1.3 to 13 wt%, 1.3 to 12 wt%, 1.3 to 11 wt%, 1.3 to 10 wt%, 1.3 to 9 wt%, 1.3 to 8 wt%, 1.3 to 7 wt%, 1.3 to 6 wt%, 1.3 to 5wt%, 1.3 to 4.5 wt%, 1.3 to 4 wt%, 1.3 to 3.5 wt%, 1.3 to 3 wt%, 1.3 to 2.5 wt%, 1.3 to 2 wt%, and 2 wt%, respectively, 1.3 to 1.9 wt%, 1.3 to 1.8 wt%, 1.3 to 1.7 wt%, 1.3 to 1.6 wt%, 1.3 to 1.5 wt%, 1.3 to 1.4 wt%, 1.4 to 15 wt%, 1.4 to 14 wt%, 1.4 to 13 wt%, 1.4 to 12 wt%, 1.4 to 11 wt%, 1.4 to 10 wt%, 1.4 to 9 wt%, 1.4 to 8 wt%, 1.4 to 7 wt%, 1.4 to 6 wt%, and 1.4 to 6 wt% 1.4 to 5 wt%, 1.4 to 4.5 wt%, 1.4 to 4 wt%, 1.4 to 3.5 wt%, 1.4 to 3 wt%, 1.4 to 2.5 wt%, 1.4 to 2 wt%, 1.4 to 1.9 wt%, 1.4 to 1.8 wt%, 1.4 to 1.7 wt%, 1.4 to 1.6 wt%, 1.4 to 1.5 wt%, 1.5 to 15 wt%, 1.5 to 14 wt%, 1.5 to 13 wt%, 1.5 to 12 wt% 1.5 to 11 wt%, 1.5 to 10 wt%, 1.5 to 9 wt%, 1.5 to 8 wt%, 1.5 to 7 wt%, 1.5 to 6 wt%, 1.5 to 5wt%, 1.5 to 4.5 wt%, 1.5 to 4 wt%, 1.5 to 3.5 wt%, 1.5 to 3 wt%, 1.5 to 2.5 wt%, 1.5 to 2 wt%, 1.5 to 1.9 wt%, 1.5 to 1.8 wt%, 1.5 to 1.7 wt%, and, 1.5 to 1.6 wt%, 1.6 to 15 wt%, 1.6 to 14 wt%, 1.6 to 13 wt%, 1.6 to 12 wt%, 1.6 to 11 wt%, 1.6 to 10 wt%, 1.6 to 9 wt%, 1.6 to 8 wt%, 1.6 to 7 wt%, 1.6 to 6 wt%, 1.6 to 5 wt%, 1.6 to 4.5 wt%, 1.6 to 4 wt%, 1.6 to 3.5 wt%, 1.6 to 3 wt%, and, 1.6 to 2.5 wt%, 1.6 to 2 wt%, 1.6 to 1.9 wt%, 1.6 to 1.8 wt%, 1.6 to 1.7 wt%, 1.7 to 15 wt%, 1.7 to 14 wt%, 1.7 to 13 wt%, 1.7 to 12 wt%, 1.7 to 11 wt%, 1.7 to 10 wt%, 1.7 to 9 wt%, 1.7 to 8 wt%, 1.7 to 7 wt%, 1.7 to 6 wt%, 1.7 to 5wt%, and, 1.7 to 4.5 wt%, 1.7 to 4 wt%, 1.7 to 3.5 wt%, 1.7 to 3 wt%, 1.7 to 2.5 wt%, 1.7 to 2 wt%, 1.7 to 1.9 wt%, 1.7 to 1.8 wt%, 1.8 to 15 wt%, 1.8 to 14 wt%, 1.8 to 13 wt%, 1.8 to 12 wt%, 1.8 to 11 wt%, 1.8 to 10 wt%, 1.8 to 9 wt%, 1.8 to 8 wt%, and the like, 1.8 to 7 wt%, 1.8 to 6 wt%, 1.8 to 5wt%, 1.8 to 4.5 wt%, 1.8 to 4 wt%, 1.8 to 3.5 wt%, 1.8 to 3 wt%, 1.8 to 2.5 wt%, 1.8 to 2 wt%, 1.8 to 1.9 wt%, 1.9 to 15 wt%, 1.9 to 14 wt%, 1.9 to 13 wt%, 1.9 to 12 wt%, 1.9 to 11 wt%, 1.9 to 10 wt%, and, 1.9 to 9 wt%, 1.9 to 8 wt%, 1.9 to 7 wt%, 1.9 to 6 wt%, 1.9 to 5 wt%, 1.9 to 4.5 wt%, 1.9 to 4 wt%, 1.9 to 3.5 wt%, 1.9 to 3 wt%, 1.9 to 2.5 wt%, 1.9 to 2 wt%, 2 to 15 wt%, 2 to 14 wt%, 2 to 13 wt%, 2 to 12 wt%, 2 to 11 wt%, 2 to 10wt%, 2 to 9 wt%, 2 to 8 wt%, 2 to 7 wt%, 2 to 6 wt%, 2 to 5 wt%, 2 to 4.5 wt%, 2 to 4 wt%, 2 to 3.5 wt%, 2 to 3 wt%, 2 to 2.5 wt%, 2.5 to 15 wt%, 2.5 to 14 wt%, 2.5 to 13 wt%, 2.5 to 12 wt%, 2.5 to 11 wt%, 2.5 to 10 wt%, 2.5 to 9 wt%, 2.5 to 8 wt%, 2.5 to 7 wt%, 2.5 to 6 wt%, 2.5 to 5 wt%, 2.5 to 4.5 wt%, 2.5 to 4 wt%, 2.5 to 3.5 wt%, 2.5 to 3 wt%, 3 to 15 wt%, 3 to 14 wt%, 3 to 13 wt%, 3 to 12 wt%, 3 to 11 wt%, 3 to 10wt%, 3 to 9 wt%, 3 to 8 wt%, 3 to 7 wt%, 3 to 6 wt%, 3 to 5 wt%, 3 to 4.5 wt%, 3 to 4 wt%, 3 to 3.5 wt%, 3.5 to 15 wt%, 3.5 to 14 wt%, 3.5 to 13 wt%, 3.5 to 12 wt%, 3.5 to 11 wt%, 3.5 to 10 wt%, 3.5 to 9 wt%, 3.5 to 8 wt%, 3.5 to 7 wt%, 3.5 to 6 wt%, 3.5 to 5 wt%, 3.5 to 4.5 wt%, 3.5 to 4 wt%, 4 to 15 wt%, 4 to 14 wt%, 4 to 13 wt%, 4 to 12 wt%, 4 to 11 wt%, 4 to 10 wt%, 4 to 9 wt%, 4 to 8 wt%, 4 to 7 wt%, 4 to 6 wt%, 4 to 5 wt%, 4 to 4.5 wt%, 4.5 to 15 wt%, 4.5 to 14 wt%, 4.5 to 13 wt%, 4.5 to 12 wt%, 4.5 to 11 wt%, 4.5 to 10 wt%, 4.5 to 9 wt%, 4.5 to 8 wt%, 4.5 to 7 wt%, 4.5 to 6 wt%, 4.5 to 5 wt%, 5 to 15 wt%, 5 to 14 wt%, 5 to 13 wt%, 5 to 12 wt%, 5 to 11 wt%, 5 to 10 wt%, 5 to 9 wt%, 5 to 8 wt%, 5 to 7 wt%, 5 to 6 wt%, 6 to 15 wt%, 6 to 14 wt%, 6 to 13 wt%, 6 to 12 wt%, 6 to 11 wt%, From 6 to 10 wt%, from 6 to 9 wt%, from 6 to 8 wt%, from 6 to 7 wt%, from 7 to 15 wt%, from 7 to 14 wt%, from 7 to 13 wt%, from 7 to 12 wt%, from 7 to 11 wt%, from 7 to 10 wt%, from 7 to 9 wt%, from 7 to 8 wt%, from 8 to 15 wt%, from 8 to 14 wt%, from 8 to 13 wt%, from 8 to 12 wt%, from 8 to 11 wt%, from 8 to 10 wt%, from 8 to 9 wt%, from 7 to 11 wt%, from 8 to 9 wt%, from, 9 to 15 wt%, 9 to 14 wt%, 9 to 13 wt%, 9 to 12 wt%, 9 to 11 wt%, 9 to 10 wt%, 10 to 15 wt%, 10 to 14 wt%, 10 to 13 wt%, 10 to 12 wt%, 10 to 11 wt%, 11 to 15 wt%, 11 to 14 wt%, 11 to 13 wt%, 11 to 12 wt%, 12 to 15 wt%, 12 to 14 wt%, 12 to 13 wt%, 13 to 13 wt%, 13 to 15 wt%, 13 to 14 wt% or 14 to 15 wt%) of a material comprising two or more polyisobutylene units connected by one or more acylating agent units.

In certain embodiments, the polyisobutylene comprises an average of at least 4 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 38 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 3 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 8 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 7 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 6 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 5 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 4 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 56 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 4 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 8 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 7 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 6 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 5 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 8 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 7 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 6 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 8 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 6 to 7 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 38 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 7 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 8 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 48 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 16 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 36 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 16 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 46 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 18 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 52 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 28 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 30 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 30 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 48 isobutylene monomer units per molecule. in certain embodiments, the polyisobutylene comprises an average of 48 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 53 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 53 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 53 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 54 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 54 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 55 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3,4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 51, 52, 53, 54, 55, or 56 isobutylene monomer units per molecule.

In certain embodiments, the free radical initiator may be any suitable free radical initiator and may include an organic peroxide initiator or a peracid initiator.

In certain embodiments, the organic peroxide initiator comprises dipentaerythritol, dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di (t-butyl) peroxide, t-butyl hydroperoxide, 3, 4-dimethyl-3, 4-diphenyl-hexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxypivalate, t-butyl peroxy-3, 5-trimethyl-hexanoate, bis (2, 4-dichlorobenzoyl) peroxide, bis (2-methylbenzoyl) peroxide, or bis (4-t-butylcyclohexyl) peroxydicarbonate. The half-life of these and other free radical initiators is widely available in the relevant scientific literature.

In certain embodiments, the ethylenically unsaturated acylating agent comprises at least one monoethylenically unsaturated C ₃-C₂₈ monocarboxylic acid or ester thereof or at least one C ₄-C₂₈ dicarboxylic acid, anhydride or ester thereof.

In certain embodiments, the ethylenically unsaturated acylating agent may comprise one or more compounds falling within the general formula:

Wherein X and X 'are the same or different, provided that at least one of X and X' is a group capable of reacting to esterify an alcohol, form an amide or amine salt with ammonia or an amine, form a metal salt with a reactive metal or substantially reactive metal compound, and additionally act as an acylating agent. In certain embodiments, X and/or X 'is-OH, -O-hydrocarbyl, OM+, wherein M+ represents one equivalent of a metal, ammonium or amine cation, -NH ₂, -Cl, -Br, and/or X and X' together may be-O-to form an anhydride. In certain embodiments, X and X' are such that both carboxyl functionalities can enter into the acylation reaction. Suitable reactants include maleic anhydride, monophenyl maleic anhydride, monomethyl maleic anhydride, dimethyl maleic anhydride, monochloromaleic anhydride, monobromomaleic anhydride, monofluorometaleic anhydride, dichloro maleic anhydride and difluoro maleic anhydride, phenyl maleimide and other substituted maleimides, isomaleimides, fumaric acid, maleic acid, alkyl hydrogen maleate and alkyl hydrogen fumarate, dialkyl fumarate and dialkyl maleate, monoanilide fumarate (fumaronilic acid) and monoanilide maleate (MALEANIC ACID), and maleic nitrile and fumaronitrile.

In certain embodiments, monoethylenically unsaturated dicarboxylic acids or anhydrides having 3 to 28 carbon atoms may be selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride and mixtures of these with one another.

In certain embodiments, the monoethylenically unsaturated C ₃-C₂₈ -monocarboxylic acid may be selected from the group consisting of acrylic acid, methacrylic acid, dimethacrylate, ethacrylic acid, crotonic acid, allylacetic acid, and vinylacetic acid. Another group of suitable monomers are C ₁-C₄₀ alkyl esters of monoethylenically unsaturated C ₃-C₁₀ monocarboxylic or dicarboxylic acids, such as ethyl acrylate, butyl acrylate, ethyl 2-acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate and esters of technical alcohol mixtures of 14 to 28 carbon atoms, ethyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octadecyl methacrylate, monobutyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate, monooctadecyl maleate and dioctadecyl maleate.

In certain embodiments, the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, or methylenemalonic anhydride.

In certain embodiments, the free radical functionalized PIBSA product comprises at least one compound of the following formula I:

In certain embodiments, each m is independently 1 to 53, 1 to 52, 1 to 51, 1 to 50, 1 to 49, 1 to 48, 1 to 46, 1 to 44, 1 to 42, 1 to 40, 1 to 38, 1 to 36, 1 to 34, 1 to 32, 1 to 30, 1 to 28, 1 to 26, 1 to 24, 1 to 22, 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12,1 to 10, 1 to 8, 1 to 7, 1 to 6, 1 to 5,1 to 4,1 to 3, 1 to 2, 2 to 54, 2 to 53, 2 to 52, 2 to 51, 2 to 50, 2 to 49, 2 to 48, 2 to 46, 2 to 44, 2 to 42, 2 to 40, 2 to 38, 2 to 36, 2 to 34, 2 to 32, 2 to 30, 2 to 28,2 to 26, 2 to 24, 2 to 22, 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8,2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 54, 3 to 53, 3 to 52, 3 to 51, 3 to 50, 3 to 49, 3 to 48, 3 to 46, 3 to 44, 3 to 42, 3 to 40, 3 to 38, 3 to 36, 3 to 34, 3 to 32, 3 to 30, 3 to 28, 3 to 26, 3 to 24, 3 to 22, 3 to 20, 3 to 18, 3 to 16, 3 to 14, 3 to 12, 3 to 10, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 54, 4 to 53, 4 to 52, 4 to 51, 4 to 50, 4 to 49, 4 to 48, 4 to 46, 4 to 44, 4 to 42, 4 to 40, 4 to 38, 4 to 36, 4 to 34, 4 to 32, 4 to 30, 4 to 28, 4 to 26, 4 to 24, 4 to 22, 4 to 20, 4 to 18, 4 to 16, 4 to 14, 4 to 12, 4 to 10, 4 to 8, 4 to 7, 4 to 6,4 to 5, 5 to 54, 5 to 53, 5 to 52, 5 to 51, 5 to 50, 5 to 49, 5 to 48, 5 to 46, 5 to 44, 5 to 42, 5 to 40, 5 to 38, 5 to 36, 5 to 34, 5 to 32, 5 to 30, 5 to 28, 5 to 26, 5 to 24, 5 to 22, 5 to 20, 5 to 18, 5 to 16, 5 to 14, 5 to 12, 5 to 10, 5 to 8, 5 to 7, 5 to 6, 6 to 54, 6 to 53, 6 to 52, 6 to 51, 6 to 50, 6 to 49, 6 to 48, 6 to 46, 6 to 44, 6 to 42, 6 to 40, 6 to 38, 6 to 36, 6 to 34, 6 to 32, 6 to 30, 6 to 28, 6 to 26, 6 to 24, 6 to 22, 6 to 20, 6 to 18, 6 to 16, 6 to 14, 6 to 12, 6 to 10, 6 to 8, 6 to 7, 7 to 54, 7 to 53, 7 to 52, 7 to 51, 7 to 50, 7 to 49, 7 to 48, 7 to 46, 7 to 44, 7 to 42, 7 to 40, 7 to 38, 7 to 36, 7 to 34, 7 to 32, 7 to 30, 7 to 28, 7 to 26, 7 to 24, 7 to 22, 7 to 20, 7 to 18, 7 to 16, 7 to 14, 7 to 12, 7 to 10, 7 to 8,8 to 54, 8 to 53, 8 to 52, 8 to 51, 8 to 50, 8 to 49, 8 to 48, 8 to 46, 8 to 44, 8 to 42, 8 to 40, 8 to 38, 8 to 36, 8 to 34, 8 to 32, 8 to 30, 8 to 28, 8 to 26, 8 to 24, 8 to 22, 8 to 20, 8 to 18,8 to 16, 8 to 14, 8 to 12, 8 to 10, 10 to 54, 10 to 53, 10 to 52, 10 to 51, 10 to 50, 10 to 49, 10 to 48, 10 to 46, 10 to 44, 10 to 42, 10 to 40, 10 to 38, 10 to 36, 10 to 34, 10 to 32, 10 to 30, 10 to 28, 10 to 26, 10 to 24, 10 to 22, 10 to 20, 10 to 18, 10 to 16, 10 to 14, 10 to 12, 12 to 54, 12 to 53, 12 to 52, 12 to 51, 12 to 50, 12 to 49, 12 to 48, 12 to 46, 12 to 44, 12 to 42, 12 to 40, 12 to 38, 12 to 36, 12 to 34, 12 to 32, 12 to 30, 12 to 28, 12 to 26, 12 to 24, 12 to 22, 12 to 20, 12 to 18, 12 to 16, 12 to 14, 14 to 54, 14 to 53, 14 to 52, 14 to 51, 14 to 50, 14 to 49, 14 to 48, 14 to 46, 14 to 44, 14 to 42, 14 to 40, 14 to 38, 14 to 36, 14 to 34, 14 to 32, 14 to 30, 14 to 28, 14 to 26, 14 to 24, 14 to 22, 14 to 20, 14 to 18, 14 to 16, 16 to 54, 16 to 53, 16 to 52, 16 to 51, 16 to 50, 16 to 49, 16 to 48, 16 to 46, 16 to 44, 16 to 42, 16 to 40, 16 to 38, 16 to 36, 16 to 34, 16 to 32, 16 to 30, 16 to 28, 16 to 26, 16 to 24, 16 to 22, 16 to 20, 16 to 18, 18 to 54, 18 to 53, 18 to 52, 18 to 51, 18 to 50, 18 to 49, 18 to 48, 18 to 46, 18 to 44, 18 to 42, 18 to 40, 18 to 38, 18 to 36, 18 to 34, 18 to 32, 18 to 30, 18 to 28, 18 to 26, 18 to 24, 18 to 22, 18 to 20, 20 to 54, 20 to 53, 20 to 52, 20 to 51, 20 to 50, 20 to 49, 20 to 48, 20 to 46, 20 to 44, 20 to 42, 20 to 40, 20 to 38, 20 to 36, 20 to 34, 20 to 32, 20 to 30, 20 to 28, 20 to 26, 20 to 24, 20 to 22, 22 to 54, 22 to 53, 22 to 52, 22 to 51, 22 to 50, 22 to 49, 22 to 48, 22 to 46, 22 to 44, 22 to 42, 22 to 40, 22 to 38, 22 to 36, 22 to 34, 22 to 32, 22 to 30, 22 to 28, 22 to 26, 22 to 24, 24 to 54, 24 to 53, 24 to 52, 24 to 51, 24 to 50, 24 to 49, 24 to 48, 24 to 46, 24 to 44, 24 to 42, 24 to 40, 24 to 38, 24 to 36, 24 to 34, 24 to 32, 24 to 30, 24 to 28, 24 to 26, 26 to 54, 26 to 53, 26 to 52, 26 to 51, 26 to 50, 26 to 49, 26 to 48, 26 to 46, 26 to 44, 26 to 42, 26 to 40, 26 to 38, 26 to 36, 26 to 34, 26 to 32, 26 to 30, 26 to 28, 28 to 54, 28 to 53, 28 to 52, 28 to 51, 28 to 50, 28 to 49, 28 to 48, 28 to 46, 28 to 44, 28 to 42, 28 to 40, 28 to 38, 28 to 36, 28 to 34, 28 to 32, 28 to 30, 30 to 54, 30 to 53, 30 to 52, 30 to 51, 30 to 50, 30 to 49, 30 to 48, 30 to 46, 30 to 44, 30 to 42, 30 to 40, 30 to 38, 30 to 36, 30 to 34, 30 to 32, 32 to 54, 32 to 53, 32 to 52, 32 to 51, 32 to 50, 32 to 49, 32 to 48, 32 to 46, 32 to 44, 32 to 42, 32 to 40, 32 to 38, 32 to 36, 32 to 34, 34 to 54, 34 to 53, 34 to 52, 34 to 51, 34 to 50, 34 to 49, 34 to 48, 34 to 46, 34 to 44, 34 to 42, 34 to 40, 34 to 38, 34 to 36, 36 to 54, 36 to 53, 36 to 52, 36 to 51, 36 to 50, 36 to 49, 36 to 48, 36 to 46, 36 to 44, 36 to 42, 36 to 40, 36 to 38, 38 to 54, 38 to 53, 38 to 52, 38 to 51, 38 to 50, 38 to 49, 38 to 48, 38 to 46, 38 to 44, 38 to 42, 38 to 40, 40 to 54, 40 to 53, 40 to 52, 40 to 51, 40 to 50, 40 to 49, 40 to 48, 40 to 46, 40 to 44, 40 to 42, 42 to 54, 42 to 53, 42 to 52, 42 to 51, 42 to 50, 42 to 49, 42 to 48, 42 to 46, 42 to 44, 44 to 54, 44 to 53, 44 to 52, 44 to 51, 44 to 50, 44 to 49, 44 to 48, 44 to 46, 46 to 54, 46 to 53, 46 to 52, 46 to 51, 46 to 50, 46 to 49, 46 to 48, 48 to 54, 48 to 53, 48 to 52, 48 to 51, 48 to 50, 48 to 49, 49 to 54, 49 to 53, 49 to 52, 49 to 51, 49 to 50, 50 to 54, 50 to 53, 50 to 52, 50 to 51, 51 to 54, 51 to 53, 51 to 52, 51 to 51, 52 to 54, 52 to 53, or an integer of 53 to 54. In certain embodiments, each m is independently 1,2,3, 4, 5, 6, 7, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 49, 50, 51, 52, 53, or 54.

