WO2024170332A1

WO2024170332A1 - Thermal resistant polyhydantoin composition

Info

Publication number: WO2024170332A1
Application number: PCT/EP2024/052834
Authority: WO
Inventors: Li Chao ZHU; Jia Yue HUANG; Liang Zhao; Feng Chao HU; Hai Sheng Wu; Dong Liang
Original assignee: BASF China Co Ltd; BASF SE
Current assignee: BASF China Co Ltd; BASF SE
Priority date: 2023-02-15
Filing date: 2024-02-06
Publication date: 2024-08-22
Anticipated expiration: 2025-08-15
Also published as: CN120712305A

Abstract

Provided is a polyhydantoin composition comprising a reaction product of at least one unsaturated carboxyl-terminated polymer containing a plurality of carboxyl groups and at least one polycarbodiimide containing a plurality of carbodiimide groups. Also provided are an article produced from the polyhydantoin composition, and its use.

Description

Thermal resistant polyhydantoin composition

Technical Field

The present disclosure relates to a thermal resistant polyhydantoin composition, an article produced from the same, and the use of the article.

Background

Polymeric materials usually are prone to thermal, UV, or chemical attacks. Thermal resistant polymer articles such as coating, molding, and seals are widely used in various applications. To enhance thermal resistance, additives including heat stabilizers are often incorporated into the polymeric matrix.

Quite several kinds of heat stabilizers have been developed. They may suffer from one or more disadvantages such as poor stability, high costs, or hazards to the environment.

Intrinsically thermal resistant polymer compositions with good mechanical strength are desired.

Summary

An objective of the present disclosure is to overcome the problems of the prior art discussed above and to provide a polymer composition that is resistant to thermal aging and mechanically strong.

Surprisingly, it has been found by the inventors that the above object can be achieved by a polyhydantoin composition comprising a reaction product of at least one unsaturated carboxyl- terminated polymer containing a plurality of carboxyl groups and at least one polycarbodiimide containing a plurality of carbodiimide groups.

According to another aspect of the present disclosure, provided is an article produced from the polyhydantoin composition.

A further aspect of the present disclosure provides a use of the article.

It has been surprisingly found that, the polyhydantoin composition according to the present disclosure shows good thermal resistance, and, at the same time, good mechanical property.

Detailed description

Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which the present disclosure belongs. As used herein, the following terms have the meanings ascribed to them below, unless specified otherwise.

As used herein, the articles "a" and "an" refer to one or to more than one (i.e. , to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element. Unless otherwise identified, all percentages (%) are “percent by weight".

Hydantoin refers to a heterocyclic structure as:

Formular (1)

Ri and R2 are independently a hydrocarbon group.

Polyhydantoin refers to a macromolecule containing one or more hydantoin ring structure in its repeating unit.

An unsaturated di- or polycarboxylic acid in the present disclosure refers to a dicarboxylic acid containing one or more unsaturated C — C bonds.

An a,p-unsaturated carboxyl group refers to a carboxyl group ( — C(=O)OH) next to an unsaturated C — C bond. An a,p-unsaturated dicarboxylic acid in the present disclosure refers to a dicarboxylic acid containing two carboxyl groups which have at least one a,p-unsaturated carboxyl group. Examples include without limitation to maleic acid, fumaric acid, and glutaconic acid.

A carbodiimide group is a functional group with the formula — N=C=N — .

A polycarbodiimide refers to a macromolecule containing a repeating unit of — N=C=N — R — , wherein R is a bivalent organic group and R is connected to the nitrogen atom by a carbon atom. For example, R may be a phenylene group ( — C6H4 — ) or a methylene group ( — CH2 — ).

Content of carbodiimide group in a polycarbodiimide refers to the weight percentage of the moiety N=C=N, based on the total weight of the polycarbodiimide.

As used herein, the term “polymer” refers to a molecule having at least one repeating unit and can include copolymers.

The term “copolymer” as used herein refers to a polymer that includes at least two different kinds of repeating units. A copolymer can include any suitable number of repeating units.

Unless otherwise identified, the temperature refers to room temperature and the pressure refers to ambient pressure.

