HK1196840A - Aliphatic polyester polyols from cyclohexane oxidation byproduct streams as precursors for polyurethane and polyisocyanurate polymers - Google Patents

Description

Aliphatic polyester polyols from cyclohexane oxidation by-product streams as precursors for polyurethane and polyisocyanurate polymers

Cross Reference to Related Applications

The present application claims priority to U.S. provisional application 61/496,268 filed on 13/2011 and 61/496,868 filed on 14/2011, the disclosures of which are incorporated herein by reference in their entireties.

Background

As petroleum-based materials rise in price and environmental pressures increase, there is an increasing demand for the maximum possible rational use of all products from petrochemical processes, including the inevitable by-products formed with the desired primary products. Reaction by-products are often mixtures that may be complex in composition, difficult to use directly, and difficult and/or economical to purify. They are often disposed of as little or no valuable material, such as discarded or used for fuel value combustion.

It is known in the manufacture of adipic acid or caprolactam from cyclohexane that because chemical conversion does not proceed perfectly with 100% yield, a byproduct stream is produced. These byproduct streams contain a variety of molecules having functional groups including one or more alcohol, olefin, carboxylic acid, lactone, ester, and ketone groups, and the like, as well as combinations thereof. These byproduct streams are complex mixtures. It is known to use some byproduct streams for their fuel value. In such applications, little or no recognition or recovery of the value of the functional groups present in the byproduct stream is realized. As a result, most of the byproduct stream from adipic acid manufacture remains underutilized.

The manufacture of adipic acid from cyclohexane typically involves two steps. First, cyclohexane is oxidized using air to a mixture of cyclohexanol (a) and cyclohexanone (K), which is referred to as KA. Second, KA was oxidized to adipic acid, a nylon-66 precursor, using nitric acid.

A similar "cyclohexane oxidation" step is also carried out in the manufacture of caprolactam from cyclohexane. In a caprolactam manufacturing process, cyclohexanone is converted to its oxime, which is then subjected to molecular rearrangement to produce caprolactam. The caprolactam can then be polymerized to provide nylon-6.

In known cyclohexane oxidation processes, cyclohexane is typically oxidized with oxygen or an oxygen-containing gas at low conversion to produce an intermediate stream containing cyclohexanol (a), cyclohexanone (K) and cyclohexyl hydroperoxide (CHHP) in cyclohexane. CHHP is an important intermediate in the oxidation of cyclohexane to KA, and various processes are known in the art to optimize the conversion of CHHP to KA to maximize the yield of KA. In addition to K, A and CHHP, cyclohexane oxidation also produces byproducts. In some cases, these byproducts have been found to interfere with subsequent processing of the conversion of CHHP to KA.

It is known that at least some of the interfering byproducts can be removed by contacting the intermediate stream containing K, A and CHHP with water or caustic, such as described in U.S. patent No. 3,365,490, which is incorporated herein by reference in its entirety. This patent describes the air oxidation of cyclohexane followed by conversion to diacids, such as adipic acid, with nitric acid, and the disposal of a by-product waste stream. This contacting or extraction produces a two-phase mixture that, after phase separation, produces a purified cyclohexane stream containing K, A and CHHP, which can be subjected to known high-yield processes to convert CHHP to KA, and a byproduct water stream. The byproduct water stream ("water wash") contains various mono-and di-acids, hydroxy-acids, and other oxidation byproducts formed during the initial oxidation of cyclohexane.

Whether or not water washing is performed as an intermediate step, the stream containing K, A and CHHP is further processed by methods well known in the art to complete the conversion of CHHP to K and A. The resulting mixture is then refined again by methods well known in the art to recover unconverted cyclohexane for recycle and to obtain purified K and a for subsequent oxidation of adipic acid or conversion to caprolactam. In general, byproduct streams, sometimes referred to herein as "byproduct" streams, which may be obtained from cyclohexane oxidation processes, include "water washes" (aqueous streams produced by water extraction of cyclohexane oxide) and "NVR" (high boiling distillation bottoms from KA refining), CAS registry numbers 68411-76-7. The "water wash" produces a stream known as "COP acid" CAS registry No. 68915-38-8 by concentration that removes at least some of the water. See also published US patent application US 2004/0054235, which describes the production of "non-volatile residue", a high boiling distillation bottom product from the distillation recovery of the cyclohexane oxidation products cyclohexanol and cyclohexanone, referred to as "NVR", which has a low chromium content, more suitable for combustion; US 2012/0064252 and US 2012/0101009, incorporated herein by reference, describe NVR, water wash or COP acid treatments by converting free acid functional groups to monomeric esters and oligomeric esters, and converting oligomeric esters to monomeric esters.

It is known that "water washes", "COP acids" and "NVRs" contain both mono-and polyfunctional substances (functional monomers) having mainly functional groups including acids, peroxides, ketones, alcohols and esters. The presence of other functional groups such as aldehydes, lactones and olefins is also known. Multiple functional groups may be combined in a single molecule, such as in a hydroxy acid, for example, hydroxycaproic acid or hydroxyvaleric acid. Typically, the acid functionality is at one end of a linear hydrocarbyl chain, and the hydroxyl groups may be present at various positions along the chain. The mono-and polyfunctional materials contained within these byproduct streams are predominantly aliphatic. Known examples of hydroxy acids include 6-hydroxyhexanoic acid, 5-hydroxyvaleric acid, 3-hydroxyvaleric acid, and 3-hydroxypropionic acid. Similarly, known examples of simple monoacids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and caproic acid. Known examples of diacids include succinic, glutaric, and adipic acids. Known examples of keto acids include 4-oxopentanoic acid (also known as levulinic acid) and 5-oxohexanoic acid. Known examples of alcohols include cyclohexanol, 1-propanol, 1-butanol, 1-pentanol and various diols such as 1, 2-, 1, 3-and 1, 4-cyclohexanediol, various butanediol isomers, and various pentane diol isomers.

SUMMARY

The inventors herein have discovered a new simple and economical process for providing polyols having new and unique compositions from cyclohexane oxidation byproducts. It has further been found that these polyols can be used to prepare new and unique polyurethanes, and that the polyurethanes thus obtained can be used in a wide variety of applications. By using the process of the present invention, it is not necessary to first separate a separate monomer such as adipic acid from the cyclohexane oxidation by-products. Surprisingly, the complex mixture can be used directly in a simple process to provide useful polyols. This finding is of great value as it can eliminate the need for costly and complex purification or separation methods. The present disclosure focuses on the utilization of the byproduct stream from the oxidation of cyclohexane to KA. Notably, the polyol compositions of the present invention can be used as a component of a resin blend, which can be combined with co-reactants, catalysts, and other ingredients to provide a prepolymer composition, which can then undergo polymerization to provide polymeric materials useful as coatings, sealants, cements, and the like, such as coatings for controlled release fertilizer compositions.

The invention can provide aliphatic polyester polyol compositions, methods of making polyol compositions from cyclohexane oxidation byproducts, methods of using aliphatic polyester polyol compositions, such as in the formation of resin blends, prepolymer compositions comprising resin blends incorporating polyol compositions, methods of making and using prepolymer compositions incorporating polyol compositions of the invention, Polyurethane (PU) and Polyisocyanurate (PIR) compositions incorporating polyol-containing prepolymer compositions for flexible applications, polyurethane compositions for semi-rigid applications, polyurethane compositions for rigid applications, foam compositions, methods of making foam compositions, methods of using foam compositions, PIR and/or PIR foams, methods of using PU and/or PIR foams, PU coating compositions, methods of making polyurethane coating compositions, methods, Methods of using the PU coating composition, the PU adhesive composition, methods of preparing the PU adhesive composition, methods of using the PU adhesive composition, the PU binder composition, methods of preparing the PU binder composition, methods of using the PU binder composition, and the like.