In certain embodiments, the free radical functionalized PIBSA product comprises at least 30mol% (such as at least 35mol%, 40mol%, 45mol%, 50mol%, 55mol%, 60mol%, 65mol%, 70mol%, 75mol%, 80mol%, 85mol%, 90mol%, 95mol%, or 99 mol%) of at least one compound of formula I. In certain embodiments, the free radical functionalized PIBSA product comprises 30mol% to 100mol% (such as 35mol% to 100mol%, 40mol% to 100mol%, 45mol% to 100mol%, 50mol% to 100mol%, 55mol% to 100mol%, 60mol% to 100mol%, 65mol% to 100mol%, 70mol% to 100mol%, 75mol% to 100mol%, 80mol% to 100mol%, 85mol% to 100mol% >, 90 to 100mol%, 95 to 100mol%, 99 to 100mol%, 30 to 99mol%, 35 to 99mol%, 40 to 99mol%, 45 to 99mol%, 50 to 99mol%, 55 to 99mol%, 60 to 99mol%, 65 to 99mol%, 70 to 99mol%, 75 to 99mol%, 80 to 99mol%, 85 to 99mol%, and the like, 90 to 99mol%, 95 to 99mol%, 30 to 95mol%, 35 to 95mol%, 40 to 95mol%, 45 to 95mol%, 50 to 95mol%, 55 to 95mol%, 60 to 95mol%, 65 to 95mol%, 70 to 95mol%, 75 to 95mol%, 80 to 95mol%, 85 to 95mol%, 90 to 95mol%, 30mol% to 90mol%, 35mol% to 90mol%, 40mol% to 90mol%, 45mol% to 90mol%, 50mol% to 90mol%, 55mol% to 90mol%, 60mol% to 90mol%, 65mol% to 90mol%, 70mol% to 90mol%, 75mol% to 90mol%, 80mol% to 90mol%, 85mol% to 90mol%, 30mol% to 85mol%, 35mol% to 85mol%, 40mol% to 85mol%, and, 45mol% to 85mol%, 50mol% to 85mol%, 55mol% to 85mol%, 60mol% to 85mol%, 65mol% to 85mol%, 70mol% to 85mol%, 75mol% to 85mol%, 80mol% to 85mol%, 30mol% to 80mol%, 35mol% to 80mol%, 40mol% to 80mol%, 45mol% to 80mol%, 50mol% to 80mol%, 55mol% to 80mol%, 60mol% to 80mol%, and, 65mol% to 80mol%, 70mol% to 80mol%, 75mol% to 80mol%, 30mol% to 75mol%, 35mol% to 75mol%, 40mol% to 75mol%, 45mol% to 75mol%, 50mol% to 75mol%, 55mol% to 75mol%, 60mol% to 75mol%, 65mol% to 75mol%, 70mol% to 75mol%, 30mol% to 70mol%, 35mol% to 70mol%, 40mol% to 70mol%, and, 45mol% to 70mol%, 50mol% to 70mol%, 55mol% to 70mol%, 60mol% to 70mol%, 65mol% to 70mol%, 30mol% to 65mol%, 35mol% to 65mol%, 40mol% to 65mol%, 45mol% to 65mol%, 50mol% to 65mol%, 55mol% to 65mol%, 60mol% to 65mol%, 30mol% to 60mol%, 35mol% to 60mol%, 40mol% to 60mol%, and, 45mol% to 60mol%, 50mol% to 60mol%, 55mol% to 60mol%, 30mol% to 55mol%, 35mol% to 55mol%, 40mol% to 55mol%, 45mol% to 55mol%, 50mol% to 55mol%, 30mol% to 50mol%, 35mol% to 50mol%, 40mol% to 50mol%, 45mol% to 50mol%, 30mol% to 45mol%, 35mol% to 45mol%, 40mol% to 45mol%, and, 30 to 40mol%, 35 to 40mol% or 30 to 35 mol%) of at least one compound of the formula I.

In certain embodiments, the free-radical functionalized PIBSA product comprises less than 40 wt% (such as less than 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7wt%, 6 wt%, 5wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%) of unreacted polyisobutylene. in certain embodiments, the free radical functionalized PIBSA product comprises from 0wt% to 40 wt% (such as from 0wt% to 35 wt%, from 0wt% to 30 wt%, from 0wt% to 25 wt%, from 0wt% to 20 wt%, from 0wt% to 15 wt%, from 0wt% to 14 wt%, from 0wt% to 13 wt%, from 0wt% to 12 wt%, from 0wt% to 11 wt%, from 0wt% to 10wt%, from 0wt% to 9 wt%, from 0wt% to 8wt%, from 0wt% to 7 wt%, from 0wt% to 6 wt%, from 0wt% to 5 wt%, from 0wt% to 4 wt% 0 to 3 wt%, 0 to 2 wt%, 0 to 1 wt%, more than 0 to 40 wt%, more than 0 to 35 wt%, more than 0 to 30 wt%, more than 0 to 25 wt%, more than 0 to 20 wt%, more than 0 to 15 wt%, more than 0 to 14 wt%, more than 0 to 13 wt%, more than 0 to 12 wt%, more than 0 to 11 wt%, more than 0 to 10 wt%, more than 0 to 9 wt%, more than 0 to 8 wt%, more than 0 to 7 wt%, From greater than 0wt% to 6 wt%, from greater than 0wt% to 5 wt%, from greater than 0wt% to 4 wt%, from greater than 0wt% to 3 wt%, from greater than 0wt% to 2 wt%, from greater than 0wt% to 1wt%, from greater than 0wt% to 35 wt%, from 1wt% to 40wt%, from 1wt% to 35 wt%, from 1wt% to 30wt%, from 1wt% to 25 wt%, from 1wt% to 20wt%, from 1wt% to 15 wt%, from 1wt% to 14 wt%, from 1wt% to 13 wt%, from 1wt% to 12 wt%, from 1wt% to 11 wt%, from 1wt% to 10wt%, from 1wt% to 30wt%, from 1wt% to 13 wt%, from 1wt% to 12 wt%, from 1wt% to 11 wt%, from 1wt% to 10wt%, from, 1 to 9 wt%, 1 to 8wt%, 1 to 7 wt%, 1 to 6 wt%, 1 to 5 wt%, 1 to 4 wt%, 1 to 3 wt%, 1 to 2 wt%, 2 to 40 wt%, 2 to 35 wt%, 2 to 30 wt%, 2 to 25 wt%, 2 to 20 wt%, 2 to 15 wt%, 2 to 14 wt%, 2 to 13 wt%, 2 to 12 wt%, 2 to 11 wt%, 2 to 10 wt%, 2 to 9 wt%, 2 to 8wt%, 2 to 7 wt%, 2 to 6 wt%, 2 to 5 wt%, 2 to 4 wt%, 2 to 3 wt%, 3 to 40 wt%, 3 to 35 wt%, 3 to 30 wt%, 3 to 25 wt%, 3 to 20 wt%, 3 to 15 wt%, 3 to 14 wt%, 3 to 13 wt%, 3 to 12 wt%, 3 to 11 wt%, 3 to 10 wt%, 3 to 9 wt%, 3 to 15 wt%, the following components are mixed together, 3 to 8wt%, 3 to 7 wt%, 3 to 6 wt%, 3 to 5 wt%, 3 to 4 wt%, 4 to 40 wt%, 4 to 35 wt%, 4 to 30 wt%, 4 to 25 wt%, 4 to 20 wt%, 4 to 15 wt%, 4 to 14 wt%, 4 to 13 wt%, 4 to 12 wt%, 4 to 11 wt%, 4 to 10 wt%, 4 to 9 wt%, 4 to 8wt%, 4 to 7 wt%, 4 to 6 wt%, 4 to 5wt%, 5 to 40 wt%, 5 to 35 wt%, 5 to 30 wt%, 5 to 25 wt%, 5 to 20 wt%, 5 to 15wt%, 5 to 14 wt%, 5 to 13 wt%, 5 to 12 wt%, 5 to 11 wt%, 5 to 10 wt%, 5 to 9 wt%, 5 to 8 wt%, 5 to 7 wt%, 5 to 6 wt%, 6 to 40 wt%, 6 to 35 wt%, 5 to 14 wt%, and, 6 to 30wt%, 6 to 25 wt%, 6 to 20wt%, 6 to 15 wt%, 6 to 14 wt%, 6 to 13 wt%, 6 to 12 wt%, 6 to 11 wt%, 6 to 10wt%, 6 to 9 wt%, 6 to 8 wt%, 6 to 7 wt%, 7 to 40wt%, 7 to 35 wt%, 7 to 30wt%, 7 to 25 wt%, 7 to 20wt%, 7 to 15 wt%, 7 to 14 wt%, 6 to 10wt%, and, 7 to 13 wt%, 7 to 12 wt%, 7 to 11 wt%, 7 to 10wt%, 7 to 9 wt%, 7 to 8 wt%, 8 to 40wt%, 8 to 35 wt%, 8 to 30wt%, 8 to 25 wt%, 8 to 20wt%, 8 to 15 wt%, 8 to 14 wt%, 8 to 13 wt%, 8 to 12 wt%, 8 to 11 wt%, 8 to 10wt%, 8 to 9 wt%, 9 to 40wt%, 9 to 35 wt%, 9 to 30wt%, 9 to 25 wt%, 9 to 20wt%, 9 to 15 wt%, 9 to 14 wt%, 9 to 13 wt%, 9 to 12 wt%, 9 to 11 wt%, 9 to 10wt%, 10 to 40wt%, 10 to 35 wt%, 10 to 30wt%, 10 to 25 wt%, 10 to 20wt%, 10 to 15 wt%, 10 to 14 wt%, 10 to 13 wt%, 10 to 12 wt%, 10 to 11 wt%, 11 to 40 wt%, 11 to 35 wt%, 11 to 30 wt%, 11 to 25 wt%, 11 to 20 wt%, 11 to 15 wt%, 11 to 14 wt%, 11 to 13 wt%, 11 to 12 wt%, 12 to 40 wt%, 12 to 35 wt%, 12 to 30 wt%, 12 to 25 wt%, 12 to 20 wt%, 12 to 15 wt%, 12 to 14 wt%, 12 to 13 wt%, 13 to 40 wt%, 13 to 35 wt%, 13 to 30 wt%, 13 to 25 wt%, 13 to 20 wt%, 13 to 15 wt%, 13 to 14 wt%, 14 to 40 wt%, 14 to 35 wt%, 14 to 30 wt%, 14 to 25 wt%, 14 to 20 wt%, 14 to 15 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt.%, 15 to 25 wt.%, 15 to 20wt.%, 20 to 40 wt.%, 20 to 35 wt.%, 20 to 30 wt.%, 20 to 25 wt.%, 25 to 40 wt.%, 25 to 35 wt.%, 25 to 30 wt.%, 30 to 40 wt.%, 30 to 35 wt.%, or 35 to 40 wt.%) of unreacted polyisobutylene.

Also provided are embodiments of the above process for preparing a free-radically functionalized PIBSA product, wherein the process comprises reacting a polyisobutylene with a free-radical initiator and an ethylenically unsaturated acylating agent added in two or more times at a reaction temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product. In certain embodiments, the free radical initiator and the ethylenically unsaturated acylating agent are added in two to ten additions, such as two to nine, two to eight, two to seven, two to six, two to five, two to four, two to three, or three additions.

In certain embodiments, each of the two or more additions independently comprises at least 5 wt% (such as at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%) of the total amount of free radical initiator to be reacted with the polyisobutylene and/or at least 5 wt% (such as at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%) of the total amount of ethylenically unsaturated acylating agent. in certain embodiments, each of the two or more additions independently comprises up to 95 wt% (such as up to 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt% or 10 wt%) of the total amount of free radical initiator to be reacted with the polyisobutylene and/or up to 95 wt% (such as up to 90 wt%, 85 wt%, 80 wt% >, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40wt%, 35 wt%, 30 wt%, 25 wt%, 20wt%, 15 wt% or 10 wt%). In certain embodiments, each of the two or more additions independently comprises 5 wt% to 95 wt% (such as 5 wt% to 90 wt%, 5 wt% to 85 wt%, 5 wt% to 80 wt%, 5 wt% to 75 wt%, 5 wt% to 70 wt%, 5 wt% to 65 wt%, 5 wt% to 60 wt%, 5 wt% to 55 wt%, 5 wt% to 50 wt%, 5 wt% to 45 wt%, 5 wt% to 40 wt%, 5 wt% to 35 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, and, 5 to 15 wt%, 5 to 10 wt%, 10 to 95 wt%, 10 to 90 wt%, 10 to 85 wt%, 10 to 80 wt%, 10 to 75 wt%, 10 to 70 wt%, 10 to 65 wt%, 10 to 60 wt%, 10 to 55 wt%, 10 to 50 wt%, 10 to 45 wt%, 10 to 40 wt%, 10 to 35 wt%, 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 15 to 95 wt%, 15 to 90 wt%, 15 to 85 wt%, 15 to 80 wt%, 15 to 75 wt%, 15 to 70 wt%, 15 to 65 wt%, 15 to 60 wt%, 15 to 55 wt%, 15 to 50 wt%, 15 to 45 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 95 wt%, 20 to 90 wt%, 20 to 85 wt%, 20 to 80 wt%, 20 to 75 wt%, 20 to 70 wt%, 20 to 65 wt%, 20 to 60 wt%, 20 to 55 wt%, 20 to 50 wt%, 20 to 45 wt%, 20 to 40 wt%, 20 to 35 wt%, 20 to 30 wt%, 20 to 25 wt%, 25 to 95 wt%, 25 to 90 wt%, 25 to 85 wt%, 25 to 80 wt%, 25 to 75 wt%, 25 to 70 wt%, 25 to 65 wt%, 25 to 60 wt%, 25 to 55 wt%, 25 to 50 wt%, 25 to 45 wt%, 25 to 40 wt%, 25 to 35 wt%, 25 to 30 wt%, 30 to 95 wt%, 30 to 90 wt%, 30 to 85 wt%, 30 to 80 wt%, 30 to 75 wt%, 30 to 70 wt%, 30 to 65 wt%, 30 to 60 wt%, 30 to 55 wt%, 30 to 50 wt%, 30 to 45 wt%, 30 to 40 wt%, 30 to 35 wt%, 35 to 95 wt%, 35 to 90 wt%, 35 to 85 wt%, 35 to 80 wt%, 35 to 75 wt%, 35 to 70 wt%, 35 to 65 wt%, 35 to 60 wt%, 35 to 55 wt%, 35 to 50 wt%, 35 to 45 wt%, 35 to 40 wt%, 40 to 95 wt%, 40 to 90 wt%, 40 to 85 wt%, 40 to 80 wt%, 40 to 75 wt%, 40 to 70 wt%, 40 to 65 wt%, 40 to 60 wt%, 40 to 55 wt%, 40 to 50 wt%, 40 to 45 wt%, 45 to 95 wt%, 45 to 90 wt%, 45 to 85%, 45 to 80%, 45 to 75%, 45 to 70%, 45 to 65%, 45 to 60%, 45 to 45%, 45 to 50%, 50 to 95%, 50 to 90%, 50 to 85%, 50 to 80%, 50 to 75%, 50 to 70%, 50 to 65%, 50 to 60% or 50 to 55%, and/or 5 to 95% (such as 5 to 90%, 5 to 90%) of the total amount of free radical initiator, 5 to 85%, 5 to 80%, 5 to 75%, 5 to 70%, 5 to 65%, 5 to 60%, 5 to 55%, 5 to 50%, 5 to 45%, 5 to 40%, 5 to 35%, 5 to 30%, 5 to 25%, 5 to 20%, 5 to 15%, 5 to 10%, 10 to 95%, 10 to 90%, 10 to 85%, 5 to 25%, and the like, 10 to 80 wt%, 10 to 75 wt%, 10 to 70 wt%, 10 to 65 wt%, 10 to 60 wt%, 10 to 55 wt%, 10 to 50 wt%, 10 to 45 wt%, 10 to 40 wt%, 10 to 35 wt%, 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 15 to 95 wt%, 15 to 90 wt%, 15 to 85 wt%, 15 to 80 wt%, 15 to 75 wt%, 15 to 70 wt%, 15 to 65 wt%, 15 to 60 wt%, 15 to 55 wt%, 15 to 50 wt%, 15 to 45 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 95 wt%, 20 to 90 wt%, 20 to 85 wt%, 20 to 80 wt%, 20 to 75 wt%, 20 to 70 wt%, 20 to 65 wt%, 20 to 60 wt%, 20 to 55 wt%, 20 to 50 wt%, 20 to 45 wt%, 20 to 40 wt%, 20 to 35 wt%, 20 to 30 wt%, 20 to 25 wt%, 25 to 95 wt%, 25 to 90 wt%, 25 to 85 wt%, 25 to 80 wt%, 25 to 75 wt%, 25 to 70 wt%, 25 to 65 wt%, 25 to 60 wt%, 25 to 55 wt%, 25 to 50 wt%, 25 to 45 wt%, 25 to 40 wt%, 25 to 35 wt%, 25 to 30 wt%, 30 to 95 wt%, 30 to 90 wt%, 30 to 85 wt%, 30 to 80 wt%, 30 to 75 wt%, 30 to 70 wt%, 30 to 65 wt%, 30 to 60 wt%, 30 to 55 wt%, 30 to 50 wt%, 30 to 45 wt%, 30 to 40 wt%, 30 to 35 wt%, 35 to 95 wt%, 35 to 90 wt%, 35 to 85 wt%, 35 to 80 wt%, 35 to 75 wt%, 35 to 70 wt%, 35 to 65 wt%, 35 to 60 wt%, 35 to 55 wt%, 35 to 50 wt%, 35 to 45 wt%, 35 to 40 wt%, 40 to 95 wt%, 40 to 90 wt%, 40 to 85 wt%, 40 to 80 wt%, 40 to 75 wt%, 40 to 70 wt%, 40 to 65 wt%, 40 to 60 wt%, 40 to 55 wt%, 40 to 50 wt%, 40 to 45 wt%, 45 to 95 wt%, 45 to 90 wt%, 45 to 85 wt%, 45 to 80 wt%, 45 to 75 wt%, 45 to 70 wt%, 45 to 65 wt%, 45 to 60 wt%, 45 to 45 wt%, 45 to 50 wt%, 50 to 95 wt%, 50 to 90 wt%, 50 to 85 wt%, 50 to 80wt%, 50 to 75 wt%, 50 to 70 wt%, 50 to 65 wt%, 50 to 60 wt% or 50 to 55 wt%) of the total amount of ethylenically unsaturated acylating agents to react with the polyisobutylene.