Polycarbodiimide

Polycarbodiimide has more than one carbodiimide groups. Polycarbodiimides according to the present disclosure react with the unsaturated oligomeric or polymeric acid and form a polyhydantoin composition. The carbodiimide group in the polycarbodiimide may react with carboxyl groups and form hydantoin ring structure. Preferably the unsaturated carboxyl- terminated polymer has at least two terminal carboxyl groups. The polycarbodiimide may be an aliphatic, cycloaliphatic, araliphatic, or aromatic polycarbodiimide. Alternatively, the polycarbodiimide may be a mixed polycarbodiimide containing repeating units of two or more different aliphatic, cycloaliphatic, araliphatic, or aromatic carbodiimide moieties.

Polycarbodiimide may be prepared according to processes known to skilled person in the art. In preparation of polycarbodiimides, a catalyst is employed preferably with an inert organic solvent and combinations of mono- and diisocyanates as desired to control the product polycarbodiimide molecular weight and functionality. The combination of two isocyanate moieties yields a carbodiimide group with evolution of carbon dioxide. Usually, this polymerization reaction is performed in the presence of a carbodiimidization catalyst. As carbodiimidization catalyst, an organophosphorus compound can be employed. Such organophosphorus carbodiimidization catalysts are highly active so that the reaction may proceed fast and under mild conditions.

The polycarbodiimide may be derived from a diisocyanate or polyisocyanate. The diisocyanate or polyisocyanate may be an adduct or a derivative of a small molecule isocyanate such as toluene diisocyanate and an active-hydrogen compound such as trimethylolpropane, etc. Preferably, the polycarbodiimide is derived from an aliphatic diisocyanate, a cycloaliphatic diisocyanate, an araliphatic diisocyanate, an aromatic diisocyanate, an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, or any mixture thereof. More preferably, the polycarbodiimide may be derived from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanates, 1 ,4-diisocyanatocyclohexane, trimethylhexane diisocyanate, 2,2-bis(4-isocyanatocyclohexyl)-propane, isophorone diisocyanates, 4,4’- dicyclohexylmethane diisocyanate, 1 ,3-bis(2-isocyanato-2-propyl)benzene, methylene diphenyl diisocyanate, toluene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, or any mixture thereof. A carbodiimidization process may use the above-mentioned diisocyanates/polyisocyanates as the raw material and produce polycarbodiimide. That being said, here the polycarbodiimide being derived from a certain diisocyanate or polyisocyanate does not mean the polycarbodiimide is necessarily obtained from condensation of said diisocyanate or polyisocyanate. It should be construed that the derived polycarbodiimide has the same hydrocarbon radical as said diisocyanate or polyisocyanate does. For instance, poly(phenylcarbodiimide) is derived from phenyl diisocyanate, but may be prepared via approaches other than condensation of the phenyl diisocyanate.

Preferably, the polycarbodiimide has a content of the carbodiimide groups in the range of 1 .0 wt.% to 20.0 wt.%, more preferably 2.0 wt.% to 10 wt.%, still more preferably 3.0 wt.% to 8.0 wt.%.

Unsaturated carboxyl -terminated polymer

Unsaturated carboxyl-terminated polymer as defined herein is an unsaturated polymer or oligomer that has one or more terminal carboxyl groups in its backbone. The carboxyl groups may react with the carbodiimide groups within the polycarbodiimide and form hydantoin ring structure. Preferably the unsaturated carboxyl-terminated polymer has at least two terminal carboxyl groups.

Preferably, the unsaturated carboxyl-terminated polymer is an a,p-unsaturated carboxyl- terminated polymer. Here, the term “a,p-unsaturated carboxyl-terminated polymer” is a polymer or an oligomer terminated by one or more a,p-unsaturated carboxyl groups.

Preferably, the unsaturated carboxyl-terminated polymer may be an unsaturated carboxyl- terminated polyether, an unsaturated carboxyl-terminated polyester, an unsaturated carboxyl- terminated polycarbonate, an unsaturated carboxyl-terminated polybutadiene, an unsaturated carboxyl-terminated polyurethane, an unsaturated carboxyl-terminated polyurea, an unsaturated carboxyl-terminated polyamide, an unsaturated carboxyl-terminated polyethyleneimine, or any mixture thereof.