For example, the present invention can provide new materials that incorporate the polyurethane and polyisocyanurate compositions of the present invention for use in coatings, adhesives, elastomers, sealants, cements, and the like. More specifically, the present invention may provide coatings for controlled release fertilizer compositions incorporating the polyol compositions prepared by the process of the present invention.

The present invention can provide a polyol composition starting from a by-product stream derived from a cyclohexane oxidation product by applying the process of the present invention, wherein the polyol composition is obtained by starting from one or more of the following: water extract (water wash), concentrated water extract (COP acid), or non-volatile residue (NVR); optionally removing at least a portion of the water and at least a portion of the free and bound monofunctional components by heating, adding a polyol, and removing at least a portion of the water and at least a portion of the free and bound monofunctional components by heating, optionally under vacuum or optionally under bubbling of an inert gas, to form the polyol composition. Thus, the present invention can provide a polyol composition from several sources through the treatment of the byproduct stream of a cyclohexane oxidation process.

For example, the present invention may provide a process for preparing a polyol composition, the process comprising:

mixing the by-products; and one or more polyols; and optionally, a catalyst; optionally under vacuum, or optionally under sparging with an inert gas to remove monofunctional components and water by distillation, the byproduct mixture comprising: i) an aqueous extract of the cyclohexane oxidation reaction product, which is optionally concentrated; or, ii) a non-volatile residue of the cyclohexane oxidation reaction product, which is optionally concentrated, or a mixture thereof.

Monofunctional components include, inter alia, monocarboxylic acids and the like such as formic acid, acetic acid and the like; and the monofunctional component also includes monohydroxy compounds, i.e., monohydric alcohols, such as cyclohexanol.

Further, the method may comprise the steps of: the by-product mixture is heated, optionally under vacuum, or optionally under sparging with an inert gas, to remove the monofunctional components and water before adding the one or more polyhydroxy compounds, after which the resulting mixture is continued to be heated. The polyol may be a diol, or may be a triol, tetraol, or higher polyol such as a saccharide, a sugar alcohol, or the like.

The method may further comprise adding a polycarboxylic acid, or an ester or anhydride thereof, before or during the heating and distillation process; or adding a hydrophobic material; or any combination thereof.

The heating and distillation process may use vacuum, inert gas sparging, superheated water vapor, specialized equipment such as various types of evaporators, or combinations thereof to enhance mass transfer and removal of water and monofunctional components.

The relative amounts of the polyhydroxy compound and other optional components added can be adjusted to provide a polyol product having a beneficially low acid number (as determined by standard ASTM methods incorporated herein by reference, preferably less than 10mg KOH/gm sample, more preferably less than 5mg KOH/gm sample) and a beneficially high OH number (standard in polyol chemistry, determined by ASTM methods incorporated herein by reference) of from about 30 to about 500mg KOH/gm sample or from about 100 to about 500mg KOH/gm sample. If the appropriate acid and OH number are not initially obtained, the product obtained can be reheated in the presence of additional polyol (diol).

For example, the residual content of monofunctional component after the heating step may be less than about 10% by weight of the reaction mixture, or may be less than about 5%, or may be less than 2%. For example, the method can include adding a catalyst to the byproduct mixture followed by heating to remove the monofunctional component; and/or, the method may include heating after the addition of the polyol to remove the monofunctional component, or may include heating before, simultaneously with, and/or after the addition of the polyol. The polyol may be: diols (diols), triols, or higher functionality polyols, including but not limited to ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, or combinations thereof.

Additionally, polyfunctional (i.e., polycarboxy) acids, esters, or anhydrides; and/or the third composition of hydrophobic material may, for example, be added before or simultaneously with heating the mixture to remove the water and monofunctional components. Examples thereof include polyfunctional aromatic acids, anhydrides, and polyfunctional esters thereof, (e.g., glycol monoesters), and polyfunctional aliphatic acids, anhydrides, and polyfunctional esters thereof.

The polycarboxylic acid may be: diacid, triacid, or higher functionality polycarboxylic acids or corresponding esters or anhydrides including, but not limited to, polyfunctional aromatic acids, polyfunctional aromatic anhydrides, and polyfunctional aromatic esters (e.g., glycol monoesters), as well as polyfunctional aliphatic acids, anhydrides, and polyfunctional esters thereof, such as succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, sebacic acid, azelaic acid, dodecanedioic acid, citric acid, succinic anhydride, phthalic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl terephthalate, and combinations thereof.

The hydrophobic material may be a vegetable oil (i.e., a vegetable-derived oil), or a fatty acid or ester derived therefrom; animal oils (i.e., oils of animal origin), or fatty acids or esters derived therefrom; or synthetic oils, synthetic fatty acids, or synthetic fatty acid esters. Oil means a hydrophobic compound regardless of its physical state at room temperature; that is, the oil may be a solid at room temperature, such as a solid fat.

Thus, more specifically, the present invention may provide a process for preparing an aliphatic polyester polyol, the process comprising treating a by-product mixture from an aqueous extract (water wash), or a concentrated aqueous extract (COP acid), or a non-volatile residue (NVR), or a mixture thereof, by: one or more polyols are added and at least a portion of the water is removed from the mixture with the free and bound monofunctional components by heating and distillation such that less than about 10%, or less than 5%, or less than 2% by weight of the total monofunctional components remain in the mixture. Optionally, a third composition, or a hydrophobic material, or both, can be added to the byproduct mixture under heat and distillation; thereby forming an aliphatic polyester polyol.

Thus, the process of the present invention may further comprise adding a polycarboxylic acid, ester or anhydride, followed by heating to remove monofunctional components; and/or the method may comprise adding a hydrophobic material followed by heating to remove the monofunctional component. Thereafter, if the acid number and OH number are not optimized for the intended use, they can be further adjusted by: additional polyol (e.g., glycol) is added and further heated, optionally in the presence of a catalyst, to remove any additional monofunctional components and/or water with distillation.

The present invention may provide a composition prepared by the method as described above. The compositions prepared by the process of the present invention may further comprise one or more other components known to those skilled in the art and depending on the end use. Such components may include other polyols, solvents, catalysts, chain extenders, cross-linking agents, curing agents (curing), surfactants, blowing agents, fillers, flame retardants, plasticizers, light stabilizers, colorants, waxes, biocides, minerals, micronutrients, inhibitors, stabilizers, or other organic or inorganic additives.

The polyol composition of or prepared by the process of the present invention may be used to form a resin blend, suitable as the "B-side" component of a prepolymer composition. The resin blend includes a polyol composition and may further include other polyols, solvents, catalysts, chain extenders, cross-linking agents, curing agents, surfactants, blowing agents, fillers, flame retardants, plasticizers, light stabilizers, colorants, waxes, biocides, minerals, micronutrients, inhibitors, stabilizers, or other organic or inorganic additives.

The resin blend of the present invention may be reacted with a multifunctional isocyanate ("a-side component"), such as methylene diphenyl diisocyanate (MDI) or polymeric MDI (pmdi), to provide the prepolymer composition of the present invention, which after reaction of the a-side and B-side components may provide the polyurethane or polyisocyanurate of the present invention depending on the particular conditions used. Accordingly, the present invention also provides polyurethane or polyisocyanurate polymer compositions, methods of making the polymer compositions, and methods of using the polymer compositions.

Thus, more specifically, the present invention may provide a process for preparing an aliphatic polyester polyol, the process comprising treating a mixture of by-products from an aqueous extract (water wash), or a concentrated aqueous extract (COP acid), or a non-volatile residue (NVR), or a mixture thereof, by: one or more polyols are added and at least a portion of the water is removed from the mixture by heating and distillation along with the free and bound monofunctional components such that less than about 10%, or less than 5%, or less than 2% by weight of the total monofunctional components remain in the mixture. Optionally, a third composition, or a hydrophobic material, or both, can be added to the byproduct mixture with heating and distillation; thereby forming an aliphatic polyester polyol.