In certain embodiments, at least two of the two or more additions are separated in time by at least the half-life of the free radical initiator. In certain embodiments, at least two of the two or more additions are separated in time by at least 1.1 times (such as at least 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, 3 times, 3.1 times, 3.2 times, 3.3 times, 3.4 times, 3.5 times, 3.6 times, 3.7 times, 3.8 times, 3.9 times, 4 times, 4.2 times, 4.4 times, a free radical initiator half-life, 4.6 times, 4.8 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 9.5 times or 10 times). In certain embodiments, each of the two or more additions is spaced in time from 1 to 10 times (such as 1.1 to 10 times, 1.2 to 10 times, 1.3 to 10 times, 1.4 to 10 times, 1.5 to 10 times, 1.6 to 10 times, 1.7 to 10 times, 1.8 to 10 times, 1.9 to 10 times, 2 to 10 times, 2.1 to 10 times, 2.2 to 10 times, 2.3 to 10 times, 2.4 to 10 times, 2.5 to 10 times, 2.6 to 10 times, 2.7 to 10 times) the half-life of the free radical initiator 2.8 to 10 times, 2.9 to 10 times, 3 to 10 times, 3.1 to 10 times, 3.2 to 10 times, 3.3 to 10 times, 3.4 to 10 times, 3.5 to 10 times, 3.6 to 10 times, 3.7 to 10 times, 3.8 to 10 times, 3.9 to 10 times, 4 to 10 times, 4.2 to 10 times, 4.4 to 10 times, 4.6 to 10 times, 4.8 to 10 times, 5 to 10 times, 5.5 to 10 times, 6 to 10 times, 6.5 to 10 times, 7 to 10 times, 7.5 to 10 times, 8 to 10 times, 8.5 to 10 times, 9 to 10 times, 9.5 to 10 times, 1 to 9.5 times, 1.1 to 9.5 times, 1.2 to 9.5 times, 1.3 to 9.5 times, 1.4 to 9.5 times, 1.5 to 9.5 times, 1.6 to 9.5 times, 1.7 to 9.5 times, 1.8 to 9.5 times, 1.9 to 9.5 times, 2 to 9.5 times, 2.1 to 9.5 times, 2.2 to 9.5 times, 2.3 to 9.5 times, 2.4 to 9.5 times, 2.5 to 9.5 times, 2.6 to 9.5 times, 2.7 to 9.5 times, 1.5 to 9.5 times, 2.8 to 9.5 times, 2.9 to 9.5 times, 3 to 9.5 times, 3.1 to 9.5 times, 3.2 to 9.5 times, 3.3 to 9.5 times, 3.4 to 9.5 times, 3.5 to 9.5 times, 3.6 to 9.5 times, 3.7 to 9.5 times, 3.8 to 9.5 times, 3.9 to 9.5 times, 4 to 9.5 times, 4.2 to 9.5 times, 4.4 to 9.5 times, 4.6 to 9.5 times, 4.8 to 9.5 times, 5 to 9.5 times, 5.5 to 9.5 times, 6 to 9.5 times, 6.5 to 9.5 times, 7 to 9.5 times, 7.5 to 9.5 times, 8 to 9.5 times, 8.5 to 9.5 times, 9 to 9.5 times, 1 to 9 times, 1.1 to 9 times, 1.2 to 9 times, 1.3 to 9 times, 1.4 to 9 times, 1.5 to 9 times, 1.6 to 9 times, 1.7 to 9 times, 1.8 to 9 times, 1.9 to 9 times, 2 to 9 times, 2.1 to 9 times, 2.2 to 9 times, 2.3 to 9 times, 2.4 to 9 times, 2.5 to 9 times, 2.6 to 9 times, 2.7 to 9 times, 2.8 to 9 times, 2.9 to 9 times, 3 to 9 times, 1.9 to 9 times, 3.1 to 9 times, 3.2 to 9 times, 3.3 to 9 times, 3.4 to 9 times, 3.5 to 9 times, 3.6 to 9 times, 3.7 to 9 times, 3.8 to 9 times, 3.9 to 9 times, 4 to 9 times, 4.2 to 9 times, 4.4 to 9 times, 4.6 to 9 times, 4.8 to 9 times, 5 to 9 times, 5.5 to 9 times, 6 to 9 times, 6.5 to 9 times, 7 to 9 times, 7.5 to 9 times, 8 to 9 times, 8.5 to 9 times, 1 to 8.5 times, 1.1 to 8.5 times, 1.2 to 8.5 times, 1.3 to 8.5 times, 1.5 to 8.5 times, 1.4 to 8.5 times, 1.5 to 8.5 times, 1.6 to 8.5 times, 1.7 to 8.5 times, 1.8 to 8.5 times, 1.9 to 8.5 times, 2 to 8.5 times, 2.1 to 8.5 times, 2.2 to 8.5 times, 2.3 to 8.5 times, 2.4 to 8.5 times, 2.5 to 8.5 times, 2.6 to 8.5 times, 2.7 to 8.5 times, 2.8 to 8.5 times, 2.9 to 8.5 times, 3 to 8.5 times, 3.1 to 8.5 times, 3.2 to 8.5 times, 3.3 to 8.5 times, 3.4 to 8.5 times, 3.5 times, 3.5 to 8.5 times, 3.6 to 8.5 times, 3.7 to 8.5 times, 3.8 to 8.5 times, 3.9 to 8.5 times, 4 to 8.5 times, 4.2 to 8.5 times, 4.4 to 8.5 times, 4.6 to 8.5 times, 4.8 to 8.5 times, 5 to 8.5 times, 5.5 to 8.5 times, 6 to 8.5 times, 6.5 to 8.5 times, 7 to 8.5 times, 7.5 to 8.5 times, 8 to 8.5 times, 1 to 8 times, 1.1 to 8 times, 1.2 to 8 times, 1.3 to 8 times, 1.4 to 8 times, 1.5 to 8 times, 1.2 to 8 times, 1.6 to 8 times, 1.7 to 8 times, 1.8 to 8 times, 1.9 to 8 times, 2 to 8 times, 2.1 to 8 times, 2.2 to 8 times, 2.3 to 8 times, 2.4 to 8 times, 2.5 to 8 times, 2.6 to 8 times, 2.7 to 8 times, 2.8 to 8 times, 2.9 to 8 times, 3 to 8 times, 3.1 to 8 times, 3.2 to 8 times, 3.3 to 8 times, 3.4 to 8 times, 3.5 to 8 times, 3.6 to 8 times, 3.7 to 8 times, 3.8 to 8 times, 3.9 to 8 times, 4 to 8 times, 4.2 to 8 times, 3.8 to 8 times, 4.4 to 8 times, 4.6 to 8 times, 4.8 to 8 times, 5 to 8 times, 5.5 to 8 times, 6 to 8 times, 6.5 to 8 times, 7 to 8 times, 7.5 to 8 times, 1 to 7.5 times, 1.1 to 7.5 times, 1.2 to 7.5 times, 1.3 to 7.5 times, 1.4 to 7.5 times, 1.5 to 7.5 times, 1.6 to 7.5 times, 1.7 to 7.5 times, 1.8 to 7.5 times, 1.9 to 7.5 times, 2 to 7.5 times, 2.1 to 7.5 times, 2.2 to 7.5 times, 2.3 to 7.5 times, 1.5 to 7.5 times, 2.4 to 7.5 times, 2.5 to 7.5 times, 2.6 to 7.5 times, 2.7 to 7.5 times, 2.8 to 7.5 times, 2.9 to 7.5 times, 3 to 7.5 times, 3.1 to 7.5 times, 3.2 to 7.5 times, 3.3 to 7.5 times, 3.4 to 7.5 times, 3.5 to 7.5 times, 3.6 to 7.5 times, 3.7 to 7.5 times, 3.8 to 7.5 times, 3.9 to 7.5 times, 4 to 7.5 times, 4.2 to 7.5 times, 4.4 to 7.5 times, 4.6 to 7.5 times, 4.8 to 7.5 times, 3.5 times, 5 to 7.5 times, 5.5 to 7.5 times, 6 to 7.5 times, 6.5 to 7.5 times, 7 to 7.5 times, 1 to 7 times, 1.1 to 7 times, 1.2 to 7 times, 1.3 to 7 times, 1.4 to 7 times, 1.5 to 7 times, 1.6 to 7 times, 1.7 to 7 times, 1.8 to 7 times, 1.9 to 7 times, 2 to 7 times, 2.1 to 7 times, 2.2 to 7 times, 2.3 to 7 times, 2.4 to 7 times, 2.5 to 7 times, 2.6 to 7 times, 2.7 to 7 times, 2.8 to 7 times, 2.9 to 7 times, 3 to 7 times, 1.9 to 7 times, 3.1 to 7 times, 3.2 to 7 times, 3.3 to 7 times, 3.4 to 7 times, 3.5 to 7 times, 3.6 to 7 times, 3.7 to 7 times, 3.8 to 7 times, 3.9 to 7 times, 4 to 7 times, 4.2 to 7 times, 4.4 to 7 times, 4.6 to 7 times, 4.8 to 7 times, 5 to 7 times, 5.5 to 7 times, 6 to 7 times, 6.5 to 7 times, 1 to 6.5 times, 1.1 to 6.5 times, 1.2 to 6.5 times, 1.3 to 6.5 times, 1.4 to 6.5 times, 1.5 to 6.5 times, 1.6 to 6.5 times, 1.5 to 6.5 times, 5 to 6.5 times, 1.7 to 6.5 times, 1.8 to 6.5 times, 1.9 to 6.5 times, 2 to 6.5 times, 2.1 to 6.5 times, 2.2 to 6.5 times, 2.3 to 6.5 times, 2.4 to 6.5 times, 2.5 to 6.5 times, 2.6 to 6.5 times, 2.7 to 6.5 times, 2.8 to 6.5 times, 2.9 to 6.5 times, 3 to 6.5 times, 3.1 to 6.5 times, 3.2 to 6.5 times, 3.3 to 6.5 times, 3.4 to 6.5 times, 3.5 to 6.5 times, 3.6 to 6.5 times, 3.7 to 6.5 times, 3.8 to 6.5 times, 3.9 to 6.5 times, 4 to 6.5 times, 4.2 to 6.5 times, 4.4 to 6.5 times, 4.6 to 6.5 times, 4.8 to 6.5 times, 5 to 6.5 times, 5.5 to 6.5 times, 6 to 6.5 times, 1 to 6 times, 1.1 to 6 times, 1.2 to 6 times, 1.3 to 6 times, 1.4 to 6 times, 1.5 to 6 times, 1.6 to 6 times, 1.7 to 6 times, 1.8 to 6 times, 1.9 to 6 times, 2 to 6 times, 2.1 to 6 times, 2.2 to 6 times, 2.3 to 6 times, 2.4 to 6 times, 2.5 to 6 times, 2.6 to 6 times, 2.7 to 6 times, 2.8 to 6 times, 2.9 to 6 times, 3 to 6 times, 3.1 to 6 times, 3.2 to 6 times, 3.3 to 6 times, 3.4 to 6 times, 3.5 to 6 times, 3.6 to 6 times, 3.7 to 6 times, 3.8 to 6 times, 3.9 to 6 times, 4 to 6 times, 4.2 to 6 times, 4.4 to 6 times, 4.6 to 6 times, 4.8 to 6 times, 5 to 6 times, 5.5 to 6 times, 1 to 5.5 times, 1.1 to 5.5 times, 1.2 to 5.5 times, 3.8 to 6 times, 1.3 to 5.5 times, 1.4 to 5.5 times, 1.5 to 5.5 times, 1.6 to 5.5 times, 1.7 to 5.5 times, 1.8 to 5.5 times, 1.9 to 5.5 times, 2 to 5.5 times, 2.1 to 5.5 times, 2.2 to 5.5 times, 2.3 to 5.5 times, 2.4 to 5.5 times, 2.5 to 5.5 times, 2.6 to 5.5 times, 2.7 to 5.5 times, 2.8 to 5.5 times, 2.9 to 5.5 times, 3 to 5.5 times, 3.1 to 5.5 times, 3.2 to 5.5 times, 3.3 to 5.5 times, 3.5 times, 3.4 to 5.5 times, 3.5 to 5.5 times, 3.6 to 5.5 times, 3.7 to 5.5 times, 3.8 to 5.5 times, 3.9 to 5.5 times, 4 to 5.5 times, 4.2 to 5.5 times, 4.4 to 5.5 times, 4.6 to 5.5 times, 4.8 to 5.5 times, 5 to 5.5 times, 1 to 5 times, 1.1 to 5 times, 1.2 to 5 times, 1.3 to 5 times, 1.4 to 5 times, 1.5 to 5 times, 1.6 to 5 times, 1.7 to 5 times, 1.8 to 5 times, 1.9 to 5 times, 2 to 5 times, 2.1 to 5 times, 1.8 to 5 times, 1.5 to 5 times, 2.2 to 5 times, 2.3 to 5 times, 2.4 to 5 times, 2.5 to 5 times, 2.6 to 5 times, 2.7 to 5 times, 2.8 to 5 times, 2.9 to 5 times, 3 to 5 times, 3.1 to 5 times, 3.2 to 5 times, 3.3 to 5 times, 3.4 to 5 times, 3.5 to 5 times, 3.6 to 5 times, 3.7 to 5 times, 3.8 to 5 times, 3.9 to 5 times, 4 to 5 times, 4.2 to 5 times, 4.4 to 5 times, 4.6 to 5 times, 4.8 to 5 times, 1 to 4.8 times, 1.1 to 4.8 times, 1.2 to 4.8 times, 1.8 times, 1.3 to 4.8 times, 1.4 to 4.8 times, 1.5 to 4.8 times, 1.6 to 4.8 times, 1.7 to 4.8 times, 1.8 to 4.8 times, 1.9 to 4.8 times, 2 to 4.8 times, 2.1 to 4.8 times, 2.2 to 4.8 times, 2.3 to 4.8 times, 2.4 to 4.8 times, 2.5 to 4.8 times, 2.6 to 4.8 times, 2.7 to 4.8 times, 2.8 to 4.8 times, 2.9 to 4.8 times, 3 to 4.8 times, 3.1 to 4.8 times, 3.2 to 4.8 times, 3.3 to 4.8 times, 3.8 times, 3.4 to 4.8 times, 3.5 to 4.8 times, 3.6 to 4.8 times, 3.7 to 4.8 times, 3.8 to 4.8 times, 3.9 to 4.8 times, 4 to 4.8 times, 4.2 to 4.8 times, 4.4 to 4.8 times, 4.6 to 4.8 times, 1.6 to 4.6 times, 1.1 to 4.6 times, 1.2 to 4.6 times, 1.3 to 4.6 times, 1.4 to 4.6 times, 1.5 to 4.6 times, 1.6 to 4.6 times, 1.7 to 4.6 times, 1.8 to 4.6 times, 1.9 to 4.6 times, 2 to 4.6 times, 1.6 times, 2.1 to 4.6 times, 2.2 to 4.6 times, 2.3 to 4.6 times, 2.4 to 4.6 times, 2.5 to 4.6 times, 2.6 to 4.6 times, 2.7 to 4.6 times, 2.8 to 4.6 times, 2.9 to 4.6 times, 3 to 4.6 times, 3.1 to 4.6 times, 3.2 to 4.6 times, 3.3 to 4.6 times, 3.4 to 4.6 times, 3.5 to 4.6 times, 3.6 to 4.6 times, 3.7 to 4.6 times, 3.8 to 4.6 times, 3.9 to 4.6 times, 4 to 4.6 times, 4.2 to 4.6 times, 3.6 to 4.6 times, 4.4 to 4.6 times, 1 to 4.4 times, 1.1 to 4.4 times, 1.2 to 4.4 times, 1.3 to 4.4 times, 1.4 to 4.4 times, 1.5 to 4.4 times, 1.6 to 4.4 times, 1.7 to 4.4 times, 1.8 to 4.4 times, 1.9 to 4.4 times, 2 to 4.4 times, 2.1 to 4.4 times, 2.2 to 4.4 times, 2.3 to 4.4 times, 2.4 to 4.4 times, 2.5 to 4.4 times, 2.6 to 4.4 times, 2.7 to 4.4 times, 2.8 to 4.4 times, 2.9 to 4.4 times, 2.4 times, 3 to 4.4 times, 3.1 to 4.4 times, 3.2 to 4.4 times, 3.3 to 4.4 times, 3.4 to 4.4 times, 3.5 to 4.4 times, 3.6 to 4.4 times, 3.7 to 4.4 times, 3.8 to 4.4 times, 3.9 to 4.4 times, 4 to 4.4 times, 4.2 to 4.4 times, 1 to 4.2 times, 1.1 to 4.2 times, 1.2 to 4.2 times, 1.3 to 4.2 times, 1.4 to 4.2 times, 1.5 to 4.2 times, 1.6 to 4.2 times, 1.7 to 4.2 times, 1.8 to 4.2 times, 1.3 to 4.2 times, 1.9 to 4.2 times, 2 to 4.2 times, 2.1 to 4.2 times, 2.2 to 4.2 times, 2.3 to 4.2 times, 2.4 to 4.2 times, 2.5 to 4.2 times, 2.6 to 4.2 times, 2.7 to 4.2 times, 2.8 to 4.2 times, 2.9 to 4.2 times, 3 to 4.2 times, 3.1 to 4.2 times, 3.2 to 4.2 times, 3.3 to 4.2 times, 3.4 to 4.2 times, 3.5 to 4.2 times, 3.6 to 4.2 times, 3.7 to 4.2 times, 3.8 to 4.2 times, 3.9 to 4.2 times, 3.4 to 4.2 times, 4 to 4.2 times, 1.1 to 4 times, 1.2 to 4 times, 1.3 to 4 times, 1.4 to 4 times, 1.5 to 4 times, 1.6 to 4 times, 1.7 to 4 times, 1.8 to 4 times, 1.9 to 4 times, 2 to 4 times, 2.1 to 4 times, 2.2 to 4 times, 2.3 to 4 times, 2.4 to 4 times, 2.5 to 4 times, 2.6 to 4 times, 2.7 to 4 times, 2.8 to 4 times, 2.9 to 4 times, 3 to 4 times, 3.1 to 4 times, 3.2 to 4 times, 3.3 to 4 times, 3.4 to 4 times, 3.5 to 4 times, 3.6 to 4 times, 3.7 to 4 times, 3.8 to 4 times, 3.9 to 4 times, 1 to 3.9 times, 1.1 to 3.9 times, 1.2 to 3.9 times, 1.3 to 3.9 times, 1.4 to 3.9 times, 1.5 to 3.9 times, 1.6 to 3.9 times, 1.7 to 3.9 times, 1.8 to 3.9 times, 1.9 to 3.9 times, 2 to 3.9 times, 2.1 to 3.9 times, 2.2 to 3.9 times, 2.3 to 3.9 times, 2.4 to 3.9 times, 2.5 to 3.9 times, 2.6 to 3.9 times, 2.4 to 3.9 times, 2.7 to 3.9 times, 2.8 to 3.9 times, 2.9 to 3.9 times, 3 to 3.9 times, 3.1 to 3.9 times, 3.2 to 3.9 times, 3.3 to 3.9 times, 3.4 to 3.9 times, 3.5 to 3.9 times, 3.6 to 3.9 times, 3.7 to 3.9 times, 3.8 to 3.9 times, 1 to 3.8 times, 1.1 to 3.8 times, 1.2 to 3.8 times, 1.3 to 3.8 times, 1.4 to 3.8 times, 1.5 to 3.8 times, 1.6 to 3.8 times, 1.7 to 3.8 times, 1.8 to 3.8 times, 1.9 to 3.8 times, 2 to 3.8 times, 2.1 to 3.8 times, 2.2 to 3.8 times, 2.3 to 3.8 times, 2.4 to 3.8 times, 2.5 to 3.8 times, 2.6 to 3.8 times, 2.7 to 3.8 times, 2.8 to 3.8 times, 2.9 to 3.8 times, 3 to 3.8 times, 3.1 to 3.8 times, 3.2 to 3.8 times, 3.3 to 3.8 times, 3.4 to 3.8 times, 3.5 to 3.8 times, 3.6 to 3.8 times, 3.7 to 3.8 times, 1 to 3.7 times, 1.1 to 3.7 times, 3.8 times, 1.2 to 3.7 times, 1.3 to 3.7 times, 1.4 to 3.7 times, 1.5 to 3.7 times, 1.6 to 3.7 times, 1.7 to 3.7 times, 1.8 to 3.7 times, 1.9 to 3.7 times, 2 to 3.7 times, 2.1 to 3.7 times, 2.2 to 3.7 times, 2.3 to 3.7 times, 2.4 to 3.7 times, 2.5 to 3.7 times, 2.6 to 3.7 times, 2.7 to 3.7 times, 2.8 to 3.7 times, 2.9 to 3.7 times, 3 to 3.7 times, 3.1 to 3.7 times, 3.2 to 3.7 times, 3.7 to 3.7 times, 3.3 to 3.7 times, 3.4 to 3.7 times, 3.5 to 3.7 times, 3.6 to 3.7 times, 1 to 3.6 times, 1.1 to 3.6 times, 1.2 to 3.6 times, 1.3 to 3.6 times, 1.4 to 3.6 times, 1.5 to 3.6 times, 1.6 to 3.6 times, 1.7 to 3.6 times, 1.8 to 3.6 times, 1.9 to 3.6 times, 2 to 3.6 times, 2.1 to 3.6 times, 2.2 to 3.6 times, 2.3 to 3.6 times, 2.4 to 3.6 times, 2.5 to 3.6 times, 2.6 to 3.6 times, 1.6 times, 2.7 to 3.6 times, 2.8 to 3.6 times, 2.9 to 3.6 times, 3 to 3.6 times, 3.1 to 3.6 times, 3.2 to 3.6 times, 3.3 to 3.6 times, 3.4 to 3.6 times, 3.5 to 3.6 times, 1 to 3.5 times, 1.1 to 3.5 times, 1.2 to 3.5 times, 1.3 to 3.5 times, 1.4 to 3.5 times, 1.5 to 3.5 times, 1.6 to 3.5 times, 1.7 to 3.5 times, 1.8 to 3.5 times, 1.9 to 3.5 times, 2 to 3.5 times, 2.1 to 3.5 times, 1.5 to 3.5 times, 2.2 to 3.5 times, 2.3 to 3.5 times, 2.4 to 3.5 times, 2.5 to 3.5 times, 2.6 to 3.5 times, 2.7 to 3.5 times, 2.8 to 3.5 times, 2.9 to 3.5 times, 3 to 3.5 times, 3.1 to 3.5 times, 3.2 to 3.5 times, 3.3 to 3.5 times, 3.4 to 3.5 times, 1 to 3.4 times, 1.1 to 3.4 times, 1.2 to 3.4 times, 1.3 to 3.4 times, 1.4 to 3.4 times, 1.5 to 3.4 times, 1.6 to 3.4 times, 1.7 to 3.4 times, 1.5 to 3.4 times, 1.8 to 3.4 times, 1.9 to 3.4 times, 2 to 3.4 times, 2.1 to 3.4 times, 2.2 to 3.4 times, 2.3 to 3.4 times, 2.4 to 3.4 times, 2.5 to 3.4 times, 2.6 to 3.4 times, 2.7 to 3.4 times, 2.8 to 3.4 times, 2.9 to 3.4 times, 3 to 3.4 times, 3.1 to 3.4 times, 3.2 to 3.4 times, 3.3 to 3.4 times, 1 to 3.3 times, 1.1 to 3.3 times, 1.2 to 3.3 times, 1.3 to 3.3 times, 1.4 to 3.3 times, 1.5 to 3.3 times, 1.6 to 3.3 times, 1.7 to 3.3 times, 1.8 to 3.3 times, 1.9 to 3.3 times, 2 to 3.3 times, 2.1 to 3.3 times, 2.2 to 3.3 times, 2.3 to 3.3 times, 2.4 to 3.3 times, 2.5 to 3.3 times, 2.6 to 3.3 times, 2.7 to 3.3 times, 2.8 to 3.3 times, 2.9 to 3.3 times, 3 to 3.3 times, 3.1 to 3.3 times, 3.2 to 3.3 times, 1 to 3.2 times, 1.1 to 3.2 times, 1.2 to 3.2 times, 2 to 3.2 times, 1.3 to 3.2 times, 1.4 to 3.2 times, 1.5 to 3.2 times, 1.6 to 3.2 times, 1.7 to 3.2 times, 1.8 to 3.2 times, 1.9 to 3.2 times, 2 to 3.2 times, 2.1 to 3.2 times, 2.2 to 3.2 times, 2.3 to 3.2 times, 2.4 to 3.2 times, 2.5 to 3.2 times, 2.6 to 3.2 times, 2.7 to 3.2 times, 2.8 to 3.2 times, 2.9 to 3.2 times, 3 to 3.2 times, 3.1 to 3.2 times, 1 to 3.1 times, 1.1 to 3.1 times, 2.4 to 3.2 times, 1.2 to 3.1 times, 1.3 to 3.1 times, 1.4 to 3.1 times, 1.5 to 3.1 times, 1.6 to 3.1 times, 1.7 to 3.1 times, 1.8 to 3.1 times, 1.9 to 3.1 times, 2 to 3.1 times, 2.1 to 3.1 times, 2.2 to 3.1 times, 2.3 to 3.1 times, 2.4 to 3.1 times, 2.5 to 3.1 times, 2.6 to 3.1 times, 2.7 to 3.1 times, 2.8 to 3.1 times, 2.9 to 3.1 times, 3 to 3.1 times, 1.1 to 3 times, 1.2 to 3.2 times, 3.1 to 3 times, 2.1 to 3 times, 1.3 to 3 times, 1.4 to 3 times, 1.5 to 3 times, 1.6 to 3 times, 1.7 to 3 times, 1.8 to 3 times, 1.9 to 3 times, 2 to 3 times, 2.1 to 3 times, 2.2 to 3 times, 2.3 to 3 times, 2.4 to 3 times, 2.5 to 3 times, 2.6 to 3 times, 2.7 to 3 times, 2.8 to 3 times, 2.9 to 3 times, 1 to 2.9 times, 1.1 to 2.9 times, 1.2 to 2.9 times, 1.5 to 2.9 times, 1.6 to 2.9 times, 1.4 to 2.9 times, 1.7 to 2.9 times, 1.8 to 2.9 times, 1.9 to 2.9 times, 2 to 2.9 times, 2.1 to 2.9 times, 2.2 to 2.9 times, 2.3 to 2.9 times, 2.4 to 2.9 times, 2.5 to 2.9 times, 2.6 to 2.9 times, 2.7 to 2.9 times, 2.8 to 2.9 times, 1 to 2.8 times, 1.1 to 2.8 times, 1.2 to 2.8 times, 1.3 to 2.8 times, 1.4 to 2.8 times, 1.5 to 2.8 times, 1.6 to 2.8 times, 1.7 to 2.8 times, 1.8 to 2.8 times, 1.9 to 2.8 times, 2 to 2.8 times, 2.1 to 2.8 times, 2.2 to 2.8 times, 2.3 to 2.8 times, 2.4 to 2.8 times, 2.5 to 2.8 times, 2.6 to 2.8 times, 2.7 to 2.8 times, 1 to 2.7 times, 1.1 to 2.7 times, 1.2 to 2.7 times, 1.3 to 2.7 times, 1.4 to 2.7 times, 1.5 to 2.7 times, 1.6 to 2.7 times, 1.7 to 2.7 times, 1.8 to 2.7 times, 1.9 to 2.7 times, 2 to 2.7 times, 2.1 to 2.7 times, 1.7 to 2.7 times, 2.2 to 2.7 times, 2.3 to 2.7 times, 2.4 to 2.7 times, 2.5 to 2.7 times, 2.6 to 2.7 times, 1 to 2.6 times, 1.1 to 2.6 times, 1.2 to 2.6 times, 1.3 to 2.6 times, 1.4 to 2.6 times, 1.5 to 2.6 times, 1.6 to 2.6 times, 1.7 to 2.6 times, 1.8 to 2.6 times, 1.9 to 2.6 times, 2 to 2.6 times, 2.1 to 2.6 times, 2.2 to 2.6 times, 2.3 to 2.6 times, 2.4 to 2.6 times, 2.5 to 2.6 times, 1.6 to 2.6 times, 1.1 to 2.5 times, 1.2 to 2.5 times, 1.3 to 2.5 times, 1.4 to 2.5 times, 1.5 to 2.5 times, 1.6 to 2.5 times, 1.7 to 2.5 times, 1.8 to 2.5 times, 1.9 to 2.5 times, 2 to 2.5 times, 2.1 to 2.5 times, 2.2 to 2.5 times, 2.3 to 2.5 times, 2.4 to 2.5 times, 1 to 2.4 times, 1.1 to 2.4 times, 1.2 to 2.4 times, 1.3 to 2.4 times, 1.4 to 2.4 times, 1.5 to 2.4 times, 1.4 to 2.4 times, 1.6 to 2.4 times, 1.7 to 2.4 times, 1.8 to 2.4 times, 1.9 to 2.4 times, 2 to 2.4 times, 2.1 to 2.4 times, 2.2 to 2.4 times, 2.3 to 2.4 times, 1 to 2.3 times, 1.1 to 2.3 times, 1.2 to 2.3 times, 1.3 to 2.3 times 1.3 to 2.3 times, 1.4 to 2.3 times, 1.5 to 2.3 times, 1.6 to 2.3 times, 1.7 to 2.3 times, 1.8 to 2.3 times, 1.9 to 2.3 times, 2 to 2.3 times, 2.1 to 2.3 times, 2.2 to 2.3 times, 2.3 to 2.3 times, 1.1 to 2.2 times, 1.2 to 2.2 times, 1.3 to 2.2 times, 1.4 to 2.2 times, 1.5 to 2.2 times, 1.6 to 2.2 times, 1.7 to 2.2 times, 1.8 to 2.2 times, 1.9 to 2.2 times, 2 to 2.2 times, 2.1 to 2.2 times, 1 to 2.1 times, 1.1 to 2.1 times, 1.2 to 2.1 times, 1.3 to 2.1 times, 1.4 to 2.1 times, 1.5 to 2.1 times, 1.6 to 2.1 times, 1.7 to 2.1 times, 1.8 to 2.1 times, 1.1 to 2.1 times, 1.9 to 2.1 times, 2 to 2.1 times, 1 to 2 times, 1.1 to 2 times, 1.2 to 2 times, 1.3 to 2 times, 1.4 to 2 times, 1.5 to 2 times, 1.6 to 2 times, 1.7 to 2 times, 1.8 to 2 times, 1.9 to 2 times, 1 to 1.9 times, 1.1 to 1.9 times, 1.2 to 1.9 times, 1.3 to 1.9 times, 1.4 to 1.9 times, 1.5 to 1.9 times, 1.6 to 1.9 times, 1.7 to 1.9 times, 1.8 to 1.9 times, 1 to 1.8 times, 1.1 to 1.8 times, 1.2 to 1.9 times, 1.2 to 1.8 times, 1.3 to 1.8 times, 1.4 to 1.8 times, 1.5 to 1.8 times, 1.6 to 1.8 times, 1.7 to 1.8 times, 1.5 to 1.6 times, 1.1 to 1.7 times, 1.2 to 1.7 times, 1.3 to 1.7 times, 1.4 to 1.7 times, 1.5 to 1.7 times, 1.6 to 1.7 times, 1 to 1.6 times, 1.1 to 1.6 times, 1.2 to 1.6 times, 1.3 to 1.6 times, 1.4 to 1.6 times, 1.5 to 1.5 times, 1.1 to 1.5 times, 1.5 to 1.5 times, 1.7 times, 1.2 to 1.5 times, 1.3 to 1.5 times, 1.4 to 1.5 times, 1 to 1.4 times, 1.1 to 1.4 times, 1.2 to 1.4 times, 1.3 to 1.4 times, 1 to 1.3 times, 1.1 to 1.3 times, 1.2 to 1.3 times, 1 to 1.2 times, 1.1 to 1.3 times, or 1 to 1.1 times.