In various embodiments, the unsaturated carboxyl-terminated polymer is a reaction product of: at least one selected from an unsaturated dicarboxylic acid, an anhydride, and an acyl halide thereof; and at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, a hydroxyl-terminated polyolefin, a hydroxyl-terminated polyurethane, an amino-terminated polyurea, an amino-terminated polyamide, a polyetheramine, a polyethyleneimine.

The reaction may be carried out by mixing and heating the raw materials optionally in the presence of a catalyst.

Alternatively, the unsaturated carboxyl-terminated polymer is a partial hydrolysis product of an unsaturated polyester. The unsaturated polyester, such as, polyethylene maleate or copolymer based on the same, when undergoing partial hydrolysis, may expose two carboxyl groups in both ends.

The unsaturated carboxyl-terminated polymer preferably has a weight average molecular weight of 250 to 10,000 g/mol, preferably 2,000 to 8,000 g/mol.

Unsaturated dicarboxylic acid

Preferably, the unsaturated dicarboxylic acid is an a,p-unsaturated dicarboxylic acid, preferably one selected from maleic acid, fumaric acid, glutaconic acid, citraconic acid, itaconic acid, mesaconic acid, ethylidenesuccinic acid, and any combination thereof.

When preparing the unsaturated carboxyl-terminated polymer, the unsaturated dicarboxylic acid, its anhydride, or its acyl halide may be used individually or in combination, as long as no side reaction occurs.

Polyether polyol, polyester polyol, and polycarbonate polyol

The polyether polyol preferably has a functionality of 2 to 3. The polyether polyol preferably has one or more repeating units selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetramethylene oxide. Preferably, the polyether polyol is a poly(tetramethylene ether) glycol, more preferably a poly(tetramethylene ether) glycol having a weight average molecular weight of 500 to 10,000 g/mol, still more preferably a poly(tetramethylene ether) glycol having a weight average molecular weight of 600 to 7,000 g/mol.

Polyether polyols, which can be obtained by known methods, may also be used as the polyhydroxy compounds. For example, polyether polyols can be produced by anionic polymerization with alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one initiator molecule containing 2 to 8, preferably 3 to 8, reactive hydrogens or by cationic polymerization with Lewis acids such as antimony pentachloride, boron trifluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides with 2 to 4 carbons in the alkylene radical.

Suitable cyclic ethers and alkylene oxides include, for example, tetrahydrofuran, ethylene oxide, 1 ,2-propylene oxide, 1 ,3-propylene oxide, 1 ,2- and 2,3-butylene oxide, styrene oxide, and preferably ethylene oxide and 1 ,2-propylene oxide. The alkylene cyclic ethers and oxides may be used individually, in alternation, one after the other or as a mixture. Examples of suitable initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N-, and N,N'-dialkyl substituted diamines with 1 to 4 carbons in the alkyl radical, such as optionally mono- and dialkylsubstituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1 ,3-propylenediamine, 1 ,3- and 1 ,4-butylenediamine, 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, and 1 ,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'-, and 2,2'- diaminodiphenylmethane.

Suitable initiator molecules also include alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl ethanolamine, N-methyl- and N-ethyl diethanolamine and triethanolamine plus ammonia.

Multivalent alcohols, especially divalent and/or trivalent alcohols are preferred such as ethanediol, 1 ,2-propanediol and 1 ,3-propanediol, diethylene glycol, dipropylene glycol, 1 ,4- butanediol, 1 ,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose.

Also suitable as polyether polyols are melamine polyether polyol dispersions according to U.S. Pat. No. 4,293,657; polymer polyether polyol dispersions prepared from polyepoxides and epoxide resin hardeners in the presence of polyether polyols according to U.S. Pat. No. 4,305,861 ; dispersions of aromatic polyesters in polyhydroxy compounds according to U.S. Pat. No. 4,435,537; dispersion of organic and/or inorganic fillers in polyhydroxy compounds according to U.S. Pat. No. 4,243,755; polyurea polyether polyol dispersions according to DE A 31 2 402, tris- (hydroxyalkyl)isocyanurate polyether polyol dispersions according to U.S. Pat. No. 4,514,526 and crystallite suspensions according to U.S. Pat. No. 4,560,708, whereby the details in the aforesaid patents are to be regarded as part of the patent disclosure, and are herein incorporated by reference.