Thus, the process of the present invention may further comprise adding a polycarboxylic acid, ester or anhydride, followed by heating to remove monofunctional components; and/or the method may comprise adding a hydrophobic material followed by heating to remove the monofunctional component. Thereafter, if the acid number and OH number are not optimized for the intended use, they can be further adjusted by: additional polyol (e.g., glycol) is added and further heat is applied, optionally in the presence of a catalyst, with distillation to remove any other monofunctional components and/or water until the acid value is sufficiently low and the OH value is sufficiently high.

The present invention may provide Polyurethane (PU) or Polyisocyanurate (PIR) polymers from the polyols of or prepared by the process of the present invention by: the polyol composition is reacted with a multifunctional isocyanate to provide a PU or PIR prepolymer composition which, upon standing under suitable conditions, can be coagulated (set up) to provide a PU or PIR polymer. It is known to use a variety of amines and polyamines as curing agents, crosslinking agents or chain extenders and it will be appreciated that urea linkages may be present in the resulting polymer when primary or secondary amines are used as such. The polymers of the present invention may be used as coatings, for example, controlled release fertilizer coatings; an adhesive; a sealant; or a cement, e.g., a wood cement. The PU or PIR polymers of the present invention or prepared by the process of the present invention may be used in fibre reinforced compositions, such as wood fibre reinforced composites. The PU or PIR polymers of the present invention may further comprise other polyols, solvents, catalysts, chain extenders, cross-linking agents, curing agents, surfactants, blowing agents, fillers, flame retardants, plasticizers, light stabilizers, colorants, waxes, biocides, minerals, micronutrients, inhibitors, stabilizers, or other organic or inorganic additives. For example, the controlled release fertilizer of the present invention may comprise a coating containing biocides, micronutrients, and the like.

For example, the PU or PIR polymers of the present invention may be used as a controlled release fertilizer coating, as taught in published U.S. patent application 2010/0307211 to Xing et Al, U.S. patent application 2010/0275665 to Ogle et Al, U.S. patent application 2010/0233332 to Xing et Al, U.S. patent application 2010/0186470 to Xing et Al, U.S. patent 7,544,736B2 to Kazemizadeh et Al, published U.S. application 2008/010878 a1 to Kazemizadeh, U.S. patent 7,267,707 to Rosenthal et Al, published U.S. patent application 2006/0222735 Al to Rosenthal, U.S. patent 5,435,821 to Duvdevani et Al, U.S. patent 5,538,531 to Hudson et Al, all of which are incorporated by reference in their entirety. The PU or PIR coated granular fertilizer of the present invention may be prepared by coating a granular fertilizer material with a prepolymer composition of the present invention, followed by allowing the prepolymer composition to coagulate to provide a polymeric coating of the fertilizer material. Fertilizers coated with the polymers of the present invention can provide improved, i.e., more extended, or better timed or controlled release fertilizer compositions. Here, the inventors have surprisingly found that by using a third component comprising an aromatic component such as an aromatic polyacid, an activated ester, a multifunctional ester or an anhydride, a coated fertilizer composition with improved extended release properties under field conditions can be obtained.

The present invention may provide a foam composition comprising a prepolymer composition of the present invention or prepared by the process of the present invention and a blowing agent. The foam composition may be a spray foam. For example, the present invention may provide a spray foam extruded fertilizer.

The present invention therefore provides a technical solution to the problem of (how to) increase the value and use of by-product streams obtained from large scale chemical industry operations, such as nylon manufacturing operations comprising a step of oxidation of cyclohexane to cyclohexanol/cyclohexanone product, by devising technically and economically viable uses of the by-product streams. The methods and compositions of the present invention provide for the use of these byproduct streams to be of higher value than merely combusting the streams to utilize their heating values. By using the organic components of these byproduct streams as a source of polyols useful in the synthesis of polymers such as polyurethanes and polyisocyanurates, the present invention solves the technical problem of increased use and economic benefit from chemical treatment operations.

Brief Description of Drawings

Fig. 1 shows a graph of fertilizer release rate under field conditions from five embodiments of controlled release fertilizer compositions having altered proportions of aromatic constituents relative to aliphatic and hydrophobic components, correlated to delay in fertilizer release.

Detailed description of the invention

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, suitable methods and materials are now described.

As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any of the methods described may be performed in the order of events described or in any other order that is logically possible.

Unless otherwise indicated, embodiments of the present disclosure will employ techniques of chemistry, polymer chemistry, foam chemistry, and the like, which are within the skill of the art. This technique is fully described in the literature.

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the methods disclosed and claimed herein can be performed and the compositions and compounds used. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in degrees Celsius, and pressure is in atmospheres. The standard temperature and pressure are defined as 20 ℃ and 1 atm absolute.

As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a vector" includes a plurality of vectors. In this specification and the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless an intent to be obvious to the contrary.

All percent compositions are given as weight percentages unless otherwise mentioned. Unless otherwise noted, when referring to a solution of components, percentages refer to weight percent of the composition including solvent (e.g., water).

Unless otherwise specified, the average molecular weight of all polymers is the weight average molecular weight.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range includes "about 'x' to about 'y'". As an example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. In this embodiment, the term "about" can include traditional rounding according to the numerical significance of the numerical value. In addition, the phrase "about 'x' to 'y'" includes "about 'x' to about 'y'".

The term "hydroxyl number" refers to the total amount of residual hydroxyl groups present in the material. The hydroxyl number, also referred to herein as the hydroxyl number, is given in mg KOH/g (i.e., mg KOH/gram of sample) and is measured according to well known methods such as standard ASTM D1957 or ASTM E1899.

The term "average functionality", or "average hydroxyl functionality", of a polyol refers to the average number of OH groups per molecule. The average functionality of the isocyanate means the average number of-NCO groups per molecule.

The term "acid number" correspondingly refers to the concentration of carboxylic acid groups present in the material and is given in mgKOH/g (i.e. mg KOH/gram sample) and is measured according to well known methods, such as the standard ASTM D4662 or ASTM D1613.

The amount of isocyanate (-NCO) present in the prepolymer composition can be expressed in terms of "isocyanate reaction index," also referred to as "isocyanate index," NCO index, "or simply" index. Herein and as is conventional in the art, an isocyanate reaction index of 100 corresponds to 1.0 isocyanate groups (-NCO) per active hydrogen atom. Additional details regarding the NCO index are described in U.S. patent 6,884,824, which is incorporated herein by reference. Typical isocyanate indices for spray Polyurethane (PU) foams are in the range of about 110 to 120. The isocyanate index is a measure of The degree of excess of isocyanate used relative to The theoretical equivalent required, as described in Huntsman's "The Polyurethanes Book" [ The Polyurethanes Book, David Randall and Steve Lee editions, Wiley (2003), ISBN0-470 and 85041-8 ]. For example, an index of 105 means that a 5% excess of isocyanate is used.

The term "aliphatic group" refers to a saturated or unsaturated straight or branched hydrocarbon group and includes, for example, alkyl, alkenyl, and alkynyl groups.

The term "polyol" or "aliphatic polyol" refers to a polyol prepared from a mixture of aliphatic functional monomers (by-products) from a cyclohexane oxidation process having an average functionality greater than 1. Such polyols can be prepared from aqueous extracts or non-volatile residues as by-product streams from cyclohexane oxidation processes.

The term "alkane" or "alkyl" refers to a straight or branched chain hydrocarbon group that may have 1 to 20 carbon atoms, such as 1 to 12 carbon atoms, for example 1 to 8 carbon atoms; including, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, dodecaneA pentyl group, a 2-ethylhexyl group, etc. Unless otherwise mentioned, alkyl is optionally substituted with one or more groups selected from: aryl (optionally substituted), heterocycle (optionally substituted), carbocycle (optionally substituted), halo, hydroxy, protected hydroxy, alkoxy (e.g., C)₁To C₇) (optionally substituted), poly (oxyalkylene) (e.g., ethoxylated or propoxylated groups), acyl (e.g., C)₁To C₇) Aryloxy (optionally substituted), alkyl ester (optionally substituted), aryl ester (optionally substituted), alkanoyl (optionally substituted), aroyl (optionally substituted), carboxy, protected carboxy, cyano, nitro, amino, substituted amino, (mono substituted) amino, (di substituted) amino, protected amino, amide, lactam, urea, carbamate, sulfonyl and the like.