Also provided are embodiments of the above process for preparing a free-radically functionalized PIBSA product, wherein the process comprises reacting a polyisobutylene (such as a high vinylidene polyisobutylene) with a free-radical initiator and an ethylenically unsaturated acylating agent at a temperature of 150 ℃ to 225 ℃ to prepare the free-radically functionalized PIBSA product, wherein the polyisobutylene is brought to a reaction temperature in a continuous reactor prior to beginning continuous addition of the free-radical initiator to the polyisobutylene in the continuous reactor, and wherein the ethylenically unsaturated acylating agent is added to the continuous reactor in such a manner that (i) as a mixture with the polyisobutylene, (ii) as a mixture with the free-radical initiator, and/or (iii) continuously and separately from the polyisobutylene or the free-radical initiator.

Illustrative non-limiting embodiments of the methods described herein for preparing a free-radically functionalized PIBSA product can include feeding polyisobutylene into a two-stage or three-stage reactor system at 170 ℃, wherein each stage includes adding a maleic anhydride acylating agent and a di-t-butyl peroxide initiator to the polyisobutylene flowing through the reactor system. In the case of a half-life of about 6 minutes for di-t-butyl peroxide, each stage is allowed to react for about 20 minutes to allow most of the initiator to be consumed before another dose is added. After two or three stages, the reaction is complete and the desired product has been obtained in about 40 to 60 minutes.

Nitrogen-containing compound

In certain embodiments, the nitrogen-containing compound has (a) a nitrogen atom capable of reacting with the free-radically functionalized PIBSA product to form an imide, and (b) at least one quaternizable amino group. In certain embodiments, the quaternizable amino groups can be primary amino groups, secondary amino groups, or tertiary amino groups. The quaternizable amino groups are any primary, secondary or tertiary amino groups on the nitrogen-containing compound that can be reacted with a quaternizing agent to become quaternary amino groups. In certain embodiments, quaternizing agents are suitable for converting quaternizable amino groups to quaternary nitrogen groups.

In certain embodiments, the nitrogen-containing compound may be represented by the formula:

Wherein X is an alkylene group containing 1 to 4 carbon atoms, R ² is hydrogen or a hydrocarbyl group, and R ³ and R ⁴ are hydrocarbyl groups.

Suitable non-limiting examples of nitrogen-containing compounds include N, N-dimethyl-aminopropylamine, N-diethyl-aminopropylamine, N-dimethyl-aminopyramine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, isomeric amines (including butanediamine, pentylene diamine, hexamethylenediamine and heptylenediamine), diethylenetriamine, dipropylenetriamine, dibutyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis (hexamethylene) triamine, diaminobenzene, diaminopyridine, N-methyl-3-amino-1-propylamine, or mixtures thereof. Nitrogen-containing compounds that are capable of reacting with an acylating agent and further have a quaternizable amino group can also include aminoalkyl-substituted heterocyclic compounds such as 1- (3-aminopropyl) imidazole and 4- (3-aminopropyl) morpholine, 1- (2-aminoethyl) piperidine, 3-diamino-N-methyl dipropylamine. In some embodiments, the nitrogen-containing compound does not include dimethylaminopropylamine.

In certain embodiments, the nitrogen-containing compound may be an imidazole, such as an imidazole of the formula:

Wherein R is an amine capable of reacting in the methods described herein and having 3 to 8 carbon atoms.

Wherein each X is independently a C ₁ to C ₆ alkylene group and each R is independently hydrogen or a C ₁ to C ₆ hydrocarbon group. In certain embodiments, X may be independently a C ₁、C₂ or C ₃ alkylene group. In certain embodiments, each R may be independently H or a C ₁、C₂ or C ₃ alkyl group.

Quaternizable compounds

In certain embodiments, the reaction to prepare the quaternizable compound can be conducted at a temperature greater than 80 ℃, such as greater than 90 ℃ or greater than 100 ℃. In certain embodiments, the reaction to prepare the quaternizable compound can be conducted at a temperature of 80 ℃ to 200 ℃ (such as 90 ℃ to 200 ℃, 100 ℃ to 200 ℃, 125 ℃ to 200 ℃, 80 ℃ to 175 ℃,90 ℃ to 175 ℃, 100 ℃ to 175 ℃, 125 ℃ to 175 ℃, 80 ℃ to 150 ℃,90 ℃ to 150 ℃, 100 ℃ to 150 ℃, or 125 ℃ to 150 ℃). In certain embodiments, the water of reaction, such as that produced during the condensation reaction, may be removed.

The free radical functionalized PIBSA product and the nitrogen-containing compound may be reacted in a ratio of 3:1 to 1:1.2, or 1.5:1 to 1:1.1, or 2:1 to 1:1.05, such as in a ratio of 1:1.

Quaternizing agent

In certain embodiments, the quaternizing agent includes at least one of dialkyl sulfate, alkyl halocyclopent, hydrocarbyl-substituted carbonate, or hydrocarbyl epoxide. In certain embodiments, the quaternizing agent includes a hydrocarbyl epoxide in combination with an acid.

In certain embodiments, the quaternizing agent can include alkyl halides such as chloride, iodide, or bromide, alkyl sulfonates, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, sultones, alkyl phosphates such as C _1-12 trialkyl phosphate, di C _1-12 alkyl phosphate, borate, C _1-12 alkyl borate, alkyl nitrite, alkyl nitrate, dialkyl carbonates such as dimethyl oxalate, alkyl alkanoates such as methyl salicylate, O-di-C _1-12 alkyl dithiophosphate, or mixtures thereof.

In certain embodiments, the quaternizing agent can be derived from dialkyl sulfate (such as dimethyl sulfate or diethyl sulfate), N-oxide, sultones (such as propane sultone and butane sultone), alkyl halides, acyl halides, or aryl halides, such as methyl chloride and ethyl chloride, methyl bromide and ethyl bromide or methyl iodide and ethyl iodide or benzyl chloride, and hydrocarbyl (or alkyl) substituted carbonates. If the alkyl halide is benzyl chloride, the aromatic ring is optionally further substituted with an alkyl or alkenyl group.

In certain embodiments, the hydrocarbyl group of the hydrocarbyl-substituted carbonate may contain from 1 to 50, from 1 to 20, from 1 to 10, or from 1 to 5 carbon atoms per group. In one embodiment, the hydrocarbyl-substituted carbonate contains two hydrocarbyl groups, which may be the same or different. Examples of suitable hydrocarbyl-substituted carbonates include dimethyl carbonate or diethyl carbonate.

In certain embodiments, the quaternizing agent can comprise a hydrocarbyl epoxide, such as one represented by the formula:

Wherein each R ¹、R²、R³ and R ⁴ is independently H or a hydrocarbyl group having 1 to 50 carbon atoms. Examples of hydrocarbon-based epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and combinations thereof. In certain embodiments, the hydrocarbyl epoxide may be an alcohol functionalized epoxide, a C ₄ to C ₁₄ epoxide, and mixtures thereof. Exemplary C ₄ to C ₁₄ epoxides are those wherein each R ¹、R²、R³ and R ⁴ is independently H or a C ₂ to C ₁₂ hydrocarbyl group. In certain embodiments, the epoxide may be a C ₄ to C ₁₄ epoxide. Epoxides suitable as quaternizing agents in the present technology may include, for example, C ₄ to C ₁₄ epoxides having linear hydrocarbyl substituents, such as 2-ethyl oxirane, 2-propyl oxirane, and the like, as well as C ₄ to C ₁₄ epoxides having branched and cyclic or aromatic substituents, such as styrene oxide. The C ₄ to C ₁₄ epoxides may also include epoxidized triglycerides, fats or oils, epoxidized alkyl esters of fatty acids, and mixtures thereof. In certain embodiments, the hydrocarbyl epoxide may be a C ₄ to C ₂₀ epoxide. Exemplary alcohol-functionalized epoxides may include those wherein each R ¹、R²、R³ and R ⁴ is independently H or a hydroxyl-containing hydrocarbyl group. In certain embodiments, the hydroxyl-containing hydrocarbyl group may contain from 2 to 32, or from 3 to 28, or even from 3 to 24 carbon atoms. Exemplary alcohol-functionalized epoxide derivatives can include, for example, glycidol and the like.

In certain embodiments, the hydrocarbyl epoxide may be used in combination with an acid. The acid used with the hydrocarbyl epoxide may be a separate component, such as acetic acid. In certain embodiments, a small amount of acid component may be present, but <0.2 moles or <0.1 moles of acid per mole of hydrocarbyl acylating agent. These acids may also be used with other quaternizing agents described herein. Suitable acids may also include, for example, carboxylic acids (such as acetic acid and/or tall oil fatty acids), propionic acid, 2-ethylhexanoic acid, and the like, as well as mixtures thereof.

In certain embodiments, the quaternizing agent can include an ester of a carboxylic acid, or an ester of a polycarboxylic acid, capable of reacting with a tertiary amine to form a quaternary ammonium salt. In certain embodiments, such materials may be described as compounds having the structure R ¹⁹-C(＝O)-O-R²⁰, wherein R ¹⁹ is an (optionally substituted) alkyl, alkenyl, aryl, or alkylaryl group, and R ²⁰ is a hydrocarbyl group containing from 1 to 22 carbon atoms. Suitable compounds include, but are not limited to, esters of carboxylic acids having a pKa of 3.5 or less. In certain embodiments, the compound is an ester of a carboxylic acid comprising at least one of a substituted aromatic carboxylic acid, an alpha-hydroxy carboxylic acid, or a polycarboxylic acid. In certain embodiments, the compound is an ester of a substituted aromatic carboxylic acid, and thus R ¹⁹ is a substituted aryl group. R ¹⁹ can be a substituted aryl group having 6 to 10 carbon atoms, a phenyl group, or a naphthyl group. R ¹⁹ may be suitably substituted with one or more groups selected from alkoxycarbonyl, nitro, cyano, hydroxy, SR ' or NR ' R ', wherein each of R ' and R ' may independently be hydrogen or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. In certain embodiments, R' and r″ are each independently hydrogen or an (optionally substituted) alkyl group containing 1 to 22, 1 to 16, 1 to 10, or 1 to 4 carbon atoms. In certain embodiments, R ¹⁹ is an aryl group substituted with one or more groups selected from hydroxy, alkoxycarbonyl, nitro, cyano, and NH ₂. R ¹⁹ may be a polysubstituted aryl group, such as a trihydroxyphenyl group, but may also be a monosubstituted aryl group, such as an ortho-substituted aryl group. R ¹⁹ may be substituted by a group selected from OH, NH ₂、NO₂ or COOMe. R ¹⁹ can be a hydroxy-substituted aryl group. In certain embodiments, R ¹⁹ is a 2-hydroxyphenyl group. R ²⁰ can be an alkyl or alkylaryl group, such as an alkyl or alkylaryl group containing from 1 to 16 carbon atoms, or from 1 to 10, or from 1 to 8 carbon atoms. R ²⁰ can be methyl, ethyl, propyl, butyl, pentyl, benzyl or their isomers. in certain embodiments, R ²⁰ is benzyl or methyl. In certain embodiments, the quaternizing agent is methyl salicylate.

In certain embodiments, the quaternizing agent can include an ester of an alpha-hydroxycarboxylic acid. Examples of suitable compounds containing residues of alpha-hydroxy carboxylic acids include (i) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-methylbutanoic acid, (ii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-ethylbutanoic acid, (iii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-ethylbutanoic acid, (iv) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of lactic acid, and (v) methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl and phenyl esters of glycolic acid. In certain embodiments, the quaternizing agent includes methyl 2-hydroxyisobutyrate.

In certain embodiments, the quaternizing agent comprises an ester of a polycarboxylic acid. Included within this definition are dicarboxylic acids and carboxylic acids having more than 2 acidic moieties. In certain embodiments, the esters are alkyl esters having an alkyl group containing 1 to 4 carbon atoms. Suitable examples include oxalic acid diesters, phthalic acid diesters, maleic acid diesters, malonic acid diesters or citric acid diesters or triesters.

In certain embodiments, the quaternizing agent is an ester of a carboxylic acid having a pKa of less than 3.5. In certain embodiments wherein the compound comprises more than one acid group, reference is made to a first dissociation constant. The quaternizing agent may be selected from esters of carboxylic acids selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, and 2,4, 6-trihydroxybenzoic acid. In certain embodiments, the quaternizing agent can include dimethyl oxalate, terephthalates (such as dimethyl terephthalate), and methyl 2-nitrobenzoate.

For example, quaternizing agents capable of coupling more than one quaternizable compound can also be used. By "coupling" more than one quaternizable compound is meant a compound in which at least two quaternizable compounds react with the same quaternizing agent to form at least two quaternizable compounds linked by the quaternizing agent. In some cases, such quaternizing agents may also be referred to herein as coupled quaternizing agents, and may include, for example, polyepoxides, such as diepoxides, or higher epoxides, polyhalides, epoxy halides, aromatic polyesters, and mixtures thereof.

In certain embodiments, the quaternizing agent can be a polyepoxide. The polyepoxide may include, for example, polyglycidyl groups which may include, for example, diglycidyl octane, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 3- (bis (glycidoxymethyl) methoxy) -1, 2-propanediol, 1, 4-cyclohexanedimethanol diglycidyl ether, diglycidyl cyclooctane, bisphenol a diglycidyl ether, 4-vinyl-1-cyclohexene diepoxide, N-diglycidyl-4, 4-glycidoxyalniline, 1, 6-hexane diglycidyl ether, trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, multi-epoxidized triglycerides, fats or oils, and mixtures thereof.