Like the polyester polyols, the polyether polyols may be used either individually or in the form of mixtures. Furthermore, they can be mixed with the aforesaid polyester polyols.

Polyester polyol preferably has a functionality of 2 to 3. The polyester polyol preferably is a copolymers of ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; and succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2,6-dicarboxylic acid, or a homopolymer or copolymer of lactide, b-valerolactone, caprolactone, or any other lactone with ethylene glycol, propylene glycol, 1 ,4-butanediol, 1 ,6- hexanediol, pentanedithiol, or a mixture thereof as initiator.

Suitable polyester polyols can be produced, for example, from organic dicarboxylic acids with 2 to 12 carbons, preferably aliphatic dicarboxylic acids with 4 to 6 carbons, and multivalent alcohols, preferably diols, with 2 to 12 carbons, preferably 2 to 6 carbons. Examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. The dicarboxylic acids can be used individually or in mixtures. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives may also be used such as dicarboxylic acid mono- or di-esters of alcohols with 1 to 4 carbons, or dicarboxylic acid anhydrides. Dicarboxylic acid mixtures of succinic acid, glutaric acid and adipic acid in quantity ratios of 20-35:35-50:20-32 parts by weight are preferred, especially adipic acid. Examples of divalent and multivalent alcohols, especially diols, include ethanediol, diethylene glycol, 1 ,2- and 1 ,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10- decanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, glycerin, and trimethylolpropane. Glycol, diethylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, or mixtures of at least two of these diols are preferred, especially mixtures of ethanediol, 1 ,4-butanediol, and 1 ,6- hexanediol.

The polyester polyols can be produced by polycondensation of organic polycarboxylic acids, e.g., aromatic or preferably aliphatic polycarboxylic acids and/or derivatives thereof and multivalent alcohols in the presence of catalysts or preferably in the presence of esterification catalysts, preferably in an atmosphere of inert gases, e.g., nitrogen, carbon dioxide, helium, argon, etc., in the melt at temperatures of 150°C to 250°C, preferably 180°C to 220°C, optionally under reduced pressure, up to the desired polymerization degree, which is preferably less than 20, especially less than 15. In a preferred embodiment, the esterification mixture is subjected to polycondensation at the temperatures mentioned above up to an acid value of less than 1 mg KOH/g, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar. Examples of suitable esterification catalysts include iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation may also be per formed in liquid phase in the presence of diluents and/or entraining agents such as benzene, toluene, xylene, or chlorobenzene for azeotropic distillation of the water of condensation.

To produce the polyester polyols, the organic polycarboxylic acids and/or derivatives thereof and multi valent alcohols are preferably polycondensed in a mole ratio of 1 :1-1.8, preferably 1 :1.05-1.2.

Alternatively, the polyester polyol can be produced by polymerization of hydroxycarboxylic acid and/or its lactone in presence of an initiator such as a small molecule diol or triol. Exemplary hydroxycarboxylic acids and their lactones include without limitation to glycolic acid, lactic acid, glycolide, lactide, b-valerolactone, caprolactone, or any other lactone.

Like the polyether polyols, the polyether polyols may be used either individually or in the form of mixtures. Furthermore, they can be mixed with the aforesaid polyether polyols.

Polycarbonate polyol preferably has a functionality of 2 to 3. The polycarbonate polyol can be produced, for example, from reaction of at least a diol with an organic carbonate optionally in the presence of a catalyst.

The diol may include one or more of ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5- pentanediol, 3-methyl-1 ,5-pentanediol, 1 ,6-hexanediol, 2-methyl-1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,2-, 1 ,3-, 1 ,4-cyclohexanediol, 1 ,2-, 1 ,3-, or 1 ,4-cyclohexanedimethanol.

Exemplary organic carbonate may be one or mixture of alkylene carbonates, diaryl carbonates, dialkyl carbonates, dioxolanones, hexanediol bis-chlorocarbonates, phosgene and urea. The alkylene carbonates include ethylene carbonate, trimethylene carbonate, 1 ,2- propylene carbonate, 5-methyl-1 ,3-dioxane-2-one, 1 ,2-butylene carbonate, 1 ,3-butylene carbonate, 1 ,2-pentylene carbonate, and the like. Moreover, dialkyl carbonates include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, and the like and the diaryl carbonates include diphenyl carbonate.