The terms "aromatic", "aryl", or "aryl" refer to a group containing an aromatic homocyclic (i.e., hydrocarbon) mono-, bi-, or tricyclic ring, e.g., having 6 to 12 members: such as phenyl, naphthyl, and biphenyl. Unless otherwise mentioned, aryl is optionally substituted with one or more groups selected from: alkyl (optionally substituted alkyl), alkenyl (optionally substituted), aryl (optionally substituted), heterocycle (optionally substituted), halo, hydroxy, alkoxy (optionally substituted), poly (oxyalkylene) (e.g., ethoxylated or propoxylated groups), aryloxy (optionally substituted), alkanoyl (optionally substituted), aroyl (optionally substituted), alkyl ester (optionally substituted), aryl ester (optionally substituted), cyano, nitro, amino, substituted amino, amide, lactam, urea, carbamate, sulfonyl, and the like. Optionally, adjacent substituents together with the atoms to which they are attached form a 3 to 7 membered ring.

The term or phrase "monofunctional component" or "monofunctional compound" refers to a compound in free form or bound to another compound via an ester linkage, wherein each monofunctional component or compound contains only a single reactive functional group. For example, methanol is the free monofunctional component, while the methyl ester of the diacid is the bound monofunctional component. The terms should be understood in the context in which they are used. For example, in the context of preparing a polyester polyol, the reactive groups will include carboxylic acids and hydroxyl groups, as these are capable of reacting with complementary functional groups in additional monomeric compounds to form ester linkages. Non-reactive functional groups such as ketones or olefins are not included in the determination of whether a component is monofunctional because such groups do not participate in the formation of the polyester polyol. In other words, a monomeric compound containing one hydroxyl group and one keto group should be considered a monofunctional compound in the context of this document. Similarly, a monomeric compound containing one hydroxyl group will be considered a monofunctional compound in the context of this document.

Monofunctional components or compounds (e.g., mono-acids, mono-alcohols, etc.) can include bound and/or unbound and include: formic acid, acetic acid, cyclohexanol (e.g., the combination can include cyclohexanol bound to adipic acid), propionic acid, butyric acid, valeric acid, hexanoic acid, propanol (e.g., 1-propanol and 2-propanol), butanol (e.g., 1-butanol, 2-butanol, etc.), pentanol (e.g., 1-pentanol, 2-pentanol, etc.), hexanol (e.g., 1-hexanol, 2-hexanol, etc.), and the like. Reference to "removing monofunctional components" monofunctional compounds, such as "removing free and bound monofunctional components" refers to those products that remove (e.g., by heating and distillation) free monofunctional components (e.g., monocarboxylic acids, mono-hydroxy compounds, etc.) from the mentioned mixtures as well as can result from cleavage of bound monofunctional components that occurs under removal conditions (e.g., heating, vacuum, acid catalysis) to produce free monofunctional components during the processing step, which are then removed along with the free monofunctional components by distillation, etc.

As used herein, "multifunctional" or "multifunctional compound" refers to a compound having more than one functional group capable of forming new bonds under heated conditions and optionally, catalysis as disclosed herein. Examples include diacids, diols, hydroxy acids, hydroxy esters, and the like.

The pressure expressed in pounds per square inch gauge (psig) is relative to one atmosphere. 1psi =6.895 kpa. One atmosphere equals 101.325 kilopascals and one atmosphere is about 14.7 pounds per square inch absolute (psia) or about 0 pounds per square inch gauge (psig).

When referring to a numerical value or range, the term "about" as used herein allows for a degree of variation in the value or range, e.g., within 10%, or within 5% of the stated value or limit of the range.

Furthermore, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will appreciate that the invention is also thereby described in terms of any individual member or subgroup of members (subgroup) of the Markush group. For example, if X is described as being selected from the group consisting of bromine, chlorine, and iodine, then the claims for X being bromine and chlorine are fully described. Furthermore, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any combination of individual members or sub-groups of members of the Markush group. Thus, for example, if X is described as being selected from the group consisting of bromine, chlorine, and iodine, and Y is described as being selected from the group consisting of methyl, ethyl, and propyl, then the claims that X is bromine and Y is methyl are fully described.

If the value of a variable that must be an integer, for example, the number of carbon atoms in an alkyl group or the number of substituents on a ring, is described as a range, for example, 0-4, this means that the value can be any integer between 0 and 4, including 0 and 4, i.e., 0, 1, 2, 3, or 4.

In various embodiments, a compound or group of compounds as used in the methods of the present invention may be any one or any combination of combinations and/or subcombinations of the above listed embodiments.

In various embodiments, there is provided a compound as shown in any of the examples, or in an exemplary compound. The provisos may apply to any disclosed class or embodiment, wherein any one or more of the other above-disclosed embodiments or classes may be excluded from such class or embodiment.

Terms such as "under conditions suitable to provide, or" under conditions sufficient to produce, and the like, refer, in the context of synthetic methods as used herein, to reaction conditions such as time, temperature, solvents, reactant concentrations, and the like, which vary within the ordinary skill of the experimenter and provide useful amounts and yields of reaction products. The desired reaction product is not necessarily the only reaction product or the starting materials are not necessarily completely consumed, provided that the desired reaction product can be isolated or otherwise used otherwise.

"chemically feasible" means a linking arrangement or compound in which the commonly understood rules of organic structure are not violated; for example, structures within the definition of claims that contain a pentavalent carbon atom not found in nature in certain instances will be understood as not being within the scope of the claims. The structures disclosed herein, in all of their embodiments, are intended to include only "chemically feasible" structures, and any such structures that are not chemically feasible, e.g., in structures shown with variable atoms or groups, are not intended to be disclosed or claimed herein.

Mixture of by-products: water wash, COP acid and non-volatile residue

The available cyclohexane oxidation process byproduct streams include "water washes" (aqueous streams produced by water extraction of cyclohexane oxide); "COP acid", a concentrate of a water wash made by removing at least some water; and a non-volatile residue "NVR" (high boiling distillation bottoms product recovered from the distillation of the main process products cyclohexanol and cyclohexanone). These byproduct streams may be converted into the polyol compositions of the present invention described and claimed herein, which may then be used, for example, in the preparation of the polyurethane and polyisocyanurate polymers of the present invention via the prepolymer compositions of the present invention, which polymers and their precursor prepolymer compositions may be used in a variety of products such as coatings, cements, and the like, as disclosed and claimed herein.

The byproduct mixture treated via the inventive process providing the inventive polyol composition herein may be derived from one or a combination of water washes, COP acid, NVR, or combinations thereof. "combination thereof" means any one or two of (water wash and COP acid; water wash and NVR; or COP and NVR) or all three of (water wash, COP acid and NVR). COP acid can be provided by contacting the cyclohexane air oxidation product with water in an extraction step and separating the water wash from the water phase, followed by concentration by evaporation or the like. The aqueous wash may be heat treated to destroy peroxides that may cause difficulties during storage and transportation. The water wash can be concentrated by partial removal of the water to reduce storage volume and transportation costs.

The wash water may contain about 70% to 90% by weight water, for example, about 85% by weight water. COP acid may typically contain about 10% to 70% by weight water, for example, about 10% to 50% by weight water. NVR may contain about 10% to 50% by weight water.