In certain embodiments, the quaternizing agent can be derived from a polyhalide, such as chloride, iodide, or bromide. Such polyhalides may include, but are not limited to, 1, 5-dibromopentane, 1, 4-diiodobutane, 1, 5-dichloropentane, 1, 12-dichlorododecane, 1, 12-dibromododecane, 1, 2-diiodoethane, 1, 2-dibromoethane, and mixtures thereof.

In certain embodiments, the quaternizing agent can be an epoxy halide, such as epichlorohydrin and the like.

In certain embodiments, the quaternizing agent can be a polyaromatic ester. Examples of polyaromatic esters may include, but are not limited to, methyl 4,4' -oxybis (benzoate), dimethyl terephthalate, and mixtures thereof.

In certain embodiments, the molar ratio of quaternizable compound to quaternizing agent is from 1:0.1 to 2, or from 1:1 to 1.5, or from 1:1 to 1.3. In certain embodiments, such as when a coupled quaternizing agent is used, the ratio of quaternizable compound to quaternizing agent can be from 2:1 to 1:1.

In certain embodiments, the quaternizing agent can be used in the presence of a protic solvent (e.g., 2-ethylhexanol, water, and combinations thereof). In certain embodiments, the quaternizing agent can be used in the presence of an acid. In certain embodiments, the quaternizing agent can be used in the presence of an acid and a protic solvent.

Composition and method for producing the same

Also provided are compositions comprising a reaction product comprising a quaternary ammonium salt. In certain embodiments, the composition may further comprise at least one other additive. In certain embodiments, the at least one other additive may be at least one of a detergent, a demulsifier, a lubricant, a cold flow improver, or an antioxidant, provided that the at least one other additive is not a reaction product comprising a quaternary ammonium salt.

In certain embodiments, the at least one other additive comprises at least one hydrocarbyl-substituted succinic acid and/or at least one hydrocarbyl-substituted quaternary ammonium salt (other than the reaction product comprising the quaternary ammonium salt). The hydrocarbyl substituent may be a polyisobutene having a number average molecular weight in the range of 100 to 5000.

The number average molecular weight (M _n) described herein can be measured using Gel Permeation Chromatography (GPC) using WATERS GPC 2000 equipped with a refractive index detector and Waters EmpowerTM data acquisition and analysis software. Samples were run against polystyrene calibration standards. The column was polystyrene (PLgel, 5 microns, available from Agilent/Polymer Laboratories, inc.). For the mobile phase, individual samples were dissolved in tetrahydrofuran and filtered with a PTFE filter, and then injected into the GPC port. WATERS GPC 2000 operating conditions, injector, column and pump/solvent chamber temperatures, 40 ℃, autoinjector control, run time, 40 minutes, injection volume, 300 microliters, pump, system pressure, about 90 bar (maximum pressure limit, 270 bar; minimum pressure limit, 0 psi), flow rate, 1.0 ml/min, differential refractometer, sensitivity, -16, scale factor, 6.

In certain embodiments, at least one other additive comprises at least one detergent/dispersant which is an amphiphilic substance having at least one hydrophobic hydrocarbon group of number average molecular weight from 100 to 10,000 and at least one polar moiety selected from (i) a mono-or polyamino group having up to 6 nitrogen atoms (at least one nitrogen atom having basic character), (ii) a hydroxyl group in combination with a mono-or polyamino group (at least one nitrogen atom having basic character), (iii) a polyoxy-C ₂ to C ₄ alkylene moiety terminated by a hydroxyl group, a mono-or polyamino group (at least one nitrogen atom having basic character) or by a carbamate group, (iv) a moiety derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups, and/or (v) a moiety obtained by mannich reaction of a substituted phenol with an aldehyde and a mono-or polyamine. In certain embodiments, the at least one other additive may include at least one Mannich compound.

In certain embodiments, the present technology provides a composition comprising a reaction product comprising a quaternary ammonium salt as described herein, and the use of the composition in a fuel composition to improve the dehydration of the fuel composition. In certain embodiments, the present technology provides a composition comprising a reaction product comprising a quaternary ammonium salt as described herein, and the use of the composition in a lubricating composition of an oil of lubricating viscosity. In certain embodiments, the fuel and/or lubricant composition may additionally comprise at least one additional additive. These additional additives may be added to any of the compositions described herein, depending on the desired result and/or the application in which the composition is to be used. When the term "additional additive (additional additive/additional additives)" is used herein, it means (unless the context requires otherwise) that the at least one additive is not (and/or does not) comprise a reaction product comprising a quaternary ammonium salt as described herein.

Although any of the additional additives described herein may be used in any fuel and/or lubricant composition of the present invention (depending on the desired result and/or application in which the composition is to be used), the following additional additives are particularly useful in fuel and/or lubricant compositions, antioxidants, corrosion inhibitors, detergents and/or dispersant additives other than the reactant products comprising the quaternary ammonium salts described herein, cold flow improvers, foam inhibitors, demulsifiers, lubricants, metal deactivators, valve seat recession additives (VALVE SEAT recession additive), biocides, antistatic agents, antifreeze agents, fluidizers, combustion improvers, seal swellers, wax control polymers, scale inhibitors, gas-hydrate inhibitors, or any combination thereof.

Demulsifiers suitable for use as additional additives may include, but are not limited to, arylsulfonates and polyalkoxylated alcohols, such as polyethylene oxide and polypropylene oxide copolymers, and the like. Demulsifiers may also include nitrogen-containing compounds such as oxazoline and imidazoline compounds and fatty amines, as well as mannich compounds. Mannich compounds are the reaction products of alkylphenols and aldehydes (such as formaldehyde) with amines (such as amine condensates and polyalkylene polyamines). The materials described in U.S. patent 3,036,003;3,236,770;3,414,347;3,448,047;3,461,172;3,539,633;3,586,629;3,591,598;3,634,515;3,725,480;3,726,882; and 3,980,569 are illustrative. Other suitable demulsifiers are, for example, alkali or alkaline earth metal salts of alkyl-substituted phenols and naphthalene sulfonates and alkali or alkaline earth metal salts of fatty acids, and also neutral compounds, such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-amyl phenol ethoxylates), fatty acids, alkylphenols, condensation products of Ethylene Oxide (EO) and Propylene Oxide (PO) (e.g., comprising polyethylene imine or another polysiloxane in the form of EO/PO block copolymers). Any commercially available demulsifier in an amount sufficient to provide a treatment level in the fuel of from 5ppm to 50ppm can be suitably employed. In certain embodiments, there is no demulsifier present as a further additive in the fuel and/or lubricant composition. The demulsifiers may be used singly or in combination.

Suitable antioxidants for use as further additives include, for example, hindered phenols or derivatives thereof and/or diarylamines or derivatives thereof. Suitable detergents/dispersants for use as further additives include, for example, polyetheramines or nitrogen-containing detergents, including, but not limited to, PIB amine detergents/dispersants, succinimide detergents/dispersants, and other quaternary salt detergents/dispersants, including polyisobutene succinimide-derived quaternized PIB/amine and/or amide dispersants/detergents. Suitable cold flow improvers for use as further additives include, for example, esterified copolymers of maleic anhydride and styrene and/or copolymers of ethylene and vinyl acetate. Suitable lubricity improvers or friction modifiers for use as further additives may be based on fatty acids or reaction products of fatty acids, including for example fatty acid esters. Examples include tall oil fatty acids, as described for example in WO 98/004656, and glycerol monooleate. Reaction products of natural or synthetic oils, such as triglycerides and alkanolamines, described in U.S. patent 6,743,266B2, are also suitable as such lubricity improvers. Additional examples include commercial tall oil fatty acids containing polycyclic hydrocarbons and/or rosin acids.

Suitable metal deactivators for use as further additives include, for example, aromatic triazoles or derivatives thereof, including but not limited to benzotriazoles. Other suitable metal deactivators include, for example, salicylic acid derivatives such as N, N' -bis-salicylidene-1, 2-propanediamine. Suitable valve seat recession additives for use as further additives include, for example, alkali metal sulfosuccinates. Suitable foam inhibitors and/or defoamers for use as further additives include, for example, organosiloxanes (such as polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, trimethyl-trifluoro-propylmethylsiloxane), polyacrylates, polymethacrylates, polyacrylamides, fluoroacrylates, and the like. Suitable fluidizers for use as further additives include, for example, mineral oils and/or poly (alpha-olefins) and/or polyethers. Combustion improvers suitable for use as further additives include, for example, octane and cetane improvers. Suitable cetane improvers for use as further additives are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.

Further additives may also include diester, diamide, ester-amide and ester-imide friction modifiers prepared by reacting an alpha-hydroxy acid with an amine and/or alcohol, optionally in the presence of known esterification catalysts. Examples of alpha-hydroxy acids include glycolic acid, lactic acid, alpha-hydroxy dicarboxylic acids (such as tartaric acid) and/or alpha-hydroxy tricarboxylic acids (such as citric acid), and amines and/or alcohols optionally in the presence of known esterification catalysts. These friction modifiers, which are typically derived from tartaric acid, citric acid, or derivatives thereof, may be derived from branched amines and/or alcohols, resulting in the friction modifier itself having a large number of branched hydrocarbon groups in its structure. Examples of suitable branched alcohols for preparing such friction modifiers include 2-ethylhexanol, isotridecyl alcohol, guerbet alcohol (Guerbet alcohol), and mixtures thereof. The friction modifier may be present from 0 wt% to 6 wt% or from 0.001 wt% to 4 wt%, or from 0.01 wt% to 2 wt% or from 0.05 wt% to 3 wt% or from 0.1 wt% to 2 wt% or from 0.1 wt% to 1 wt% or from 0.001 wt% to 0.01 wt% based on the total weight of the composition.

Further additives may include detergent/dispersants comprising hydrocarbyl-substituted acylating agents. The acylating agent may be, for example, a hydrocarbyl-substituted succinic acid, or a condensation product of a hydrocarbyl-substituted succinic acid with an amine or alcohol, i.e., a hydrocarbyl-substituted succinimide or a hydrocarbyl-substituted succinic acid ester. In certain embodiments, the detergent/dispersant may be a polyisobutenyl substituted succinic acid, amide or ester, wherein the polyisobutenyl substituent has a number average molecular weight of 100 to 5000. In certain embodiments, the detergent may be a C ₆ to C ₁₈ substituted succinic acid, amide or ester. A more complete description of hydrocarbyl-substituted acylating agent detergents can be found in paragraphs [0017] to [0036] of U.S. 2011/0219674 A1.

In certain embodiments, the detergent/dispersants used as additional additives may be quaternary ammonium salts other than those found in the reaction products of the present technology. These different quaternary ammonium salts may be quaternary ammonium salts prepared from hydrocarbyl-substituted acylating agents such as polyisobutylsuccinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight greater than 1200, polyisobutylsuccinic anhydride having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or polyisobutylsuccinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight of 1000. In certain embodiments, such quaternary ammonium salts prepared from the reaction of a nitrogen-containing compound and a hydrocarbyl-substituted acylating agent having a hydrocarbyl substituent having a number average molecular weight of 1300 to 3000 can be imides. In certain embodiments, such quaternary ammonium salts prepared from the reaction of a nitrogen-containing compound and a hydrocarbyl-substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight greater than 1200 or a hydrocarbyl substituent with a number average molecular weight of 300 to 750 can be an amide or an ester. In certain embodiments, the hydrocarbyl-substituted acylating agent may comprise a monocarboxylic acid, dimer carboxylic acid, or trimer carboxylic acid having from 8 to 54 carbon atoms, and is reacted with a primary or secondary amine. Suitable acids include, but are not limited to, mono-, dimer-or trimer acids of caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, lignoceric, cerotic, palmitoleic, hexadecenoic, oleic, elaidic, isooleic, linoleic, elaidic, alpha-linolenic, arachidonic, eicosapentaenoic, erucic and docosahexaenoic acids. The hydrocarbyl-substituted acylating agent may also be a copolymer formed by copolymerizing at least one monomer that is an ethylenically unsaturated hydrocarbon having from 2 to 100 carbon atoms. The monomers may be linear, branched or cyclic. The monomer may have an oxygen or nitrogen substituent but will not react with an amine or alcohol. The monomer may be reacted with a second monomer which is a carboxylic acid or carboxylic acid derivative having 3 to 12 carbon atoms. The second monomer may have one or two carboxylic acid functional groups and be reacted with an amine or alcohol. When prepared using this method, the hydrocarbyl-substituted acylating agent copolymer has a number average molecular weight of 500 to 20,000. Alternatively, the hydrocarbyl-substituted acylating agent may be a terpolymer of ethylene and at least one monomer that is an ethylenically unsaturated monomer having at least one tertiary nitrogen atom with (i) an alkenyl ester of one or more aliphatic monocarboxylic acids having 1 to 24 carbon atoms or (ii) an alkyl ester of acrylic or methacrylic acid. In certain embodiments, the nitrogen-containing compound of a different quaternary ammonium salt can be an imidazole or nitrogen-containing compound having any one of the following formulas:

Wherein R may be a C ₁ to C ₆ alkylene group, each of R ₁ and R ₂ may be independently a C ₁ to C ₆ alkylene group, and each of R ₃、R₄、R₅ and R ₆ may be independently hydrogen or a C ₁ to C ₆ hydrocarbon group. In certain embodiments, R ₁ or R ₂ can be, for example, a C ₁、C₂ or C ₃ alkylene group. In certain embodiments, each R ₃、R₄、R₅、R₆ can be, for example, H or a C ₁、C₂ or C ₃ alkyl group. In certain embodiments, the quaternizing agent used to prepare the different quaternary ammonium salts can be dialkyl sulfate, alkyl halide, hydrocarbyl-substituted carbonate, hydrocarbyl epoxide, carboxylate, alkyl ester, or mixtures thereof. In certain embodiments, the quaternizing agent can be a hydrocarbon-based epoxide. In certain embodiments, the quaternizing agent can be a hydrocarbyl epoxide in combination with an acid. In certain embodiments, the quaternizing agent can be a salicylate, oxalate, or terephthalate. In certain embodiments, the hydrocarbyl epoxide may be an alcohol-functionalized epoxide or a C ₄ to C ₁₄ epoxide. In certain embodiments, the hydrocarbyl epoxide may be an alcohol-functionalized epoxide or a C ₄ to C ₂₀ epoxide. In certain embodiments, the quaternizing agent is multifunctional, resulting in the additional quaternary ammonium salt being a coupled quaternary ammonium salt. The different quaternary ammonium salts can include, but are not limited to, quaternary ammonium salts having a hydrophobic moiety in the anion. Exemplary compounds include quaternary ammonium compounds having the formula:

Wherein R ⁰、R¹、R² and R ³ are each independently an optionally substituted alkyl, alkenyl, or aryl group, and R comprises an optionally substituted hydrocarbyl moiety having at least 5 carbon atoms. The different quaternary ammonium salts can also include polyetheramines, which are the reaction products of polyether substituted amines comprising at least one tertiary quaternizable amino group and quaternizing agents that convert the tertiary amino group to a quaternary ammonium group.

In certain embodiments, the dispersant may be post-treated by reaction with any of a variety of agents. Among the various agents are urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds and phosphorus compounds. References to such treatment are detailed in U.S. Pat. No. 4,654,403.

The fuel and/or lubricant compositions described herein may comprise a detergent as a further additive. Many detergents used in the field of engine lubrication acquire most or all of their basicity or total base number ("TBN") from the presence of basic metal-containing compounds (metal hydroxides, oxides or carbonates, such as those based on metals like calcium, magnesium or sodium). Such metal overbased detergents (also referred to as overbased or superbased salts) are typically single phase homogeneous newtonian systems (Newtonian systems) characterized by a metal content exceeding that which would be present for neutralization based on the stoichiometric amount of the metal and the particular acidic organic compound reacted with the metal. The overbased materials may be prepared by reacting an acidic material, such as an inorganic acid or a lower carboxylic acid, such as carbon dioxide, with a mixture of an acidic organic compound (also referred to as a substrate), a stoichiometric excess of a metal base, possibly in a reaction medium of an inert organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic substrate. In certain embodiments, a small amount of an accelerator, such as a phenol or alcohol, and in some cases, a small amount of water, is present. The acidic organic substrate may have a sufficient number of carbon atoms to provide solubility in the oil. Such overbased materials and methods of preparing them are well known to those skilled in the art. Patents describing techniques for preparing basic metal salts of sulfonic acids, carboxylic acids, phenols, phosphonic acids, and mixtures of any two or more of these include U.S. patent 2,501,731;2,616,905;2,616,911;2,616,925;2,777,874;3,256,186;3,384,585;3,365,396;3,320,162;3,318,809;3,488,284; and 3,629,109. Liu Fang acid salt (Salixarate) detergents are described in U.S. Pat. No.6,200,936. In certain embodiments, the detergent may contain a metal-containing salicylate detergent, such as an overbased, hydrocarbyl-substituted calcium salicylate detergent, which is described in U.S. Pat. nos. 5,688,751 and 4,627,928.

Viscosity modifiers (sometimes also referred to as viscosity index improvers or viscosity modifiers) may be used as additional additives in the compositions described herein. The viscosity modifier may be a polymer including polyisobutylene, polymethacrylates (polymethacrylates) ("PMA") and polymethacrylates (polymethacrylic ACID ESTERS), hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenyl arene-conjugated diene copolymers, and polyolefins. PMA is prepared from a mixture of methacrylate monomers with different alkyl groups. The alkyl group may be a straight or branched chain group containing 1 to 18 carbon atoms. Most PMAs are viscosity modifiers and pour point depressants.

Multifunctional viscosity modifiers that also have dispersant and/or antioxidant properties are known and may optionally be used as further additives in fuel and/or lubricant compositions. Dispersant viscosity modifiers ("DVM") are one example of such polyfunctional additives. DVM may be prepared by copolymerizing a small amount of a nitrogen-containing monomer with an alkyl methacrylate to provide an additive having some combination of dispersibility, viscosity adjustment, pour point reduction, and/or dispersibility. Vinylpyridine, N-vinylpyrrolidone and N, N' -dimethylaminoethyl methacrylate are examples of nitrogen-containing monomers. Polyacrylates obtained from the polymerization or copolymerization of one or more alkyl acrylates may also be used as such viscosity modifiers.

Antiwear agents may be used as further additives in the fuel and/or lubricant compositions described herein. Antiwear agents may include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphates and salts thereof, phosphorus-containing carboxylic acids, esters, ethers and amides, and phosphites. In certain embodiments, the phosphorus antiwear agent may be present in an amount that delivers from 0.01 wt% to 0.2 wt%, or from 0.015 wt% to 0.15 wt%, or from 0.02 wt% to 0.1 wt%, or from 0.025 wt% to 0.08 wt% phosphorus. The antiwear agent may be Zinc Dialkyldithiophosphate (ZDP). For certain ZDPs that may contain 11% P, suitable amounts may include 0.09 wt% to 0.82 wt%. Non-phosphorus containing antiwear agents include borates (including borated epoxides), dithiocarbamate compounds, molybdenum containing compounds, and sulfurized olefins. In certain embodiments, the fuel and/or lubricant compositions of the present invention are free of phosphorus-containing antiwear/extreme pressure agents.

Foam inhibitors useful as additional additives in the fuel and/or lubricant compositions described herein include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, optionally vinyl acetate, demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers. In certain embodiments, the composition may comprise a silicone-containing defoamer in combination with a C ₅–C₁₇ alcohol.

Pour point depressants that may be used as additional additives in fuel and/or lubricant compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly (meth) acrylates, polyacrylates, and/or polyacrylamides.

The metal deactivator may be selected from the group consisting of benzotriazole (such as tolyltriazole), 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-amino-2-propanol, derivatives of dimercaptothiadiazole, octylamine octoate (octylamine octanoate), condensation products of PIBSA or dodecenylsuccinic anhydride, and/or fatty acids such as oleic acid with polyamines. Metal deactivators may also be described as corrosion inhibitors.

Seal swelling agents that may be used as additional additives in the compositions described herein may include sulfolane derivatives, which are commercially available from Exxon under the trade names Necton-37 ^TM (FN 1380) and MINERAL SEAL Oil ^TM (FN 3200).

Fuel composition

Also provided are fuel compositions comprising a fuel and a reaction product comprising a quaternary ammonium salt, and optionally also comprising at least one of the above further additives. In certain embodiments, the fuel may be diesel fuel. In certain embodiments, the fuel may comprise gasoline. In certain embodiments, the fuel composition is used in a fuel cell, based on the total weight of the fuel composition, the reaction product comprising the quaternary ammonium salt may be in the range of 5 to 1,000 wt ppm (such as 5 to 750 wt ppm, 5 to 500 wt ppm, 5 to 250 wt ppm, 5 to 200 wt ppm, 5 to 150 wt ppm, 5 to 100 wt ppm, 10 to 1,000 wt ppm, 10 to 750 wt ppm, 10 to 500 wt ppm, 10 to 250 wt ppm, 10 to 200 wt ppm, 10 to 150 wt ppm, 10 to 100 wt ppm, 15 to 1,000 wt ppm, 15 to 750 wt ppm, 15 to 500 wt ppm, 15 to 250 wt ppm 15 to 200 ppm by weight, 15 to 150 ppm by weight, 15 to 100 ppm by weight, 20 to 1,000 ppm by weight, 20 to 750 ppm by weight, 20 to 500 ppm by weight, 20 to 250 ppm by weight, 20 to 200 ppm by weight, 20 to 150 ppm by weight, 20 to 100 ppm by weight, 25 to 1,000 ppm by weight, 25 to 750 ppm by weight, 25 to 500 ppm by weight, 25 to 250 ppm by weight, 25 to 200 ppm by weight, 25 to 150 ppm by weight, or 25 to 100 ppm by weight) is added to the fuel composition.