Examples of the catalyst may include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, cobalt, zinc, aluminum, germanium, tin, lead, antimony, arsenic, cerium, and mixture thereof. As the metallic compounds, oxides, hydroxides, salts, alkoxides, organic compounds, and the like may be mentioned. Of these catalysts, it is preferred to use titanium compounds such as titanium tetrabutoxide, titanium tetra-n-propoxide, titanium tetra-isopropoxide, and titanium 2-ethyl hexanoate, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide, and dibutyltin diacetate, lead compounds such as lead acetate and lead stearate. The catalyst may be used in an amount of 1 to 10,000 ppm relative to the total weight of the raw materials.

The polycarbonate polyols may be used either individually or in the form of mixtures. Furthermore, they can be mixed with the aforesaid polyether or polyester polyols.

Hydroxyl-terminated polyolefin

The hydroxyl-terminated polyolefin has a functionality of 2 to 3. Preferably, the hydroxyl-terminated polyolefin is a hydroxyl-terminated polydiene. The hydroxyl-terminated polydiene comprises polymerized diene units. For purposes of the subject disclosure, the term “diene units” is used to describe units within a polymer which were formed from a diene or diolefin, i.e. , a hydrocarbon having two carbon-carbon double bonds. Examples of dienes which can be used to from the polydiene include, but are not limited to, 1 ,2-propadiene, isoprene, and 1 ,3-butadiene.

Preferably, the hydroxyl-terminated polydiene is a hydroxyl-terminated polybutadiene, i.e., is formed from 1 ,3-butadiene and thus comprises butadiene units. 1 ,3-butadiene can polymerize to form 1 ,4-cis units, 1 ,4-trans units, and 1 ,2-vinyl units. The hydroxyl-terminated polybutadiene typically includes, no less than about 5, alternatively no less than about 25, alternatively no less than about 50, alternatively no less than about 55, alternatively no less than about 60, alternatively no less than about 65, percent by weight 1 ,2-vinyl units based the total weight of the hydroxyl- terminated polybutadiene.

The hydroxyl-terminated polydiene typically has a nominal functionality of greater than about 2, alternatively from about 2 to 5, alternatively from about 2 to 3, alternatively about 2. In one embodiment, the hydroxyl-terminated polydiene is hydroxyl-terminated. In another embodiment, the hydroxyl-terminated polydiene is a hydroxyl-terminated polybutadiene, i.e., is a linear polybutadiene having two primary hydroxyl functional groups.

Hydroxyl-terminated polyurethane, an ami no-terminated polyurea

Hydroxyl-terminated polyurethane can be obtained in employing polyols such as those described above, diisocyanates/polyisocyanates and optional catalysts, the proportions of polyol and polyisocyanate being such as to result in hydroxyl-termination in the resulting product. Thus, for example, in the case of a diol and a diisocyanate, a molar excess of the former will be used thereby resulting in hydroxyl-terminated polyurethane.

The hydroxyl-terminated polyurethane prepolymer can also be prepared from a reaction mixture containing one or more chain extenders and/or one or more other polyols. Examples of suitable chain extenders are polyhydric alcohols such as ethylene glycol, propylene glycol, 1 ,3- propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and the like. Additional polyols can be chosen from polyols described above and include polyether polyols, polyester polyols, polycarbonate polyols, hydroxyl- terminated polybutadienes, and the like, all of which possess at least two primary hydroxyl groups.

Suitable organic di- or polyisocyanates used in preparing hydroxyl-terminated polyurethane include any of the known and conventional species.

Amino-terminated polyurea can be obtained in employing diamines and/or polyamines such as those described above, diisocyanates/polyisocyanates and optional catalysts, the proportions of polyol and polyisocyanate being such as to result in amino-termination in the resulting product. Thus, for example, in the case of a diamine and a diisocyanate, a molar excess of the former will be used thereby resulting in amino-terminated polyurea.

Amino-terminated polyamide

Amino-terminated polyamide can be formed by reacting diamines and/or polyamines such as those described above and dicarboxylic acid optionally in the presence of catalysts, the proportions of di- and/or polyamine and carboxylic acid being such as to result in aminotermination in the resulting product. Thus, for example, in the case of a diamine and a dicarboxylic acid, a molar excess of the former will be used thereby resulting in amino-terminated polyamide.