The water wash, COP acid or NVR, or combinations thereof, may include monofunctional and multifunctional byproducts of the cyclohexane oxidation reaction or process in free and/or bound form. By "free form" is meant a monofunctional compound that is not covalently bound to other compounds by a bond (e.g., an ester bond) that is cleaved during heating and distillation (optionally in the presence of a transesterification catalyst). By "bound form" is meant that the monofunctional compound is bound by a covalent bond that is cleaved (e.g., an ester bond) during heating and distillation, optionally in the presence of a transesterification catalyst. During the heating, the free monofunctional compound present in the by-product mixture may be distilled off from the mixture. The bound monofunctional compound may undergo hydrolysis or transesterification, releasing the monofunctional compound in free form, which may then also be removed from the mixture by distillation.

The type of functional group or groups present in the organic component of the compounds present in the byproduct mixture of the cyclohexane oxidation reaction may include: acids (e.g., monocarboxylic acids and dicarboxylic acids), peroxides (e.g., hydroperoxides, dialkyl peroxides), ketones (e.g., aliphatic or cycloaliphatic ketones), alcohols (e.g., aliphatic alcohols, cycloaliphatic alcohols), esters (e.g., aliphatic esters, cycloaliphatic esters), aldehydes (e.g., aliphatic aldehydes, aldehyde-acids), lactones (e.g., aliphatic lactones), and olefins (e.g., ketone-olefins, olefin acids, olefin alcohols); or a combination of functional groups (e.g., hydroxy acids, di-acids, keto-acids, aldehyde-acids, glycols, or acid-hydroperoxides) that may be the same or different in a single molecule.

For example, in a byproduct mixture, prior to heat treatment, the monoacid (monofunctional compound) may include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and the like. These may be present in free form or in bound form as formates, acetates, propionates, and similar esters with hydroxy compounds. The diacid can include malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, oxalic acid, hex-2-enedioic acid, and the like. These may also be present in free or bound form, but are not removed to any significant extent in the heating step by distillation. The peroxides may include cyclohexyl hydroperoxide, hydroxycaproic acid hydroperoxide, and the like. The ketone may include cyclohexanone, cyclopentanone, and the like.

Keto acids can include alpha-keto acids (e.g., 2-oxo acids such as pyruvic acid), beta-keto acids (e.g., 3-oxo acids such as acetoacetic acid), gamma-keto acids (e.g., 4-oxo acids such as levulinic acid), 5-oxohexanoic acid, and the like. Keto acids containing only one carboxylic acid group and no hydroxyl group, as in the above examples, are considered monofunctional compounds herein, and can be removed during the heating/distillation process.

In the byproduct mixture, the monofunctional alcohol may include cyclohexanol, propanol (e.g., 1-propanol and 2-propanol), butanol (e.g., 1-butanol, 2-butanol, etc.), pentanol (e.g., 1-pentanol, 2-pentanol, etc.), hexanol (e.g., 1-hexanol, 2-hexanol, etc.) before the heat treatment. These may be present in free form and also in bound form, for example in combination with carboxylic acid groups as esters thereof. In the byproduct mixture, the diols may include 1, 2-, 1, 3-, and 1, 4-cyclohexanediols, butanediol isomers, pentanediol isomers, and the like.

The components of the by-product wash water, COP acid, and NVR may include free and bound monofunctional compounds, as well as multifunctional compounds, including alcohols, carboxylic acids, and other types of functional compounds such as ketones, aldehydes, peroxides, and other oxidation products (oxygenates). The alcohol may form ester and/or polyester linkages with acid functionality present in the water wash, COP acid, NVR, or combinations thereof. When the carboxylic acid is mono-formic acid, or the alcohol is a mono-alcohol, the acid or alcohol moiety, respectively, is a bound monofunctional that can be released and removed during the heating and distillation steps, optionally in the presence of a catalyst such as an acid or organometallic compound. When the carboxylic acid is a diacid, or the alcohol is a diol, the polyfunctional compound may be incorporated into the polyol composition of the present invention. These can also be incorporated into the polyol composition of the present invention by the processing steps disclosed and claimed herein for the components of the byproduct mixture having two different reactive functional groups. For example, hydroxy acids may form ester or polyester linkages with themselves or with other multifunctional materials present in the mixture.

More specifically, adipic acid may form ester linkages (e.g., condensation reaction products) with the alcohol functional group in hydroxycaproic acid. In one embodiment, hydroxycaproic acid can form an ester linkage (e.g., a condensation reaction product) with an alcohol functional group in another hydroxycaproic acid. Thereafter, such diesters themselves may undergo transesterification upon removal of the monofunctional alcohol and formation of an ester with a polyhydroxy component, such as a diol.

The hydroxy acid may include hydroxycaproic acid, hydroxyvaleric acid, hydroxybutyric acid, hydroxypropionic acid or glycolic acid. In one embodiment, the acid functional group is at one end of a straight chain (e.g., hydrocarbyl chain) and the hydroxyl groups may be present at multiple positions along the chain. The hydroxycaproic acid may include 2-hydroxy-hexanoic acid, 3-hydroxycaproic acid, 4-hydroxycaproic acid, 5-hydroxycaproic acid and 6-hydroxycaproic acid, where the hydroxyl groups may be free or bound to bound mono-or poly-acids. The hydroxypentanoic acid may include 2-hydroxypentanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid and 5-hydroxypentanoic acid. The hydroxybutyric acid may include 2-hydroxybutyric acid, 3-hydroxybutyric acid and 4-hydroxybutyric acid. The hydroxypropionic acid can include 2-hydroxypropionic acid and 3-hydroxypropionic acid.

The byproduct mixtures from two or more different reactions, for example, a byproduct mixture from adipic acid production and another byproduct mixture from caprolactam production, may be combined into a single byproduct mixture that may be further processed into the polyol composition of the present invention.

Polyol process and composition

The inventors of the present invention have found that the process of heating, optionally in the presence of a catalyst such as a transesterification or hydrolysis catalyst, brings about rearrangement in the various compounds present in the byproduct mixture in free and bound form, in particular, of carboxylic acids and their esters, and of hydroxy compounds (alcohols) such as their esters. Bond scission and formation, and it has been unexpectedly discovered that with the removal of monofunctional compounds by distillation, the residual product can comprise the polyol composition of the present invention, which can be used to prepare Polyurethane (PU) and Polyisocyanurate (PIR) polymers for use in a variety of applications. When this transesterification and removal of monofunctional components is carried out in the presence of a polyol, for example, a diol, triol, tetraol or higher polyol, the inventors of the present invention have found that the resulting composition has a beneficially low acid number and a beneficially high OH number to serve as a polyol composition particularly suitable for preparing prepolymer compositions with polyisocyanates, which react with each other and polymerize to form the polyurethane and polyisocyanurate polymers of the present invention.

Accordingly, the present invention may provide a process for preparing a polyol composition, the process comprising:

heating a byproduct mixture and one or more polyhydroxy compounds, and optionally a catalyst, optionally under vacuum, or optionally under sparging with an inert gas, to remove monofunctional components and water by distillation, the byproduct mixture comprising:

i) an aqueous extract of the cyclohexane oxidation reaction product, which is optionally concentrated; alternatively, the first and second electrodes may be,

ii) a non-volatile residue of the cyclohexane oxidation reaction product, which is optionally concentrated; or mixtures thereof.

The method of the present invention may further comprise the steps of: heating the byproduct mixture, optionally under vacuum, or optionally under sparging with an inert gas, to remove monofunctional components and water prior to adding the one or more polyols, and thereafter continuing to heat the resulting mixture after adding the one or more polyols. When this additional heating and distillation step (optionally in the presence of a catalyst such as one suitable for transesterification reactions) occurs prior to the addition of the polyhydroxy compound, it is believed that as the monofunctional component is removed by distillation, transesterification and transesterification occur between the polyfunctional components of the byproduct mixture. Thereafter, upon addition of a polyol, e.g., a diol, triol, etc., and further optionally heating in the presence of the same or other catalyst, further esterification and transesterification occur as the monofunctional components are distilled away with water. The amount of polyol used may be about 3% to 50% by weight. The removal of water and monofunctional compounds can help drive the formation of esters from the polyfunctional acids and added polyhydroxy compounds present in the byproduct mixture.