Also provided are methods of improving the dewatering (i.e., demulsification) properties of a fuel composition, the methods comprising incorporating the above-described compositions into a fuel composition. The use of the above composition for providing improved dewatering performance in fuels such as fuels that are liquid at room temperature is also provided.

Also provided are methods of reducing and/or preventing injector deposits in an engine, the method comprising supplying a fuel composition as described herein to a fuel injector of the engine and operating the engine.

Also provided is the use of the fuel composition described herein for reducing and/or preventing internal deposits in an engine operated with the fuel composition.

In certain embodiments, the fuel composition may comprise a fuel that is liquid at room temperature and that may be used to fuel an engine. The fuel may be liquid at ambient conditions, such as room temperature (20 ℃ to 30 ℃). The fuel may be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. Hydrocarbon fuels can be obtained by refining or optionally (hydro) treating a crude oil source. It may be a single stream from a refinery stream or a mixture of different fractions.

In certain embodiments, the fuel is gasoline, while in other embodiments, the fuel is leaded gasoline or unleaded gasoline. In certain embodiments, the fuel is diesel fuel. The hydrocarbon fuel may be a hydrocarbon produced by a process such as the Fischer-Tropsch process. Examples of such fuels include Gas To Liquids (GTL) processes, biomass To Liquids (BTL) processes, and Coal To Liquids (CTL) processes. The hydrocarbon fraction may alternatively be produced by hydrocracking or hydrogenation of vegetable oils. These hydrocarbon fuels may be used alone or in combination with other hydrocarbon or non-hydrocarbon fuels. The hydrocarbon fuel may be a petroleum distillate including gasoline as defined by EN228 or ASTM specification D4814, or diesel fuel as defined by EN590 or ASTM specification D975.

The non-hydrocarbon fuel may be an oxygenate composition, commonly referred to as an oxygenate, including alcohols, ethers, ketones, carboxylic esters, nitroalkanes, or mixtures thereof. The non-hydrocarbon fuels may include, for example, methanol, ethanol, methyl tertiary butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals, such as rapeseed methyl ester and soybean methyl ester, and nitromethane. Mixtures of hydrocarbon and non-hydrocarbon fuels may include, for example, gasoline and methanol and/or ethanol, diesel fuel and transesterified vegetable oils (such as rapeseed methyl ester).

In certain embodiments, the liquid fuel is an aqueous emulsion in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. In certain embodiments, the fuel may have a sulfur content of 5000ppm or less, 1000ppm or less, 300ppm or less, 200ppm or less, 30ppm or less, or 10ppm or less by weight. In certain embodiments, the fuel may have a sulfur content of 1ppm to 100ppm by weight. In certain embodiments, the fuel comprises from 0ppm to 1000ppm, or from 0ppm to 500ppm, or from 0ppm to 100ppm, or from 0ppm to 50ppm, or from 0ppm to 25ppm, or from 0ppm to 10ppm, or from 0ppm to 5ppm of an alkali metal, alkaline earth metal, transition metal, or mixtures thereof. In certain embodiments, the fuel contains 1 to 10ppm by weight of alkali metal, alkaline earth metal, transition metal, or mixtures thereof. It is well known in the art that fuels containing alkali metals, alkaline earth metals, transition metals, or mixtures thereof may have a greater tendency to form deposits, thus contaminating or plugging the common rail injectors. The fuel of the present invention is present in the fuel composition in a major amount, typically greater than 50 wt%, and in certain embodiments, greater than 90 wt%, greater than 95 wt%, greater than 99.5 wt%, or greater than 99.8 wt%.

The rate of treatment of the fuel composition with the reaction product comprising the quaternary ammonium salt may be in the range of 5ppm to 750ppm, 5ppm to 1000ppm, or 5ppm to 500ppm, or 10ppm to 250ppm, or 10ppm to 150ppm, or 15ppm to 100ppm, based on the total weight of the fuel composition. In certain embodiments, the treatment rate may range from 250ppm to 1000ppm, or from 250ppm to 750ppm, or from 500ppm to 750ppm, or from 250ppm to 500ppm, based on the total weight of the fuel composition.

In certain embodiments, the fuel composition may further comprise at least one additional additive as described above. In certain embodiments, the at least one additional additive may include at least one demulsifier. Suitable demulsifiers may include, but are not limited to, arylsulfonates and polyalkoxylated alcohols, such as polyethylene oxide and polypropylene oxide copolymers, and the like. Demulsifiers may also include nitrogen-containing compounds such as oxazoline and imidazoline compounds and fatty amines, as well as mannich compounds. Mannich compounds are the reaction products of alkylphenols and aldehydes (especially formaldehyde) with amines (especially amine condensates and polyalkylene polyamines). The materials described in U.S. patent 3,036,003;3,236,770;3,414,347;3,448,047;3,461,172;3,539,633;3,586,629;3,591,598;3,634,515;3,725,480;3,726,882; and 3,980,569 are illustrative. Other suitable demulsifiers are, for example, alkali or alkaline earth metal salts of alkyl-substituted phenols and naphthalene sulfonates and alkali or alkaline earth metal salts of fatty acids, and also neutral compounds, such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-amyl phenol ethoxylates), fatty acids, alkylphenols, condensation products of Ethylene Oxide (EO) and Propylene Oxide (PO) (e.g., comprising polyethylene imine or another polysiloxane in the form of EO/PO block copolymers). Suitable demulsifiers also include hydrocarbyl-substituted dicarboxylic acids in the free acid form or in the anhydride form, which may be an intramolecular anhydride such as succinic, glutaric or phthalic anhydride, or an intermolecular anhydride that links two dicarboxylic acid molecules together. The hydrocarbyl substituent may have from 12 to 2000 carbon atoms and may comprise polyisobutenyl substituents having a number average molecular weight of from 300 to 2800. Exemplary hydrocarbyl-substituted dicarboxylic acids include, but are not limited to, hydrocarbyl-substituted acids derived from malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecanedioic, phthalic, isophthalic, terephthalic, phthalic, isophthalic or terephthalic acid, maleic, fumaric or glutaconic acid. In one embodiment, the fuel composition of the present invention does not comprise a demulsifier as a further additive. Suitable treatment rates for the demulsifier to the fuel may be from 0ppm to 50ppm (such as, for example, from 1ppm to 50ppm, from 5ppm to 50ppm, from 1ppm to 25ppm, from 5ppm to 25ppm, from 1ppm to 20ppm, or from 5ppm to 20 ppm) based on the total weight of the fuel.

In certain embodiments, the at least one additional additive may comprise at least one detergent/dispersant. Suitable detergents/dispersants may include an amphiphilic material having at least one hydrophobic hydrocarbon group having a number average molecular weight of 100 to 10000 and at least one of (i) a mono-or polyamino group having up to 6 nitrogen atoms (at least one nitrogen atom having basic character), (ii) a hydroxyl group in combination with a mono-or polyamino group (at least one nitrogen atom having basic character), (iii) a carboxyl group or an alkali metal or alkaline earth metal salt thereof, (iv) a sulfonic acid group or an alkali metal or alkaline earth metal salt thereof, (v) a polyoxy-C ₂ to C ₄ alkylene moiety terminated by a hydroxyl group, a mono-or polyamino group (at least one nitrogen atom having basic character) or by a carbamate group, (vi) a carboxylate group, (vii) a moiety derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups, and/or (viii) a moiety obtained by mannich reaction of a substituted phenol with an aldehyde and a mono-or polyamine.

In certain embodiments, the hydrophobic hydrocarbyl groups in these detergents/dispersants (which ensure adequate solubility in the fuel) have a number average molecular weight of 85 to 20,000, 1113 to 10,000, or 300 to 5000. In certain embodiments, the detergent/dispersant has an M _n of 300 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. In certain embodiments, the hydrophobic hydrocarbyl group may be a polypropylene, polybutylene, and/or polyisobutenyl group having a number average molecular weight of 300 to 5000, 300 to 3000, 500 to 2500, or 700 to 2500. In certain embodiments, the detergent/dispersant has a number average molecular weight of 800 to 1500.

In certain embodiments, the at least one additional additive may comprise at least one high TBN nitrogen-containing detergent/dispersant, such as a succinimide, which is the condensation product of a hydrocarbyl-substituted succinic anhydride and a poly (alkylene amine). Exemplary succinimide detergents/dispersants are more fully described in U.S. Pat. nos. 4,234,435 and 3,172,892. Another class of ashless dispersants are high molecular weight esters prepared by the reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol, such as glycerol, pentaerythritol or sorbitol. Such materials are described in more detail in U.S. Pat. No. 3,381,022.

The nitrogen-containing detergent/dispersant may be the reaction product of a carboxylic acid-derived acylating agent and an amine. The acylating agent may vary between formic acid and its acylated derivatives to acylating agents having up to 5,000, 10,000 or 20,000 carbon atoms high molecular weight aliphatic substituents. Amino compounds can vary from ammonia itself to amines (typically aliphatic substituents having up to 30 carbon atoms and up to 11 nitrogen atoms). Suitable acylated amino compounds may be those formed by reacting an acylating agent having a hydrocarbyl substituent of at least 8 carbon atoms with a compound comprising at least one primary or secondary amine group. The acylating agent may be a monocarboxylic acid or a polycarboxylic acid (or reactive equivalents thereof), such as a substituted succinic acid, phthalic acid, or propionic acid, and the amino compound may be a polyamine or a mixture of polyamines, such as a mixture of ethylenepolyamines. Alternatively, the amine may be a hydroxyalkyl substituted polyamine. The hydrocarbyl substituents in such acylating agents may contain at least 10 carbon atoms. In certain embodiments, the hydrocarbyl substituent may comprise at least 12, such as 30 or 50 carbon atoms. In certain embodiments, it may contain up to 200 carbon atoms. The number average molecular weight (M _n) of the hydrocarbyl substituent of the acylating agent may be 170 to 2800, for example 250 to 1500. In certain embodiments, M _n of the substituents may range from 500 to 1500, or alternatively from 500 to 1100. In certain embodiments, M _n of the substituents may range from 700 to 1300. In certain embodiments, the hydrocarbyl substituent may have a number average molecular weight of 700 to 1000, or 700 to 850, or e.g., 750.

Another class of ashless dispersants is mannich bases. These are materials formed from the condensation of higher molecular weight, alkyl substituted phenols, alkylene polyamines, and aldehydes (such as formaldehyde) and are described in more detail in U.S. Pat. No. 3,634,515.

Useful nitrogen-containing dispersants include the product of a mannich reaction between (a) an aldehyde, (b) a polyamine, and (c) an optionally substituted phenol. The phenol may be substituted such that the molecular weight of the mannich product is less than 7500. Optionally, the molecular weight may be less than 2000, less than 1500, less than 1300, or for example less than 1200, less than 1100, less than 1000. In certain embodiments, the mannich product has a molecular weight of less than 900, less than 850, or less than 800, less than 500, or less than 400. The substituted phenols may be substituted on the aromatic ring by up to 4 groups. For example, it may be a trisubstituted or disubstituted phenol. In certain embodiments, the phenol may be a monosubstituted phenol. Substitution may be in one or more ortho and/or meta and/or para positions. To form the Mannich product, the molar ratio of aldehyde to amine is 4:1 to 1:1 or 2:1 to 1:1. The molar ratio of aldehyde to phenol may be at least 0.75:1, such as 0.75:1 to 4:1, preferably 1:1 to 4;1, or 1:1 to 2:1. To form the mannich product, the molar ratio of phenol to amine may be at least 1.5:1, such as at least 1.6:1, at least 1.7:1, at least 1.8:1, or at least 1.9:1. The molar ratio of phenol to amine may be up to 5:1, for example, it may be up to 4:1, or up to 3.5:1. In certain embodiments, it is at most 3.25:1, at most 3:1, at most 2.5:1, at most 2.3:1, or at most 2.1:1.

Other dispersants used as additional additives can include polymeric dispersant additives, which are typically hydrocarbon-based polymers containing polar functionality to impart dispersion characteristics to the polymer. The amines can be used to prepare high TBN nitrogen containing dispersants. One or more poly (alkylene amines) may be used, and these poly (alkylene amines) may include one or more poly (ethylene amines) having 3 to 5 ethylene units and 4 to 6 nitrogen units. Such materials include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and Pentaethylenehexamine (PEHA). Such materials are commercially available as mixtures of various isomers containing a range of numbers of ethylene units and nitrogen atoms, and various isomeric structures (including various cyclic structures). The poly (alkylene amine) may also contain relatively higher molecular weight amines known in the industry as vinylamine pot substrates.

In certain embodiments, the fuel composition may additionally comprise a quaternary ammonium salt in addition to the reaction product comprising a quaternary ammonium salt described herein. These may include alkyl amine quaternary ammonium salts. Other quaternary ammonium salts may comprise (a) a compound comprising (i) at least one tertiary amino group as described above, and (ii) a hydrocarbyl substituent having a number average molecular weight of 100 to 5000, or 250 to 4000, or 100 to 2500 or 3000, and (b) a quaternizing agent suitable for converting the tertiary amino group of (a) (i) as described above to a quaternary nitrogen. Other quaternary ammonium salts are more fully described in U.S. patent 7,951,211, published in 2011, month 5, 31; and 8,083814, release No. 12, month 27 in 2011; and U.S. publication 2013/0118062, publication No. 16, 5, 2013; 2012/0010112, 2013/01333243, 2013/013243, 2008/011080, 2008/5, and 2011/0219674, 2011/9, US 2012/0149617, 2012/0225463, 2013/8, 29, 2011/0258917, 2011/10, 27, 2011/0315107, 20112, 29, 2013/007494, 28, 2012/0255512, 2012, 11, 2013/0333649, 2013/12, 19, 2013/0118062, 2013/16, international WO 2011/731, 20111/17, 2011/889, 2013/888, 2013/889, 2013/887, 2013/889, 20115, 2013/887, 2013/889, 2013/887, 2013/883, 2013/889, 2013/883, 2013/2019, 2013/2015, 2017, 2013/2013, 2015, 2011, 2013, and WO 2013/2015, respectively.

The quaternary ammonium salt used as a further additive may be a quaternary ammonium salt prepared from a hydrocarbyl-substituted acylating agent such as a polyisobutylsuccinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight greater than 1200, a polyisobutylsuccinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or a polyisobutylsuccinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight of 1000.

In certain embodiments, the fuel composition may further comprise additional quaternary ammonium salts as additional additives. These additional salts may be imides prepared from the reaction of nitrogen-containing compounds with hydrocarbyl-substituted acylating agents having a hydrocarbyl substituent with a number average molecular weight of 1300 to 3000. In certain embodiments, the quaternary ammonium salt produced from the reaction of a nitrogen-containing compound and a hydrocarbyl-substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight greater than 1200 or a hydrocarbyl substituent with a number average molecular weight of 300 to 750 is an amide or ester.

In certain embodiments, the nitrogen-containing compound of the additional quaternary ammonium salts may be an imidazole or nitrogen-containing compound having any one of the following formulas:

Wherein R may be a C ₁ to C ₆ alkylene group, each of R ₁ and R ₂ may be independently a C ₁ to C ₆ alkylene group, and each of R ₃、R₄、R₅ and R ₆ may be independently hydrogen or a C ₁ to C ₆ hydrocarbon group.

In certain embodiments, the quaternizing agent used to prepare these additional quaternary ammonium salts can be dialkyl sulfate, alkyl halide, hydrocarbyl-substituted carbonate, hydrocarbyl epoxide, carboxylate, alkyl ester, or mixtures thereof. In certain embodiments, the quaternizing agent can be a hydrocarbon-based epoxide. In certain embodiments, the quaternizing agent can be a hydrocarbyl epoxide in combination with an acid. In certain embodiments, the quaternizing agent can be a salicylate, oxalate, or terephthalate. In certain embodiments, the hydrocarbyl epoxide is an alcohol functionalized epoxide or a C ₄ to C ₁₄ epoxide.

In certain embodiments, the quaternizing agent is multifunctional, resulting in the additional quaternary ammonium salt being a coupled quaternary ammonium salt.

Exemplary treatment rates for the fuel compositions described herein for additional detergent/dispersants are from 0ppm to 500ppm, or from 0ppm to 250ppm, or from 0ppm to 100ppm, or from 5ppm to 250ppm, or from 5ppm to 100ppm, or from 10ppm to 100ppm.

In certain embodiments, the at least one additional additive may comprise at least one cold flow improver. The cold flow improver may be at least one of (1) a copolymer of a C ₂ to C ₄₀ -olefin with at least one additional ethylenically unsaturated monomer, (2) a comb polymer, (3) a polyalkylene oxide, (4) a polar nitrogen compound, (5) a sulfocarboxylic or sulphonic acid or derivative thereof, or (6) a poly (meth) acrylate. It is possible to use mixtures of different representatives from one of the specific classes (1) to (6) and/or mixtures of representatives from the different classes (1) to (6).

Suitable C ₂ to C ₄₀ olefin monomers for the copolymers of class (1) are, for example, those having from 2 to 20, or from 2 to 10, or from 1 to 3, or 1 or 2 carbon-carbon double bonds, such as those having one carbon-carbon double bond. In the latter case, the carbon-carbon double bond may be disposed at the terminal (alpha-olefin) or internally. Suitable olefin monomers include alpha-olefins such as alpha-olefins having from 2 to 6 carbon atoms, for example propylene, 1-butene, 1-pentene, 1-hexene and/or ethylene. The at least one further ethylenically unsaturated monomer of category (1) may be selected from alkenyl carboxylates, for example C ₂ to C ₁₄ alkenyl esters of carboxylic acids having 2 to 21 carbon atoms, for example vinyl esters and propenyl esters, wherein the hydrocarbon radical of the carboxylic acid may be linear or branched, such as vinyl esters, examples of suitable alkenyl carboxylates being vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate, vinyl pivalate, vinyl caproate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, (meth) acrylic acid, for example with C ₁ to C ₂₀ alkanols, in particular C ₁ to C ₁₀ alkanols, such as with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, Nonanol and decanol, as well as their structural isomers and esters of further olefins, such as the olefin base monomers mentioned above having a molecular weight of from C ₂ to C ₄₀, for example ethylene or propylene, suitable further olefins being in particular from C ₁₀ to C ₄₀ -alpha-olefins.

Suitable exemplary copolymers of class (1) are also those comprising two or more different alkenyl carboxylates in copolymerized form, which differ in alkenyl functionality and/or carboxylic acid group. Also suitable are copolymers, which as well as alkenyl carboxylates comprise at least one olefin and/or at least one (meth) acrylate in copolymerized form.

Terpolymers of C ₂ to C ₄₀ -alpha-olefins, C ₁ to C ₂₀ alkyl esters of ethylenically unsaturated monocarboxylic acids having 3 to 15 carbon atoms and C ₂ to C ₁₄ alkenyl esters of saturated monocarboxylic acids having 2 to 21 carbon atoms are also suitable as copolymers of class (1). Terpolymers of this type are described in WO 2005/054314. An exemplary terpolymer of this type is formed from ethylene, 2-ethylhexyl acrylate, and vinyl acetate.

In certain embodiments, at least one or additional ethylenically unsaturated monomer is copolymerized in the copolymer of class (1) in an amount of 1 to 50 wt%, such as 10 to 45 wt% or 20 to 40 wt%, based on the total copolymer. Thus, the major proportion in terms of the weight of monomer units in the copolymer of class (1) may be derived from the C ₂ to C ₄₀ base olefins. The copolymers of category (1) may have a number average molecular weight of 1000 to 20,000, or 1000 to 10,000, or 1000 to 8000.

An exemplary comb polymer of component (2) can be obtained, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer (e.g., with an a-olefin or unsaturated ester such as vinyl acetate), followed by esterification of the anhydride or acid functionality with an alcohol having at least 10 carbon atoms. Other suitable comb polymers are copolymers of alpha-olefins with esterified comonomers, for example, esterified copolymers of styrene with maleic anhydride or esterified copolymers of styrene with fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleates. Homopolymers and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (2) are also those described, for example, in WO 2004/035715 and in pages "Comb-Like Polymers.Structure and Properties",N.A.Platéand V.P.Shibaev,J.Poly.Sci.Macromolecular Revs.8,, 117 to 253 (1974). Mixtures of comb polymers are also suitable.

Suitable polyalkylene oxides as components of class (3) are, for example, polyalkylene oxide esters, polyalkylene oxide ethers, mixed polyalkylene oxide esters/ethers and mixtures thereof. These polyoxyalkylene compounds may comprise at least one linear alkyl group, such as at least two linear alkyl groups, each having from 10 to 30 carbon atoms, and polyoxyalkylene groups having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A061 895 and U.S. Pat. No. 4,491,455. Suitable polyoxyalkylene compounds are polyethylene glycols and polypropylene glycols having a number average molecular weight of from 100 to 5000. In addition, suitable are polyoxyalkylene monoesters and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.