Alternatively, amino-terminated polyamide can be synthesized by ring-opening reaction of a lactam in presence of an initiator diamine. Suitable lactam may include p-propiolactam, y- butyrolactam, b-valerolactam, and e-caprolactam. The initiator diamine may include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexamine, hexaethyleneheptaamine, 1 ,2- or 1 ,3-diaminopropane, 1 ,6- diaminohexane, diamino-terminated polyoxyethylene, diamino-terminated polyoxypropylene, diamino-terminated poly(tetramethylene ether).

Polyetheramine

Polyetheramines are amino-terminated polyethers formed by propylene oxide, ethylene oxide, tetramethylene oxide, other alkylene oxide, or any mixture thereof. Polyetheramines have alkylene oxide as repeating units. Polyetheramines contain primary amino groups (-NH₂) attached to polyether backbones.

Suitable polyetheramine for producing the carboxyl-terminated polymer includes without limitation to diamines or triamines based on polyethylene glycol (PEG), polypropylene glycol (PPG), poly(tetramethylene ether) glycol (PTMEG), or copolymer of at least two of ethylene oxide, propylene oxide, and tetramethylene oxide. They are commercially available from various manufacturers, e.g., as Baxxodur® EC from BASF, Jeffamine® D series polyetheramines, Jeffamine® ED series polyetheramines, Jeffamine® THF series polyetheramines, Jeffamine® T series polyetheramines from Huntsman.

Polyalkyleneimine

Polyalkyleneimine refers to a polymer having a repeating unit composed of an amine group and an alkyl spacer such as CH2CH2, CH2CH2CH2. Polyethyleneimines contain terminal amino groups.

In a preferred embodiment, the polyalkyleneimine is. In a preferred embodiment, the polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyethyleneimine (PEI) or polypropyleneimine. In a more preferred embodiment, the polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyethyleneimine (PEI). In a more preferred embodiment is unsubstituted branched polyethyleneimine.

Known polyalkyleneimine suitable for producing carboxyl-terminated polymer includes without limitation to a substituted or unsubstituted, linear, branched or dendrimeric polyalkyleneimine selected from the group consisting of: polyethyleneimine, polypropyleneimine, polybutyleneimine polypentyleneimine, polyhexyleneimine, polyheptyleneimine, and polyoctyleneimine. Preferred polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyethyleneimine. More preferably, the polyalkyleneimine is a linear polyethyleneimine such as, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, or a branched polyethyleneimines with varying molecular weight. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, and acetic acid.

Other additives

Optionally other additives may be incorporated into the polyhydantoin composition. Examples include an antioxidant, a UV stabilizer, a lubricant, a levelling agent, a defoamer, a dispersant, a wetting agent, a matting agent, a nucleating agent, a plasticizer, a solvent, a flame retardant, a catalyst, a crosslinker, an adhesion promoter, a filler, a dye, a pigment, a hydrolysis preventing agent, a fungistatic agent, and a bacteriostatic agent. The kinds and/or dosage of the additives may be determined according to the specific application where the polyhydantoin composition is used. For example, a coating composition may be prepared by incorporating a solvent and/or a plasticizer into the polyhydantoin composition.

The additives may be added into the polyhydantoin composition after the reaction of the unsaturated carboxyl-terminated polymer and the polycarbodiimide. Alternatively, the additives may be mixed with the unsaturated carboxyl-terminated polymer or the polycarbodiimide before the reaction. For instance, additives including catalyst, filler, plasticizer, and solvent may be mixed with the unsaturated carboxyl-terminated polymer to form a mixture. The mixture then may be blended and react with the polycarbodiimide.

Preparation

Preparation of thermal resistant polyhydantoin composition involves reaction of the unsaturated carboxyl-terminated polymer and the polycarbodiimide optionally in the presence of a catalyst.

When preparing the thermal resistant polyhydantoin composition, the carbodiimide groups in the polycarbodiimide and the carboxyl groups in the unsaturated carboxyl-terminated polymer are preferably in a molar ratio of 0.6 to 2.5, more preferably 0.8 to 1.5. Applications

Various articles may be produced from the polyhydantoin composition according to the present disclosure. Preferably, the article may be a waterproof coating, a protective coating, a paint, a cable sheathing, a hose, or a pipeline.