The heating and distillation process after the addition of the polyhydroxy component may be continued for any suitable period to complete the removal of the water and monofunctional components, for example, the distillation process may be continued until the residual level of monofunctional compound after the heating and removal step by distillation is about 10% or less, or about 5% or less, or about 2% or less, by weight of the composition. For some end uses, more complete removal of the monofunctional compound may be beneficial, while for other end uses, removal need not be so harsh. This may be determined by the end user of a particular application.

The addition of a catalyst, or more than a single catalyst, can promote esterification and especially transesterification of the various carboxylic acid and hydroxylated components in the byproduct mixture and the added polyol. As is well known in the art, the catalyst lowers the activation barrier for the reaction to occur, and together with the heating and distillative removal of water and monofunctional components, the presence of the catalyst can more quickly and efficiently enable the reaction mixture to reach the beneficial conditions for condensation of its polyfunctional components to provide a polyol composition having suitable properties for the desired use. The catalyst may be a transesterification or hydrolysis catalyst such as an acid or an organometallic compound, as discussed in more detail below.

The polyol composition of the present invention can be prepared by removing water and monofunctional compounds from the by-product mixture as described above. In one embodiment, the method comprises heating (e.g., at about 100 to 300 ℃, or at about 150 ℃ to 250 ℃, or at about 180 ℃ to 200 ℃, or at about 235 ℃) a mixture of functional monomers from one or more of: water extract (water wash), concentrated water extract (COP acid) and non-volatile residue (NVR), or mixtures thereof, and removing the monofunctional components and optionally water to form the polyol composition of the present invention. In one embodiment, heating is used in combination with a vacuum (e.g., 10-400mm Hg, or 40-300mm Hg, or 50mm Hg). In one embodiment, heating is used in combination with bubbling or introduction of gaseous species below the liquid surface of the mixture to enhance the removal of water and monofunctional compounds (e.g., inert gases such as nitrogen, or superheated water vapor).

The monofunctional compound and any accompanying water may be removed using the following method (or system): such as distillation, gas-liquid separation (e.g., single stage flash separation, evaporation (short path, wiped film, falling film, atmospheric, sub-atmospheric), multi-stage distillation, various examples of these, or combinations of these), liquid-liquid separation by poor solubility, solid-liquid separation (e.g., fractional crystallization), separation by molecular size and shape (e.g., membrane separation), post-treatment (e.g., carbon decolorization, clay treatment, etc.), and combinations of each of these (e.g., extractive distillation, post-treatment after distillation, etc.).

The polyol component may be selected for the preparation of the polyol composition based on the desired properties of the polyol composition. Any suitable polyol may be used; for example, the polyhydroxy compound may be a dihydroxy compound (diol), a trihydroxy compound (triol), a tetrahydroxy compound (tetraol), or higher. More specifically, the polyol can be ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerin, trimethylolpropane, pentaerythritol, or sorbitol, or a combination thereof.

While not wishing to be bound by theory, it is believed that polyols suitable for use as a component of PU or PIR polymers can be produced by, for example, transesterification of a methyl ester of a compound, such as adipylhydroxypropylhexanoate (adipylhydroxypropylhexanoate), with a polyol, such as by the process exemplified with diethylene glycol as shown below in scheme 1, where the R group is either hydrogen or a monovalent organic group, e.g., cyclohexyl, which upon hydrolysis produces a monofunctional alcohol, ROH, e.g., cyclohexanol. The by-product monofunctional alcohol, e.g., cyclohexanol, is removed, e.g., by distillation. This reaction is exemplary of the various reactions that can occur under esterification and transesterification conditions, optionally in the presence of a suitable catalyst, under conditions of heat and distillative removal of water and monofunctional components.

When R is other than hydrogen, scheme 1 shows an example of a monofunctional hydroxy compound ROH bound to a multifunctional carboxylic acid in a reaction with diethylene glycol, in other words, a transesterification reaction to produce the bis (diethylene glycol) ester of the dicarboxylic acid.

Related reactions include other monofunctional compounds such as monoacids as shown in scheme 2. Scheme 2 illustrates the displacement of bound monofunctional carboxylic acid (pentanoic acid) by polycarboxylic acid (adipic acid), after which the liberated pentanoic acid can be removed by distillation and the remaining adipyl hydroxycaproate reacted with diethylene glycol to form the polyol polyester, the water of the esterification reaction (not illustrated) being removed by distillation.

Under conditions of heating and removal of monofunctional components (optionally in the presence of a catalyst suitable for catalyzing esterification and transesterification), removal of monofunctional components such as monofunctional acids and alcohols results in an equilibrium towards ester drive only between the polyfunctional components. An additional polyol, such as a diol, is further subjected to the set of reactions such that the carboxylic acid is esterified with at least one hydroxyl group of the polyol. For example, when a diol is used, one hydroxyl group may be esterified with a carboxylic acid group from a polyfunctional acid and the other hydroxyl group may remain unesterified, resulting in a composition containing hydroxyl groups and comprising ester linkages. Such hydroxyl groups are then available for reaction with isocyanates to form urethane linkages in PU and PIR polymers.

Scheme 1: formation of esters of polyfunctional alcohol diethylene glycols

In the above example, when R is H, the reaction of diethylene glycol with the dicarboxylic acid is esterification and releases water, which can be removed by distillation. When R is a group such as alkyl or cycloalkyl, the reaction with diethylene glycol is a transesterification and a monofunctional alcohol, for example cyclohexanol, is liberated and then removed by distillation.

Scheme 2: transesterification of esters of monofunctional valeric acids to esters of polyfunctional adipic acids followed by esterification with diethylene glycol Transforming

Thus, one polyol prepared by the process of the present invention is a dihydroxy triester, which may be classified as a polyol-polyester. As will be apparent to those skilled in the art, further transesterification steps may occur to provide higher molecular weight hybrid oligomers. Other di-, tri-, and higher multifunctional esters remaining in the byproduct mixture after removal of the monofunctional component may similarly undergo transesterification reactions with various polyols disclosed and claimed herein to provide various polyol-polyesters useful for condensation with diisocyanates, triisocyanates, and higher polyisocyanates to provide the PU and PIR polymers of the present invention as further described below. Removal of the monofunctional component reduces the concentration of chain terminating moieties in the heated mixture; for example, an ester of a bound monofunctional component such as a monofunctional alcohol or a monofunctional carboxylic acid would be used to eliminate reactive groups on the ends of the molecule, as such an ester does not include additional functionality that can, for example, react with an isocyanate to form a urethane (urethane) bond. However, by displacement and removal of the monofunctional compound from the environment, esterification can occur with difunctional or trifunctional, or higher polyfunctional compounds (diols, polycarboxyl compounds, hydroxyl esters, etc.), forming esters with additional functionality that will be available for urethane bond formation in a subsequent process to form the polyurethane polymer. Thus, removal of the monofunctional component can be used to increase the chain length and available reactive functionality of the polyol composition of the present invention.

A third component comprising a polyfunctional acid, or an activated ester thereof, or a polyfunctional ester or anhydride thereof, or a combination thereof, may be added to the mixture whereby the monofunctional component may be removed by distillation to a level of 10% or less, or 5% or less, or 2% or less on a weight basis. "polyfunctional acid" means a carboxylic acid having two or more carboxylate groups. By "activated ester thereof" is meant an ester of a polyfunctional acid that can undergo transesterification or hydrolysis under heating of the byproduct mixture. By "polyfunctional ester thereof" is meant an ester of a polyfunctional carboxylic acid with one or more polyfunctional alcohols, such as an ester of a glycol. "anhydride thereof" means an intramolecular or intermolecular anhydride of one or two polycarboxylic acids, respectively, as defined above.