Polar nitrogen compounds suitable for use as components of class (4) may be ionic or nonionic and may have at least one substituent, or at least two substituents, in the form of tertiary nitrogen atoms having the general formula > NR ⁷, wherein R ⁷ is a C ₈ to C ₄₀ hydrocarbyl group. The nitrogen substituents may also be quaternized, i.e., in cationic form. Examples of such nitrogen compounds are the ideas of ammonium salts and/or amides, which can be obtained by reaction of at least one amine substituted by at least one hydrocarbyl group with carboxylic acids having 1 to 4 carboxyl groups or with suitable derivatives thereof. The amine may comprise at least one linear C ₈ to C ₄₀ alkyl group. Suitable primary amines for the preparation of the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and higher linear homologs. Secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenamine. Also suitable for this purpose are amine mixtures, in particular those which are obtainable on an industrial scale, such as fatty amines or hydrogenated tallow amines, as described, for example, in Ullmann' sEncyclopedia of Industrial Chemistry, 6 th edition, section "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1, 2-dicarboxylic acid, cyclohexene-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acid substituted by long-chain hydrocarbon groups.

Suitable sulfocarboxylic acids, sulphonic acids or their derivatives as cold flow improvers of class (5) are, for example, the oil-soluble carboxamides and carboxylic esters of o-sulfobenzoic acid, in which the sulphonic acid function is present as a sulphonic acid salt with an alkyl-substituted ammonium cation, as described in EP-A261 957.

Poly (meth) acrylates suitable as cold flow improvers of type (6) are homo-or copolymers of acrylic and methacrylic esters. Also suitable are copolymers of at least two different (meth) acrylates which differ with respect to the esterified alcohol. The copolymer optionally comprises another different ethylenically unsaturated monomer in copolymerized form. The weight average molecular weight of the polymer is preferably 50,000 to 500,000. The polymer may be a copolymer of methacrylic acid and a methacrylate ester of saturated C ₁₄ and C ₁₅ alcohols, the acid groups having been neutralized with hydrogenated tallow amine. Suitable poly (meth) acrylates are described, for example, in WO 00/44857.

Further additives comprising at least one cold flow improver may be added to the fuel composition in an amount of from 0 to 5000 ppm by weight, or from 10 to 5000 ppm by weight, or from 20 to 2000 ppm by weight, or from 50 to 1000 ppm by weight, or from 100 to 700 ppm by weight, or from 200 to 500 ppm by weight, based on the total weight of the fuel composition.

Lubricating composition

Also provided are lubricating compositions comprising an oil of lubricating viscosity and the above compositions. The reaction product comprising the quaternary ammonium salt may be present in the lubricating composition in an amount of from 1 wt.% to 5 wt.%, based on the total weight of the lubricating composition. In certain embodiments, the oil of lubricating viscosity may have a total sulfated ash level of less than 1 weight percent, based on the total weight of the lubricating composition. In certain embodiments, the oil of lubricating viscosity may have a total phosphorus content of less than 0.11 wt.%, based on the total weight of the lubricating composition.

Also provided is a method of lubricating a crankcase of an engine, the method comprising supplying to the engine and operating the engine a lubricating composition as described herein.

Also provided is the use of the lubricating composition described herein for lubricating the crankcase of an engine.

Oils of lubricating viscosity may include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and/or hydrofinishing, unrefined oils, refined oils, re-refined oils or mixtures thereof. More detailed descriptions of unrefined, refined, and re-refined oils are provided in WO2008/147704, paragraphs [0054] to [0056 ]. More detailed descriptions of natural and synthetic lubricating oils are provided in paragraphs [0058] to [0059] of WO 2008/147704. The synthetic oil may also be produced by a Fischer-Tropsch reaction and may be hydroisomerised Fischer-Tropsch hydrocarbon or wax. In certain embodiments, the oil may be prepared by a Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

The oil of lubricating viscosity may also be selected from any of the group I-V base oils as specified in the American Petroleum Institute (API) base oil interchange guidelines. Five base oils are classified as group I, >0.03% sulfur or <90% saturates, and viscosity index 80-120, group II, <0.03% sulfur and ≡90% saturates, and viscosity index 80-120, group III, <0.03% sulfur and ≡90% saturates, and viscosity index ≡120, all polyalphaolefins, group V, all other base oils. Class I, class II and class III may be referred to as mineral oil sources.

Exemplary treatment rates of the reaction product comprising the quaternary ammonium salt to the lubricating oil are from 0.1 wt.% to 10 wt.%, or from 0.5 wt.% to 5 wt.%, or from 0.5 wt.% to 2.5 wt.%, or from 0.5 wt.% to 1 wt.%, or from 0.1 wt.% to 0.5 wt.%, or from 1 wt.% to 2 wt.%, based on the total weight of the lubricating oil.

The amount of oil of lubricating viscosity present in the lubricating composition described herein is the balance remaining after subtracting the total amount of all additives, including the reaction product comprising the quaternary ammonium salt described herein, and any additional additives as described herein.

The lubricating composition described herein can be in the form of a concentrate or a fully formulated lubricant. If the lubricating composition is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of these additives to the oil of lubricating viscosity and/or diluent oil includes the range of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.

In certain embodiments, the lubricating compositions described herein may be used in internal combustion engines. The internal combustion engine may be of the spark ignition type or the compression ignition type. The internal combustion engine may be a 2-stroke or 4-stroke engine. The internal combustion engine may be a passenger car engine, a light diesel engine, a heavy diesel engine, a motorcycle engine or a 2-stroke or 4-stroke marine diesel engine. The internal combustion engine may be a passenger car engine or a heavy duty diesel internal combustion engine.

In certain embodiments, a lubricating composition as described herein may comprise an overbased metal-containing detergent as a further additive. Overbased detergents are known in the art. Overbased materials (otherwise referred to as overbased or superbased salts) are generally single phase homogeneous systems characterized by a metal content exceeding that which would be present based on the stoichiometric neutralization of the metal and the particular acidic organic compound reacting with the metal. The overbased materials are prepared by reacting an acidic material (such as an inorganic acid or lower carboxylic acid, such as carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one organic solvent inert to the acidic organic material (mineral oil, naphtha, toluene, xylene, etc.), a stoichiometric excess of a metal base, and an accelerator (such as calcium chloride, acetic acid, phenol, or alcohol). The acidic organic material may have a sufficient number of carbon atoms to provide solubility in the oil. The amount of "excess" metal (stoichiometry) is typically expressed in terms of metal ratios. The term "metal ratio" is the ratio of the total equivalents of metal to the equivalents of acidic organic compound. The metal ratio of the neutral metal salt is one. Salts with 4.5 times the metal present in the normal salt will have 3.5 equivalents or a ratio of 4.5 metal excess. The term "metal ratio" is also explained in "CHEMISTRY AND Technology of Lubricants", third edition, edited by r.m. mortier and s.t. orszulik, copyright 2010, page 219, subheading 7.25.

The overbased metal-containing detergent may be selected from the group consisting of non-sulfur-containing phenates, sulfonates, liu Fang acid salts, salicylates, carboxylates, and mixtures thereof or borated equivalents thereof. The overbased detergent may be borated with a borated agent, such as boric acid.

The overbased detergent may be a non-sulfur-containing phenate, sulfonate, or mixtures thereof.

In certain embodiments, the overbased sulfonate detergent may be present in the lubricating composition in an amount of from 0.01 wt.% to 0.9 wt.%, or from 0.05 wt.% to 0.8 wt.%, or from 0.1 wt.% to 0.7 wt.%, or from 0.2 wt.% to 0.6 wt.%, based on the total weight of the lubricating composition.

In certain embodiments, the overbased sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.

The overbased sulfonates may have a total base number of from 250 to 600, or 300 to 500 (on an oil free basis). Overbased detergents are known in the art. In certain embodiments, the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of U.S. patent application 2005065045. The linear alkylbenzene may have a benzene ring attached at any position on the linear chain, such as at the 2-, 3-, or 4-position, or mixtures thereof. The primary linear alkylbenzene sulfonate detergent may be useful to assist in improving fuel economy. In certain embodiments, the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds as disclosed in paragraphs [0046] to [0053] of U.S. patent application 2008/0119378.

In certain embodiments, the overbased sulfonate detergent comprises overbased calcium sulfonate. The calcium sulfonate detergent may have a metal ratio of 18 to 40 and a TBN of 300 to 500 or 325 to 425.

Other detergents may also include "hybrid" detergents formed from mixed surfactant systems that include the phenate and/or sulfonate components described, such as phenate/salicylate, sulfonate/phenate, sulfonate/salicylate, sulfonate/phenate/salicylate, for example, in U.S. Pat. Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. In the case of, for example, a hybrid sulfonate/phenate detergent, the hybrid detergent will be considered to be equivalent to the amount of different phenate and sulfonate detergents that incorporate similar amounts of phenate and sulfonate detergents, respectively.

Other detergents may have alkali, alkaline earth or zinc counter ions. In certain embodiments, the metal may be sodium, calcium, barium, or magnesium. Other detergents may be sodium, calcium or magnesium containing detergents.

Other detergents may be overbased detergents of sodium, calcium or magnesium salts of phenolates, sulfur-containing phenates, liu Fang acid salts and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 450TBN (on an oil free basis).

The phenate detergent may be derived from p-hydrocarbyl phenol. This type of alkylphenol may be coupled with sulfur and overbased, coupled with aldehydes and overbased or carboxylated to form a salicylate detergent. Suitable alkylphenols include alkylphenols alkylated with oligomers of propylene, such as tetrapropenyl phenol (e.g., p-dodecyl phenol or PDDP) and pentapropenyl phenol. Other suitable alkylphenols include alkylphenols alkylated with alpha-olefins, isomerized alpha-olefins, and polyolefins like polyisobutylenes. In certain embodiments, the lubricating composition comprises less than 0.2 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.% of a phenate detergent derived from PDDP. In certain embodiments, the lubricating composition comprises a phenate detergent that is not derived from PDDP.

The overbased detergent may be present in the lubricating composition in an amount of from 0wt% to 10 wt%, or from 0.1 wt% to 10 wt%, or from 0.2 wt% to 8 wt%, or from 0.2 wt% to 3wt%, based on the total weight of the lubricating composition. For example, in heavy duty diesel engine lubricating compositions, the detergent may be present at 2 wt% to 3wt% of the lubricating composition. For passenger car engines, the detergent may be present in the lubricating composition in an amount of from 0.2 wt.% to 1 wt.%, based on the total weight of the lubricating composition. In certain embodiments, the lubricating composition comprises at least one overbased detergent having a metal ratio of at least 3 or at least 8 or at least 15.

In certain embodiments, the lubricating composition comprises at least one dispersant as a further additive. The dispersant may be selected from succinimide dispersants, mannich dispersants (MANNICH DISPERSANT), succinamide dispersants, polyolefin succinic acid esters, amides, or ester-amides, or mixtures thereof.

Succinimide dispersants may be derived from aliphatic polyamines. The aliphatic polyamine may be ethylene polyamine, propylene polyamine, butylene polyamine or mixtures thereof. In certain embodiments, the aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine bottoms, and mixtures thereof.

In certain embodiments, the dispersant may be a polyolefin succinate, amide, or ester-amide. For example, the polyolefin succinate may be a polyisobutylene succinate of pentaerythritol or a mixture thereof. The polyolefin succinate-amide may be polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as diamine or diethylamine).

The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is a polyisobutylene succinimide. The polyisobutene from which the polyisobutene succinic anhydride can be derived can have a number average molecular weight of 350 to 5000, or 550 to 3000, or 750 to 2500. Succinimide dispersants and methods for their preparation are disclosed in, for example, U.S. Pat. nos. 3,172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444,170、3,467,668、3,501,405、3,542,680、3,576,743、3,632,511、4,234,435、Re 26,433 and 6,165,235, 7,238,650 and EP patent application 0 355 895a.

The dispersant may also be post-treated by reaction with any of a variety of agents using conventional methods. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes and ketones, carboxylic acids (such as terephthalic acid), hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In certain embodiments, the post-treated dispersant is borated. In certain embodiments, the post-treated dispersant may be reacted with dimercaptothiadiazole. In certain embodiments, the post-treated dispersant may be reacted with phosphoric acid or phosphorous acid. In certain embodiments, the post-treated dispersant may be reacted with terephthalic acid and boric acid (as described in U.S. patent application US 2009/0054278).

In certain embodiments, the dispersant may be borated or non-borated. The borated dispersant may be a succinimide dispersant. In certain embodiments, the ashless dispersant may be boron-containing, i.e., boron has been incorporated and delivered into the lubricant composition. The boron-containing dispersant may be present in an amount that delivers at least 25ppm boron, at least 50ppm boron, or at least 100ppm boron to the lubricating composition. In certain embodiments, the lubricating composition may be free of boron-containing dispersants. In certain embodiments, the lubricating composition has no more than 10ppm boron.

Dispersants useful as additional additives in the lubricating compositions described herein can be prepared/obtained/obtainable from the reaction of succinic anhydride by an "ene" reaction or a "thermal" reaction, by what may be referred to as a "direct alkylation process. The "ene" reaction mechanism and general reaction conditions are summarized in "MALEIC ANHYDRIDE", pages 147-149, which were compiled by B.CTrivedi and B.C.Culbertson, and published by Plenum Press in 1982. Dispersants prepared by a process involving an "ene" reaction can be polyisobutene succinimides having carbocycles present on less than 50 mole% or 0 to less than 30 mole% or 0 to less than 20 mole% or 0 mole% of the dispersant molecules. The "ene" reaction may have a reaction temperature of 180 ℃ to less than 300 ℃, or 200 ℃ to 250 ℃, or 200 ℃ to 220 ℃.

Dispersants may also be obtained/obtainable from chlorine-assisted processes, typically involving Diels-Alder (Diels-Alder) chemical reactions, resulting in the formation of carbon ring bonds. The dispersant produced by the chlorine-assisted process may be a polyisobutene succinimide having a carbocyclic ring present on 50 mole% or more, or 60 to 100 mole% of the dispersant molecules. The heat and chlorine assist process is described in more detail in U.S. patent 7,615,521, columns 4 to 5, and preparation examples a and B.

The dispersant may have a carbonyl to nitrogen ratio (CO: N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2. In certain embodiments, the dispersant may have a CO to N ratio of 2:1 to 1:10 or 2:1 to 1:5 or 2:1 to 1:2 or 1:1.4 to 1:0.6.

In certain embodiments, the dispersant may be a succinimide dispersant and may include a polyisobutylene succinimide, wherein the polyisobutylene from which the polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000 or 750 to 2500. The dispersant may be present in the lubricating composition in an amount of from 0 wt.% to 20 wt.%, from 0.1 wt.% to 15 wt.%, or from 0.5 wt.% to 9 wt.%, or from 1 wt.% to 8.5 wt.%, or from 1.5 wt.% to 5 wt.%, based on the total weight of the lubricating composition.

In certain embodiments, the lubricating composition may comprise a molybdenum compound as a further additive. The molybdenum compound may be an antiwear agent or an antioxidant. The molybdenum compound may be selected from molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide the lubricating composition with 0ppm to 1000ppm, 5ppm to 1000ppm, 10ppm to 750ppm, 5ppm to 300ppm, or 20ppm to 250ppm molybdenum.

In certain embodiments, the lubricating composition may further comprise an antioxidant as a further additive. Antioxidants include sulfurized olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxy sulfides, or mixtures thereof. The antioxidant may be present in the lubricating composition in an amount of from 0 wt% to 15 wt%, or from 0.1 wt% to 10 wt%, or from 0.5 wt% to 5wt%, or from 0.5 wt% to 3wt%, or from 0.3wt% to 1.5 wt%, based on the total weight of the lubricating composition.

In certain embodiments, the lubricating composition may further comprise a phenolic or aminic antioxidant or mixtures thereof as a further additive, and optionally, the antioxidant may be present in an amount of 0.1 wt% to 3 wt%, or 0.5 wt% to 2.75 wt%, or 1 wt% to 2.5 wt%, based on the total weight of the lubricating composition.

The diarylamine or alkylated diarylamine may be phenyl-alpha-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenyl-naphthylamine, or mixtures thereof. Alkylated diphenylamines may include dinonylated diphenylamines, nonylanilines, octyldiphenylamines, dioctylated diphenylamines, didecylated diphenylamines, decyldiphenylamines, and mixtures thereof. In certain embodiments, the diphenylamine can comprise nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, or mixtures thereof. In certain embodiments, the alkylated diphenylamine can comprise nonyldiphenylamine or dinonyldiphenylamine. The alkylated diarylamines may include octyl, dioctyl, nonyl, dinonyl, decyl or didecylphenyl naphthylamine.

The hindered phenol antioxidant may contain a sec-butyl and/or tert-butyl group as a steric hindrance group. The phenolic group may typically be further substituted with a hydrocarbyl group (typically a straight or branched chain alkyl group) and/or a bridging group attached to the second aromatic group. Examples of suitable hindered phenol antioxidants include 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 4-ethyl-2, 6-di-tert-butylphenol, 4-propyl-2, 6-di-tert-butylphenol or 4-butyl-2, 6-di-tert-butylphenol or 4-dodecyl-2, 6-di-tert-butylphenol. In certain embodiments, the hindered phenol antioxidant may be an ester and may include, for example, irganox ^TM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistries can be found in U.S. patent 6,559,105.

Examples of molybdenum dithiocarbamates that may be used as antioxidants include commercially available materials sold under the trade name such as those available from r.t. vanderbilt co AndAnd Adeka Sakura-Lube ^TM S-100, S-165, S-600 and 525, or mixtures thereof.

In certain embodiments, the lubricating composition may further comprise a viscosity modifier as a further additive. Viscosity modifiers are known in the art and may include hydrogenated styrene-butadiene rubber, ethylene-propylene copolymers, copolymers of ethylene with propylene and higher olefins, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkylstyrenes, polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in international application WO 2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures thereof. The viscosity modifier may comprise a block copolymer (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-isoprene copolymer), a polymethacrylate, an ethylene-alpha olefin copolymer, a hydrogenated star polymer comprising conjugated diene monomers (such as butadiene or isoprene), or a star polymer of polymethacrylate, or a mixture thereof, comprising (i) vinyl aromatic monomer blocks and (ii) conjugated diene olefin monomer blocks.

In certain embodiments, the viscosity modifier may be a dispersant viscosity modifier. Dispersant viscosity modifiers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with acylating agents such as maleic anhydride and amines.

In certain embodiments, the dispersant viscosity modifier comprises an olefin copolymer further functionalized with dispersant amine groups. The olefin copolymer may be an ethylene-propylene copolymer. The olefin copolymer may have a number average molecular weight of 5000 to 20,000, or 6000 to 18,000, or 7000 to 15,000. The olefin copolymer may have a shear stability index of 0 to 20, or 0 to 10, or 0 to 5, as measured by the Orbahn shear test (ASTM D6278).

The formation of dispersant viscosity modifiers is well known in the art. Dispersant viscosity modifiers may include, for example, those described in U.S. Pat. No. 7,790,661, column 2, line 48 to column 10, line 38.

In certain embodiments, the dispersant viscosity modifier may be prepared by grafting an olefinic carboxylic acid acylating agent onto a polymer of 15 to 80 mole% ethylene, 20 to 85 mole% C _3-10 alpha-mono-olefin, and 0 to 15 mole% non-conjugated diene or triene (the polymer), and further reacting the grafted polymer with an amine (typically an aromatic amine).

Dispersant viscosity modifiers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with acylating agents such as maleic anhydride and amines, polymethacrylates functionalized with amines, or styrene-maleic anhydride copolymers reacted with amines. Suitable amines may be aliphatic or aromatic amines and polyamines. Examples of suitable aromatic amines include nitroanilines, aminodiphenylamines (ADPA), hydrocarbylene-coupled polyaromatic amines, and mixtures thereof. More detailed descriptions of dispersant viscosity modifiers are provided in International publication WO2006/015130 or U.S. Pat. Nos. 4,863,623, 6,107,257, 6,107,258, 6,117,825, and U.S. Pat. No. 7,790,661.

In certain embodiments, dispersant viscosity modifiers may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or International publication WO2006/015130 (see page 2, paragraph [0008] and paragraphs [0065] to [0073 ].

In certain embodiments, the lubricating compositions disclosed herein may further comprise a dispersant viscosity modifier, which may be present at 0wt% to 5 wt%, or 0wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.2 wt% to 1.2 wt%, based on the total weight of the lubricating composition.

In certain embodiments, the lubricating composition may further comprise at least one friction modifier as a further additive. In certain embodiments, the friction modifier may be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters or derivatives of long chain fatty epoxides, fatty imidazolines, amine salts of alkyl phosphates, fatty alkyl tartrates, fatty alkyl tartrimides, fatty maleates and imides, fatty (poly) glycolates, and fatty hydroxyacetamides. The friction modifier may be present in the lubricating composition in an amount of 0 wt.% to 6 wt.%, or 0.01 wt.% to 4 wt.%, or 0.05 wt.% to 2 wt.%, or 0.1 wt.% to 2 wt.%, based on the total weight of the lubricating composition. In certain embodiments, as used herein, the term "fatty alkyl" or "fat" with respect to a friction modifier means a carbon chain having 10 to 22 carbon atoms, such as a straight carbon chain.

Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty acid esters or fatty epoxides, fatty imidazolines such as condensation products of carboxylic acids and polyalkylene polyamines, amine salts of alkylphosphoric acids, fatty alkyl tartrates of tartaric acid, fatty alkyl tartrates of imides, fatty alkyl tartrates of tartaric acid, fatty phosphonates, fatty phosphites, borated phospholipids, borated fatty epoxides, glycerides such as glycerol monooleate, borated glycerides, fatty amines, alkoxylated fatty amines, borated alkoxylated fatty amines, hydroxy and polyhydroxy fatty amines including tertiary hydroxy fatty amines, hydroxyalkylamides, metal salts of fatty acids, metal salts of alkylsalicylic acids, fatty oxazolines, fatty ethoxylated alcohols, condensation products of carboxylic acids and polyalkylene polyamines, or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and salts thereof.

Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil of polyols or soybean oil monoesters and aliphatic carboxylic acids.

In certain embodiments, the friction modifier may be a long chain fatty acid ester. In certain embodiments, the long chain fatty acid esters may be monoesters and/or triglycerides.

In certain embodiments, the lubricating composition may further comprise at least one antiwear agent as a further additive. Examples of suitable antiwear agents include titanium compounds, tartaric acid derivatives (such as tartrates, amides or tartrimides), malic acid derivatives, citric acid derivatives, glycolic acid derivatives, oil-soluble amine salts of phosphorus compounds different from the present invention, sulfurized olefins, metal dihydrocarbyl dithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates and bis (S-alkyl dithiocarbamoyl) disulfide.

The antiwear agent may comprise tartrate or tartrimide as disclosed in International publication WO 2006/044411 or Canadian patent CA 1 183125. The tartrate or tartrimide may contain alkyl ester groups wherein the sum of carbon atoms on the alkyl groups is at least 8. Antiwear agents may include citrates as disclosed in us patent application 20050198894.

Another class of additives includes oil-soluble titanium compounds, as disclosed in US 7,727,943 and US 2006/0014651. The oil-soluble titanium compound may be used as an antiwear agent, friction modifier, antioxidant, deposit control additive, or more than one of these functions. The oil-soluble titanium compound may be a titanium (IV) alkoxide. The titanium alkoxide is formed from a monohydric alcohol, a polyhydric alcohol, or a mixture thereof. The monoalkoxides may have from 2 to 16 carbon atoms or from 3 to 10 carbon atoms. The titanium alkoxide may be titanium (IV) isopropoxide. The titanium alkoxide may be titanium (IV) 2-ethylhexanoate. The titanium compound may include an alkoxide of an o-1, 2-diol or polyol. The 1, 2-o-diol may comprise a fatty acid monoester of glycerol, such as in the case where the fatty acid is oleic acid. The oil-soluble titanium compound may be titanium carboxylate. The titanium (IV) carboxylate may be titanium neodecanoate.

In certain embodiments, the lubricating composition may further comprise at least one phosphorus-containing antiwear agent as a further additive. The phosphorus-containing antiwear agent may be zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salt or mixtures thereof. Examples of zinc dithiophosphates include zinc isopropyl methylpentyl dithiophosphate, zinc isopropyl isooctyl dithiophosphate, zinc bis (cyclohexyl) dithiophosphate, zinc isobutyl 2-ethylhexyl dithiophosphate, zinc isopropyl 2-ethylhexyl dithiophosphate, zinc isobutyl isopentyl dithiophosphate, zinc isopropyl n-butyl dithiophosphate, and combinations thereof. The zinc dialkyldithiophosphate can be present in the lubricating composition in an amount that provides from 0.01 weight percent to 0.1 weight percent phosphorus to the lubricating composition, or from 0.015 weight percent to 0.075 weight percent phosphorus to the lubricating composition, or from 0.02 weight percent to 0.05 weight percent phosphorus. In certain embodiments, the lubricating composition is free or substantially free of zinc dialkyldithiophosphate. The antiwear agent may be present in the lubricating composition in an amount of from 0 wt.% to 3 wt.%, or from 0.1 wt.% to 1.5 wt.%, or from 0.5 wt.% to 0.9 wt.%, based on the total weight of the lubricating composition.

In certain embodiments, the lubricating composition may further comprise at least one ashless antiwear agent (e.g., present in an amount of 0.01 wt.% to 5 wt.% or 0.1 wt.% to 2 wt.% based on the total weight of the lubricating composition), such as an ashless antiwear agent represented by the formula:

Wherein the method comprises the steps of

Y and Y 'are independently-O-, - > NH, - > NR ³, or an imide group formed by bringing together Y and Y' groups and forming a R ¹ -N < group between two > C=O groups;

X is independently -Z-O-Z'-、>CH₂、>CHR⁴、>CR⁴R⁵、>C(OH)(CO₂R²)、>C(CO₂R²)₂ or > CHOR ⁶;

z and Z' are independently > CH ₂、>CHR⁴、>CR⁴R⁵、>C(OH)(CO₂R²) or > CHOR ⁶;

n is 0 to 10, provided that when n=1, X is not > CH ₂, and when n=2, two X are not > CH ₂;

m is 0 or 1;

r ¹ is independently hydrogen or a hydrocarbyl group typically containing 1 to 150 carbon atoms, provided that when R ¹ is hydrogen, m is 0 and n is greater than or equal to 1;

r ² is a hydrocarbyl group typically containing 1 to 150 carbon atoms;

R ³、R⁴ and R ⁵ are independently a hydrocarbon radical, and

R ⁶ is hydrogen or a hydrocarbyl group typically containing 1 to 150 carbon atoms.

In certain embodiments, the ashless antiwear agent may be a compound obtained/obtainable by a process comprising reacting glycolic acid, 2-haloacetic acid or lactic acid or an alkali metal salt or alkali metal salt thereof (such as glycolic acid or 2-haloacetic acid) with at least one member selected from the group consisting of amines, alcohols and amino alcohols. For example, the compound may be represented by at least one of the following formulas:

Wherein the method comprises the steps of

Y is independently oxygen or > NH or > NR ¹;

R ¹ is independently a hydrocarbyl group typically containing from 4 to 30 or from 6 to 20 or from 8 to 18 carbon atoms;

z is hydrogen or methyl;

q is the residue of a diol, triol or higher polyol, diamine, triamine or higher polyamine, or amino alcohol (e.g., Q is a diol, diamine or amino alcohol)

G is 2 to 6, or 2 to 3, or 2;

q is 1 to 4, or 1 to 3, or 1 to 2;

n is 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3, and

Ak ¹ is an alkylene group having 1 to 5, or 2 to 4 or 2 to 3 carbon atoms (such as ethylene), and

B is 1 to 10, or 2 to 8, or 4 to 6, or 4.

Exemplary Industrial applications

The compositions described herein may be used as/for liquid fuel compositions, for oils of lubricating viscosity (e.g., lubricating compositions), and/or as lubricating compositions, such as in internal combustion engines. The internal combustion engine may be a gasoline or diesel engine. Exemplary internal combustion engines include, but are not limited to, spark-ignition and compression-ignition engines, 2-stroke or 4-stroke cycles, liquid fuel supplied via direct injection, indirect injection, port injection, and carburetors, homogeneous charge compression-ignition engines, common rail and unit injector systems, light duty (e.g., passenger car) and heavy duty (e.g., commercial truck) engines, and engines fueled with hydrocarbon and non-hydrocarbon fuel check mixtures thereof. The engine may be part of an integrated exhaust system incorporating the elements of an EGR system, aftertreatment including three-way catalysts, oxidation catalysts, NO _x absorbers and catalysts, catalytic and non-catalytic particulate traps, optionally using fuel borne catalysts, variable valve timing, and injection timing and rate shaping.

In certain embodiments, the subject matter disclosed herein may be used with a diesel engine having a direct fuel injection system in which fuel is injected directly into the combustion chamber of the engine. The firing pressure may be greater than 1000 bar and in one embodiment, the firing pressure may be greater than 1350 bar. Thus, the direct fuel injection system may be a high pressure direct fuel injection system having an ignition pressure greater than 1350 bar. Exemplary types of high pressure direct fuel injection systems include, but are not limited to, unit direct injection (or "pump and nozzle") systems and common rail systems. In unit direct injection systems, a high pressure fuel pump, a fuel metering system, and a fuel injector are combined into one device. The common rail system has a series of injectors connected to the same accumulator or rail. The rail is in turn connected to a high pressure fuel pump. The unit direct injection or common rail system may also include an optional turbocharged or supercharged direct injection system.

In certain embodiments, the subject matter disclosed herein may be used to provide at least comparable, if not improved, stain removal (deposit reduction and/or prevention) performance in conventional and modern diesel engines as compared to conventional additives. Furthermore, the technique may provide similar or improved dewatering (or demulsification) performance as compared to conventional compounds in conventional and modern diesel engines.

In another embodiment, a lubricating composition comprising a reaction product comprising a quaternary ammonium salt may be used to lubricate an internal combustion engine (e.g., for crankcase lubrication).

Embodiments of the present technology may provide at least one of antiwear performance, friction modulation (particularly for improving fuel economy), detergent performance (particularly deposit control or varnish control), or dispersancy (particularly soot control, sludge control, or corrosion control).

Examples

The subject matter disclosed herein may be better understood with reference to the following examples, which are merely intended to further illustrate the subject matter disclosed herein. The exemplary embodiments should not be construed as limiting the subject matter in any way.

Preparation of Material A

Polyisobutylene succinic anhydride (1113.6 g:1.74 mol) prepared by reacting 550M _n high vinylidene polyisobutylene with maleic anhydride using the radical functionalization process described herein (which produces a radical functionalized PIBSA product) was heated to 70 ℃ and charged to a 2L round bottom flange flask equipped with a stirrer, condenser with Dean-Stark trap, nitrogen inlet, split addition line (subline addition pipe), and thermocouple/temperature control system. N, N-dimethylaminopropylamine (179.3 g:1.74 mol) was then charged via the split addition line over 90 minutes, maintaining the batch temperature below 120 ℃. The batch was then heated to 150 ℃ and maintained at that temperature for 3 hours, and about 30mL of water was collected. The resulting product comprising the non-quaternized free-radically functionalized succinimide detergent is cooled and collected.

Preparation of Material B

Polyisobutylene succinic anhydride (1899.7 g:1.72 mol) prepared by reacting 1000M _n high vinylidene polyisobutylene with maleic anhydride using the radical functionalization process described herein (which produces a radical functionalized PIBSA product) was heated to 70 ℃ and charged to a 3L round bottom flange flask equipped with a stirrer, condenser with Dean-Stark trap, nitrogen inlet, split addition line, and thermocouple/temperature control system. N, N-dimethylaminopropylamine (176.0 g:1.72 mol) was then charged via the split addition line over 60 minutes, maintaining the batch temperature below 120 ℃. The batch was then heated to 150 ℃ and maintained at that temperature for 3 hours, and about 30mL of water was collected. The resulting product comprising the non-quaternized free-radically functionalized succinimide detergent is cooled and collected.

Preparation of Material C

Polyisobutylene succinic anhydride (700.3 g:1.10 mol) prepared by reacting 550M _n high vinylidene polyisobutylene with maleic anhydride using a conventional "ene" reaction was heated to 70 ℃ and charged to a 2L round bottom flask equipped with a stirrer, condenser with Dean-Stark trap, nitrogen inlet, split addition line, and thermocouple/temperature control system. N, N-dimethylaminopropylamine (112.3 g:1.10 mol) was then charged via the split addition line over 90 minutes, maintaining the batch temperature below 120 ℃. The batch was then heated to 150 ℃ and maintained at that temperature for 3 hours, and about 30mL of water was collected. The resulting product comprising the non-quaternized succinimide detergent is cooled and collected.

Preparation of Material D

Polyisobutylene succinic anhydride (2000 g:1.81 mol) prepared by reacting 1000M _n high vinylidene polyisobutylene with maleic anhydride using a conventional "ene" reaction was heated to 70 ℃ and charged to a 3 liter round bottom flask equipped with a stirrer, condenser with Dean-Stark trap, nitrogen inlet, split addition line, and thermocouple/temperature control system. N-N-dimethylaminopropylamine (185.2 g:1.81 mol) was then charged via the split addition line over 60 minutes, maintaining the batch temperature below 120 ℃. The batch was then heated to 150 ℃ and maintained at that temperature for 3 hours, and about 30mL of water was collected. The resulting product comprising the non-quaternized succinimide detergent is cooled and collected.

Example 1

Preparation material A (848.8 g:1.13 mol) was charged into a2L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (255.6 g:1.96 mol), acetic acid (68.1 g:1.13 mol) and water (26.6 g:1.46 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (139.7 g:2.41 mol) was then added to the subsurface via a PTFE-head peristaltic pump over a period of about 2 hours. The batch was held at 70 ℃ for 4 hours. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the free radical functionalized quaternized succinimide detergent with acetate counter ion is cooled and collected.

Example 2

Preparation material A (321.2 g:0.44 mol) was charged into a 1L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (116.4 g:0.90 mol), tall oil fatty acid (TOFA, 113.8g:0.44 mol) and water (8.7 g:0.48 mol) were added to the flask and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (54.1 g:0.93 mol) was then added to the subsurface via a PTFE-head peristaltic pump over a period of about 60 minutes. The batch was held at 70 ℃ for 4 hours. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the radical functionalized quaternized succinimide detergent with TOFA counterion is cooled and collected.

Example 3

Preparation material B (399.5 g:0.34 mol) was charged to a 1L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (153.6 g:1.18 mol), acetic acid (21.0 g:0.35 mol) and water (4.0 g:0.22 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (36.4 g:0.63 mol) was then added to the subsurface via a syringe pump over a period of about 2 hours. The batch was held at 70 ℃ for 4 hours. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the free radical functionalized quaternized succinimide detergent with acetate counter ion is cooled and collected.

Example 4

Preparation material C (952.6 g:1.32 mol) was charged into a 2L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (305.9 g:2.35 mol), acetic acid (83.8 g:1.39 mol) and water (28.7 g:1.58 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (154 g:2.65 mol) was then added to the subsurface via a PTFE-head peristaltic pump over a period of about 2 hours. The batch was held at 70 ℃ for 90 minutes. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the quaternized succinimide detergent with acetate counter ion is cooled and collected.

Example 5

Preparation material C (337.1 g:0.45 mol) was charged into a 1L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (122.8 g: mol), TOFA (112 g:0.45 mol) and water (10.1 g:0.56 mol) were added to the flask and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (56.8 g:0.98 mol) was then added to the subsurface via a PTFE-head peristaltic pump over a period of about 60 minutes. The batch was held at 70 ℃ for 4 hours. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the quaternized succinimide detergent with TOFA counterions is cooled and collected.

Example 6

Preparation material D (726.2 g:0.70 mol) was charged into a 2L round bottom flange flask equipped with a stirrer, condenser with dry ice/acetone trap, nitrogen inlet and thermocouple/temperature control system. 2-ethylhexanol (306.3 g:2.35 mol), acetic acid (42.6 g:0.71 mol) and water (12.8 g:0.71 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70 ℃. Propylene oxide (89.7 g:1.54 mol) was then added to the subsurface via a PTFE-head peristaltic pump over a period of about 2 hours. The batch was held at 70 ℃ for 90 minutes. The heating was then turned off and the batch was blown via subsurface dip tube (dip-leg) for 60 minutes to remove residual propylene oxide. The resulting product comprising the quaternized succinimide detergent with acetate counter ion is cooled and collected.

Solubility test

The solubility of the examples in the fuel can be tested using a test method where 0.1 wt% of the example compound can be added to a reference fuel RF79-07 (referred to as RF 79) and mixed lightly. The solution may then be further diluted with reference fuel RF-79 to prepare a 15ppm (by weight) solution. If the sample shows precipitation, the tested example compounds may not be suitable for use in fuels.

Demulsification test

A demulsification test (ASTM D1094-07, "standard test method for water reaction for aviation fuels") was performed to measure the ability of the examples to demulsify fuel and water mixtures. The example compounds were added to room temperature fuels at various weight ppm based on the total weight of the fuel.

The fuel containing the compound of the example (80 mL, rf79) was then added to a clean 100mL graduated cylinder. Phosphate buffer solution (20 mL) at pH 7.0 was then added to the cylinder and the cylinder was stoppered. The cylinder was shaken for 2 minutes at 2 to 3 strokes per second and placed on a flat surface. The volume of the aqueous layer or water recovery is then measured at several time points, such as at intervals of 3 minutes, 5 minutes, 7 minutes, 10 minutes, 15 minutes and 30 minutes. The results are reported as the average of 2 measurements.

Examples 1 to 6 were tested according to the demulsification test at the amounts (weight ppm) shown in table 1, with the amounts of water recovered at each time interval reported in mL, as shown in table 1.

TABLE 1

Embodiments based on free radical functionalized PIBSA products typically break water/fuel mixtures faster than embodiments based on conventionally prepared PIBSA.

Packaging test

A series of 4 packages was prepared as shown in table 2, the amounts of which are shown as parts of each additive added to the packages.

TABLE 2

Component (A)	Packaging 1	Package 2	Packaging 3	Packaging 4
					Example 4	27.26	-----	-----	-----
Example 1	-----	27.26	-----	-----
					Example 5	-----	-----	27.26	-----
Example 2	-----	-----	-----	27.26
					Demulsifier	1.60	1.60	1.60	1.60
Solvent(s)	71.14	71.14	71.14	71.14

Each of packages 1 to 4 was added to RF79 at a treatment rate (reported in ppm by weight) to deliver quaternary ammonium salt levels ("quaternary ammonium levels", reported in ppm by weight) in each fuel as shown in table 3.

TABLE 3 Table 3

The fuels of examples a to L were tested according to the demulsification test, with the amounts of water recovered at each time interval reported in mL, as shown in table 4.

TABLE 4 Table 4

All numerical quantities in this specification specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., are to be understood as modified by the word "about" unless explicitly indicated in the examples or otherwise explicitly indicated or required by the context. As used herein, the term "about" means that a given amount of value is within ±20% of a specified value. In other embodiments, the value is within ±15% of the specified value. In other embodiments, the value is within ±10% of the specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value. In other embodiments, the values are within the explicitly described ranges of values that would be understood by one of ordinary skill in the art based on the disclosure provided herein, implemented in a composition that is substantially similar to the literal amounts that comprise the text described herein.

It should be understood that the upper and lower limits of the amounts, ranges, and ratios described herein may be independently combined, and any amount within the disclosed ranges is considered to provide a narrower range of minimum or maximum values in alternative embodiments (provided, of course, that the minimum amount of range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein can be used with ranges or amounts for any other element.

While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject matter. In this regard, the scope of the invention is limited only by the following claims.

Claims

1. A method for preparing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt.

2. The method of claim 1, wherein the nitrogen-containing compound has: (a) a nitrogen atom capable of reacting with the free radical functionalized PIBSA product to form an imide; and

(b) at least one quaternizable amino group.

3. A process according to claim 1 or claim 2, wherein the quaternizing agent is suitable for converting the quaternizable amino groups into quaternary nitrogen groups.

4. The method of any one of claims 1 to 3, wherein the quaternizing agent comprises at least one of an alkyl sulfonate, a dialkyl sulfate, an alkyl halide, a sultone, an alkyl phosphate, a borate, an alkyl nitrite, an alkyl nitrate, a dialkyl carbonate, an alkyl alkanoate, a hydrocarbyl-substituted carbonate, or a hydrocarbyl epoxide.

5. The method of any one of claims 1 to 4, wherein the quaternizing agent comprises a hydrocarbyl epoxide in combination with an acid.

6. The method of any one of claims 1 to 5, wherein the free radical functionalized PIBSA product is the product of a process comprising the steps of:

reacting polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150° C. to 225° C. to produce the product;

wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and

wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

7. The process of claim 6 wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the process.

8. The method of claim 6, combining the ethylenically unsaturated acylating agent with the free radical initiator for addition to the polyisobutylene after bringing the polyisobutylene to the reaction temperature.

9. The method of any one of claims 6 to 8, wherein the free radical functionalized PIBSA product comprises less than 15 wt% of material comprising two or more polyisobutylene units linked by one or more acylating agent units.

10. The process according to any one of claims 6 to 9, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

11. The method of any one of claims 6 to 10, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

12. The method according to claim 11, wherein the organic peroxide initiator comprises diglutaryl, dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di(tert-butyl) peroxide, tert-butyl hydroperoxide, 3,4-dimethyl-3,4-diphenyl-hexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-3,5,5-trimethyl-hexanoate, di(2,4-dichlorobenzoyl) peroxide, di(2-methylbenzoyl) peroxide, or di(4-tert-butylcyclohexyl) peroxydicarbonate.

13. The method of any one of claims 6 to 12, wherein the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride or methylenemalonic anhydride.

14. The method according to any one of claims 6 to 13, wherein the free radical functionalized PIBSA product comprises at least one compound of the following general formula I:

in:

Each R ¹ independently represents: -(CH ₂ )-(C(CH ₂ ))-(CH ₃ ); H; or absent; wherein when R ¹ is absent, the dashed double bond represents a double bond, and when R ¹ is present, the dashed double bond represents a single bond;

Each m is independently an integer from 1 to 52; and

Each n is independently 0, 1 or 2.

15. The process according to any one of claims 6 to 14, wherein the free radical functionalized PIBSA product comprises at least 30 mol% of the at least one compound of formula I.

16. The method of any one of claims 6 to 15, wherein the free radical functionalized PIBSA product comprises less than 40 wt% unreacted polyisobutylene.

17. A composition comprising the reaction product of the method of any one of claims 1 to 16.

18. A fuel composition comprising a fuel and the composition according to claim 17.

19. A lubricating composition comprising an oil of lubricating viscosity and the composition of claim 17.

20. A method of improving the dehydration properties of a fuel composition, the method comprising incorporating the composition of claim 17 into the fuel composition.

21. A method of reducing and/or preventing injector deposits in an engine, the method comprising supplying a fuel composition according to claim 18 to a fuel injector of the engine and operating the engine.

22. A method of lubricating a crankcase of an engine, the method comprising supplying the lubricating composition of claim 19 to the engine and operating the engine.