These articles may find applications in transportation vehicles, home appliances, house or office furniture, constructions, clean room, electrical devices, electronic devices, utilities such as gas, electricity, water, or heat services, etc.

Examples

Measuring and test methods

Tensile strength and elongation at break were measured according to test standard DIN 53504 by using Zwick/Roell testing machine available from Zwick Roell Instrument & Technology Co, Ltd.

The content of carbodiimide groups in polycarbodiimide was tested and calculated using infrared spectroscopy using toluene as solvent and bis(2,6-diisopropylphenyl) carbodiimide as standard.

Solvent: Toluene (analytical grade);

Standard: Bis(2,6-diisopropylphenyl) carbodiimide (CAS no.: 2162-74-5);

IR spectrophotometer: Thermo Nicolet NEXUS 670 FTIR;

Detector: DTGS KBr;

Sampling: Transmission; and

Scanning: 4000-400 cm^-1.

The standard was dissolved in toluene to prepare a series of standard solutions, which were used for obtaining a calibration curve between a peak area of the standard at 2170 cm^-1 and the weight percentage of carbodiimide in the standard. Weight percentage of carbodiimide groups in the analyte was determined according to the calibration curve and the peak area at 2170 cm^-1 of the analyte.

Materials

The materials used in the examples are as follows.

Filler, calcium carbonate.

Plasticizer, di-2-ethylhexyl phthalate.

Solvent, ethyl acetate.

CTP (carboxyl-term inated polymer) 1 (saturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and succinic anhydride, weight average molecular weight -2,200 g/mol, functionality 2. CTP 2 (unsaturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and maleic anhydride, weight average molecular weight -2,200 g/mol, functionality 2.

CTP 3 (saturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and succinic acid, weight average molecular weight -4,300 g/mol, functionality 2.

CTP 4 (unsaturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and maleic anhydride, weight average molecular weight -4,300 g/mol, functionality 2.

CTP 5 (saturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and succinic anhydride, weight average molecular weight -6,500 g/mol, functionality 2.

CTP 6 (unsaturated), based on poly(tetramethylene ether) glycol (number average molecular weight 2,000 g/mol) and maleic anhydride, weight average molecular weight -6,500 g/mol, functionality 2.

Polycarbodiimide 1 , based on aromatic diisocyanate, having a content of carbodiimide of 3.0 to 5.0 %, from BASF SE.

To prepare the thermal resistant polyhydantoin composition, polycarbodiimides, additives, and carboxyl-term inated polymer were mixed with a SpeedMixer at 1 ,500 rpm for 2 minutes in a 5L reactor. The reactor was heated to 75 °C. Formulations of the thermal resistant polyhydantoin compositions in the Examples (Ex.) and Comparative Examples (CEx.) are given in Tables 1 and 2.

The thermal resistant polyhydantoin composition was sprayed to a substrate of cement in a thickness of 1 to 2 mm and coating samples were formed.

Tensile strength and elongation at break of the coating samples before and after aging experiment were measured and the results are summarized in Table 3.

The aging experiments was conducted to test the thermal resistance performance. The coating samples were placed in an incubator. The incubator was heated and kept at 70 °C for 7 days. Table 1

Table 2

Table 3 Properties of coating samples

From Table 3, it is indicated that after aging under 70 °C for 7 days, the coating prepared from polyhydantoin compositions exhibited varying degrees of impact in terms of tensile strength and/or elongation at break. In general, Comparative Examples 6 through 10 all exhibited significant deterioration of tensile strength. Comparative Examples 6, 7, and 10 also deteriorated in terms of elongation at break. The deterioration of mechanical properties indicated a severe damage of thermal aging to the polyhydantoin compositions based on saturated carboxyl- terminated polymer. In contrast to the corresponding Comparative Examples 6 through 10, Examples 6 through 10 had an increase or maintenance of tensile strength and elongation at break, indicating resistance to the thermal aging.

Claims

What is claimed:

1. A polyhydantoin composition comprising a reaction product of: at least one unsaturated carboxyl-terminated polymer containing a plurality of carboxyl groups; and at least one polycarbodiimide containing a plurality of carbodiimide groups.