For example, the third component may include or may be a polyfunctional aromatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof, or mixtures thereof. More specifically, the polyfunctional aromatic acid, activated ester thereof, polyfunctional ester thereof, or anhydride thereof, may include or may be terephthalic acid, isophthalic acid, ortho-phthalic acid, trimellitic acid, pyromellitic acid, or any combination thereof. The amount of the third component used may be about 1% to 30% by weight.

For example, the third component may include, or may be, a polyfunctional aliphatic acid, or an activated ester thereof, or a polyfunctional ester thereof, or an anhydride thereof; or mixtures thereof. More specifically, the third component may include, or may be, glycolic acid, citric acid, lactic acid, malic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, or adipic acid; or an activated ester thereof; or a polyfunctional ester thereof; or an anhydride thereof; or mixtures thereof. The amount of the third component used may be about 1% to 30% by weight.

The selection of the characteristics of the third component comprising the polyfunctional carboxylic acid may affect the properties of the product in which the polyol composition of the present invention is used. For example, as described below, a polyurethane polymer comprising an aromatic acid or derivative thereof in a polyol component prepared as described above, when used as a coating for a granular fertilizer, can provide a more advantageous (i.e., extended) release period of the fertilizer after application to soil under comparable conditions as compared to a polyurethane polymer that does not comprise an aromatic acid or derivative thereof.

In preparing the polyol composition of the present invention, a multifunctional crosslinking or chain extender having more than two reactive hydroxyl or amino functional groups may be added during the heating/distillation stage. For example, the polyfunctional crosslinking or chain extender may be ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether, neopentyl glycol, glycerol mono-oleate, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, phenyldiethanolamine, trimethylolpropane, 1, 2, 6-hexanetriol, pentaerythritol, N, N, N ', N' -tetrakis- (2-hydroxypropyl) ethylenediamine, diethyltoluenediamine, or dimethylthiotoluenediamine; or any mixture thereof.

More specifically, the multifunctional crosslinker or chain extender may have more than three reactive hydroxyl or amino functional groups; for example, the multifunctional crosslinker or chain extender may be glycerol, triethanolamine, trimethylolpropane, 1, 2, 6-hexanetriol, pentaerythritol or N, N' -tetrakis- (2-hydroxypropyl) ethylenediamine; or any mixture thereof.

In practicing the process of the present invention, the use of a catalyst, such as a transesterification catalyst, can increase the rate and completeness of the reactions involved in preparing the polyol composition. For example, the catalyst may be an acid, e.g., toluene sulfonic acid or xylene sulfonic acid; alternatively the catalyst may be a carboxylate, for example potassium acetate or potassium octoate; alternatively, the catalyst may comprise an organometallic compound, for example, an organomercury, organolead, organoiron, organotin, organobismuth or organozinc compound. More specifically, the organometallic compound may be tetraisopropyl titanate or dibutyltin dilaurate, which are known as effective transesterification catalysts. The particular catalyst and concentration used is determined by methods known to those skilled in the art. The catalyst is typically about 0.01 to 1 wt% of the resin blend composition, but may be higher or lower as desired depending on the catalyst activity.

Additional components that may be added to the byproduct mixture may include hydrophobic materials, which addition may be after heating and removal of the monofunctional components by distillation. The use of a hydrophobic material in the preparation of the polyol composition of the present invention may vary, for example, the nature of a polyurethane polymer which is subsequently prepared in the formation of a polyurethane polymer by using the polyol composition of the present invention as a polyol component in combination with a polyisocyanate. For example, the hydrophobic material may include a natural oil, a fatty acid, or a fatty acid ester derived therefrom; or mixtures thereof. More specifically, the hydrophobic material may include vegetable oils, fatty acids, or fatty acid esters derived therefrom; or mixtures thereof. Alternatively, the hydrophobic material comprises animal oils, fatty acids or fatty acid esters derived therefrom, and mixtures thereof. In detail, the hydrophobic material may include one or more of the following: tallow, tall oil fatty acids, soybean oil, coconut oil, castor oil, linseed oil, inedible vegetable-derived oils, or edible vegetable-derived oils. Alternatively, the hydrophobic material may comprise a synthetic oil, a synthetic fatty acid, or a synthetic fatty acid ester. Alternatively, the hydrophobic material may be an aminated material, a hydroxylated material, or a combination thereof, such as an amine, an amino alcohol, a hydroxy acid, or a combination thereof.

Optionally, one or more additional ingredients selected from the group consisting of: another polyol, solvent, catalyst, chain extender, cross-linker, curing agent, surfactant, blowing agent, filler, flame retardant, plasticizer, light stabilizer, colorant, wax, biocide, mineral, micronutrient, inhibitor, stabilizer, or organic and inorganic additive.

In the preparation of the polyol composition of the present invention, the components may be added and the mixture further processed, for example, by heating and distillation of the monofunctional components until the beneficial properties of the product are obtained. For example, polyol compositions having beneficial properties for the preparation of PU/PIR polymers have relatively low free carboxylic acid content (which can be expressed as acid number as defined above). More specifically, polyol compositions suitable for preparing PU/PRI polymers may have an OH number of about 100 to 500mg KOH/gm sample; alternatively, it may have an acid number of less than 10mg KOH/gm sample, or less than 5mg KOH/gm sample, or preferably less than 1mg KOH/gm sample; or any combination thereof. Polyols having low acid numbers, such as less than 10mg KOH/gm of the sample, or less than 5mg KOH/gm of the sample, or preferably less than 1mg KOH/gm of the sample, have relatively few free, unesterified carboxylic acid groups. Polyols having high OH values, such as those of about 100 to 500mg KOH/gm samples, have a relatively high proportion of reactive hydroxyl groups per mass available for condensation with the isocyanate groups of the polyfunctional isocyanate to produce the urethane (urethane) groups of the resulting PU or PIR polymer.

Thus, the present invention may provide a polyol composition prepared using any combination or subcombination of the above-recited methods and variations thereof. As described below, these polyol compositions find use in many end products, giving higher value as waste products of chemical processes to date.

Resin blends and prepolymer compositions for forming PU and PIR polymer compositions

The present invention may provide resin blend compositions for foamed and non-foamed applications comprising as a component the polyol composition of the present invention. Embodiments of the resin blend include a polyester polyol prepared as described herein, and additionally one or more other components, such as catalysts and modifiers known to those skilled in the art and depending on the end use. Such components may include, in addition to the catalyst for the reaction, other modifier polyols, solvents, chain extenders, cross-linking agents, curing agents, surfactants, blowing agents, fillers, flame retardants, plasticizers, light stabilizers, colorants, waxes, biocides, inhibitors, stabilizers, minerals, micronutrients, or other organic or inorganic additives. The resin blend may be a composition having sufficient stability for shipping or long term storage while maintaining sufficient reactivity with the intended co-reactants to form prepolymers and polymers having properties suitable for the intended function. The resin blend may contain a co-reactant, provided that the co-reactant component and the polyol component of the resin blend react at a rate that is sufficiently low for the intended purpose.

The resin blend may comprise a polyol prepared as described herein and one or more of the above components, co-reactive components such as polyisocyanates may be excluded. Resin blends that do not include a co-reactive component have longer shelf life than resin blends containing such ingredients and may be blended with a co-reactive component, such as an isocyanate, when used. However, the resin blend may, in some particular cases, also include coreactants under conditions where premature reaction is not an issue. However, resin blends typically do not contain coreactants until a coreactant, e.g., a polyisocyanate, suitable for the prepolymer composition and preparation of the resulting polymer, e.g., polyurethane, is added at the time of use.