2. The polyhydantoin composition according to claim 1 , wherein the unsaturated carboxyl- terminated polymer is an a,p-unsaturated carboxyl-terminated polymer.

3. The polyhydantoin composition according to claim 1 , wherein the unsaturated carboxyl- terminated polymer includes an unsaturated carboxyl-terminated polyether, an unsaturated carboxyl-terminated polyester, an unsaturated carboxyl-terminated polycarbonate, an unsaturated carboxyl-terminated polyolefin, an unsaturated carboxyl-terminated polyurethane, an unsaturated carboxyl-terminated polyurea, an unsaturated carboxyl-terminated polyamide, an unsaturated carboxyl-terminated polyethyleneimine, or any mixture thereof.

4. The polyhydantoin composition according to claim 1 , wherein the unsaturated carboxyl- terminated polymer is a product of: at least one selected from an unsaturated dicarboxylic acid, an anhydride, and an acyl halide thereof; and at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, a hydroxyl-terminated polyolefin, a hydroxyl-terminated polyurethane, an amino-terminated polyurea, an amino-terminated polyamide, a polyetheramine, a polyethyleneimine.

5. The polyhydantoin composition according to claim 4, wherein the unsaturated dicarboxylic acid is an a,p-unsaturated dicarboxylic acid, preferably one selected from maleic acid, fumaric acid, glutaconic acid, citraconic acid, itaconic acid, mesaconic acid, ethylidenesuccinic acid, and any combination thereof.

6. The polyhydantoin composition according to claim 4, wherein the polyether polyol is a poly(tetramethylene ether) glycol, preferably a poly(tetramethylene ether) glycol having a weight average molecular weight of 500 to 10,000 g/mol, more preferably a poly(tetramethylene ether) glycol having a weight average molecular weight of 600 to 7,000 g/mol.

7. The polyhydantoin composition according to claim 1 , wherein the unsaturated carboxyl- terminated polymer has a weight average molecular weight of 250 to 10,000 g/mol, preferably 2,000 to 8,000 g/mol.

8. The polyhydantoin composition according to claim 1 , wherein the polycarbodiimide is derived from an aliphatic diisocyanate, a cycloaliphatic diisocyanate, an araliphatic diisocyanate, an aromatic diisocyanate, an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, or any mixture thereof.

9. The polyhydantoin composition according to claim 9, wherein the polycarbodiimide is derived from tetramethylene diisocyanates, pentamethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1 ,4- diisocyanatocyclohexane, trimethylhexane diisocyanate, 2,2-bis(4-isocyanatocyclohexyl)- propane, isophorone diisocyanates, 4,4’-dicyclohexylmethane diisocyanate, 1 ,3-bis(2- isocyanato-2-propyl)benzene, methylene diphenyl diisocyanate, toluene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, or any mixture thereof.

10. The polyhydantoin composition according to claim 1 , wherein the polycarbodiimide has a content of the carbodiimide groups in the range of 1.0 wt.% to 20.0 wt.%, preferably 2.0 wt.% to 10 wt.%, more preferably 3.0 wt.% to 8.0 wt.%.

11. The polyhydantoin composition according to claim 1 , wherein the carbodiimide groups in the polycarbodiimide and the carboxyl groups in the unsaturated carboxyl-terminated polymer are in a molar ratio of 0.6 to 2.5, preferably 0.8 to 1 .5.

12. The polyhydantoin composition according to claim 1 , further comprising one or more additives selected from an antioxidant, a UV stabilizer, a lubricant, a levelling agent, a defoamer, a dispersant, a wetting agent, a matting agent, a nucleating agent, a plasticizer, a solvent, a flame retardant, a catalyst, a crosslinker, an adhesion promoter, a filler, a dye, a pigment, a hydrolysis preventing agent, a fungistatic agent, and a bacteriostatic agent.

13. An article produced from the polyhydantoin composition according to any of claims 1 through 12.

14. The article according to claim 13, wherein the article is a waterproof coating, a protective coating, a paint, an adhesive, a sealant, an elastomer, a cable sheathing, a hose, or a pipeline.

15. Use of the article according to any of claims 12 through 14 in constructions, transportation vehicles, sports items, electronics, semiconductors, utilities, consumer goods, mechanics, industrial manufacture.