By "prepolymer composition" is meant a composition which may be semi-liquid or flowable prior to the interaction of the polyol component and the co-reactant, and which may be obtained by mixing the two mutually reactive components, which after reaction may be "coagulated" to form a solid polymeric material. For example, a polyurethane-forming prepolymer composition may include the polyol composition or resin blend of the present invention, plus a polyfunctional isocyanate as a co-reactant, and other optional ingredients such as catalysts as listed above. The physical state of the prepolymer composition prior to the interaction of the polyol composition with the coreactant, such as the "B-side" polyfunctional isocyanate, may be a liquid or semi-liquid, depending on the particular component, having a greater or lesser viscosity, or may be a malleable soft gel. When a reaction occurs between the polyol composition of the present invention and a reactive group of a co-reactant, e.g., an isocyanate group, the hydroxyl groups of the polyol may react with the isocyanate groups to form urethane (urethane) linkages. The urea group can also be generated by reaction with an isocyanate group in the range where a modifier containing an amino group or the like is present in the resin blend. As the covalent reaction proceeds in the prepolymer composition, the physical state of the material changes from a liquid or semi-liquid state to a solid state, where the polymerization product is present. When the prepolymer composition cures into a solid polymer product, it is described as the material "setting" or "coagulating". If a solvent is present in the prepolymer composition, the solvent may be at least partially evaporated during the concentration or "coagulation".

In this way, when the prepolymer composition is flowable, sprayable or spreadable, application of the prepolymer composition to one or more objects can be accomplished as a coating, adhesive, sealant, bonding agent, or the like, but left for a suitable period of time, such as from minutes to hours, and at a suitable temperature, such as above room temperature (or in certain combinations, below room temperature), the mixture undergoes polymerization/crosslinking and produces a solid material, if flexible. Room temperature means a temperature in the range of about 20 ℃ to 25 ℃. Alternatively, coatings, adhesives, sealants, cements, etc. may be applied to one or more objects by: the resin blend and the co-reactant are separately coated, either simultaneously or sequentially, such that the prepolymer composition is formed in situ on one or more surfaces of one or more objects.

It should be understood that the resulting polyurethane or polyisocyanurate polymer may still have a sticky texture and may still contain residues of optional solvents and the like, but that liquid to solid phase transfer has occurred. The solid material then provides a coating or sealing effect and, if adhered to one or more objects, an adhesive effect.

The liquid or semi-liquid prepolymer composition can be foamed by using a blowing agent, i.e., a volatile material that liquefies and expands within the cured prepolymer composition, thereby creating a foam in the material that is then present in the final foam structure containing the solid polymer reaction product. Foams can likewise be viscous, depending on the nature of the object they contact, and can be used as insulators, packaging, and the like. Alternatively, the foam may set without adhesion, creating a solid foam barrier, sheet, packaging bead (packing bead), and the like.

The prepolymer composition comprising the polyol composition of the present invention and a polyfunctional isocyanate, depending on the conditions and the ratio of reactants present in the blend, may produce a polyurethane polymer, or a polyisocyanurate polymer, or may comprise a polymer of both functional groups, as is known in the art. The polyurethane polymer contains predominantly carbamate groups of the formula R-NH-C (= O) -O-R ', where R and the attached nitrogen-carbonyl group are derived from an isocyanate co-reactant and R ' -O is derived from a polyol, it being understood that R and R ' have other functional groups attached thereto, which are themselves further linked, providing a high molecular weight polymeric species. Polyisocyanurate polymers contain a triazine ring in addition to the urethane linkage, which is believed to be formed via reaction of three diisocyanate molecules to produce an intermediate of the formula

Which can then be reacted with polyol hydroxyl groups at the exocyclic isocyanate groups to produce PIR polymers, a variant of PU polymers. Thus, PIR polymers may be more highly crosslinked and more rigid than some PU polymers, although both types of polymers contain linear polyurethane domains. It is known to use a variety of amines and polyamines as curing agents, crosslinking agents or chain extenders, and it will be appreciated that when primary or secondary amines are so used, urea linkages may be present in the resulting polymer. The urea linkage has the structure R-NH-C (= O) -NR 'R ", where R and the attached nitrogen-carbonyl are derived from an isocyanate co-reactant and-NR' R" is derived from a primary or secondary amine, it being understood that either R 'or R "may be, but are not both, H, and R, R' and R" have other functional groups attached thereto which are themselves further linked to provide a high molecular weight polymeric species.

It is known in the art that the formation of polyisocyanurate linkages in excess of urethane linkages can be facilitated by the use of higher relative amounts of co-reactant isocyanates, such as MDI, and by the use of polyester polyols, such as the polyol compositions of the present invention.

Accordingly, the present invention may provide a prepolymer composition for forming a polymer comprising a polyol of the present invention, a co-reactant, and optionally, a catalyst, and optionally, a solvent. For example, the co-reactant may be a polyfunctional isocyanate for forming PU or PIR polymers.

The prepolymer composition may include a polyester polyol of the present invention, a coreactant such as a diisocyanate, and optionally a catalyst for non-foaming applications such as polyurethane-based coatings, cements, adhesives, sealants, and elastomers. The prepolymer composition may include a polyol composition, a co-reactant, and a catalyst for coating applications. Other components may include; for example, solvents that may be used in coating applications. The prepolymer composition comprising the polyol composition of the present invention may also include any one or combination of polyurethane formulation components known to those skilled in the art, as described in the Polyurethanes Chemistry, Technology, and Applications (Ellis Horwood, 1993) by z.

Accordingly, the present invention may provide a process and composition for polyurethane polymers, said process of preparation comprising mixing the polyol composition of the present invention, or prepared by the process of the present invention, and a polyfunctional isocyanate. The polyfunctional isocyanate is an isocyanate having at least 2 isocyanate functional groups per molecule. For example, the polyfunctional isocyanate may include, or may be, monomeric methylene diphenyl diisocyanate (MDI), polymeric MDI, aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, polyfunctional aromatic isocyanates, organic polyisocyanates, modified polyisocyanates, isocyanate-based prepolymers, or mixtures thereof. More specifically, the polyfunctional isocyanate may include an average of more than two isocyanate groups per molecule. For example, the polyfunctional isocyanate may be a polymeric mdi (pmdi) having an average functionality of about 2.1 to about 3.3.

When the polyol composition and the polyfunctional isocyanate are mixed, a catalyst may be added. For example, the catalyst may include an amine, e.g., triethanolamine or diazobicyclooctane; or the catalyst may include an organometallic compound such as tetraisopropyl titanate or dibutyltin dilaurate; or the catalyst may comprise a metal carboxylate such as potassium acetate or potassium octoate.

Depending on the use of the PU or PIR polymer, a solvent may be added when mixing the resin blend and the polyfunctional isocyanate. For example, the solvent may include a hydrocarbon, such as toluene.

Similarly, the present invention may provide a process for preparing a polyisocyanurate polymer comprising mixing the resin blend of the present invention, or the resin blend prepared by the process of the present invention, and MDI. When mixing the resin composition and the MDI, the method may further comprise adding a catalyst, such as an amine, e.g., triethanolamine or diazobicyclooctane (e.g., from Air Products corp.)Series of catalysts).

Examples of PU/PIR polymers prepared using the polyol compositions of the present invention are described in more detail in the examples below.

The present invention may provide a foam composition comprising the resin blend of the present invention or prepared by the process of the present invention, and a polyfunctional isocyanate, and a blowing agent. The foam compositions incorporating the polyester polyol resins of or prepared by the methods of the present invention can be used in rigid applications such as appliances, spray and other pour-in-place applications. The foam compositions incorporating the polyester polyol blend resins of or prepared by the methods of the present invention can be used in flexible applications such as in slab or molded foams for automotive applications, furniture/bed cushioning applications, packaging applications, and the like.

The prepolymer composition used to prepare the PU or PIR polymers may include the polyol composition or resin blend of the present invention, and the co-reactant, such as a diisocyanate or polyisocyanate, may also include a surfactant, a catalyst, and a blowing agent for foaming applications.

Surfactants for use in foaming applications include any surfactant known to those skilled in the art for the purpose of preparing suitable PU and/or PIR spray foams. In one embodiment, the surfactant may include silicone-based surfactants, organic-based surfactants, and mixtures thereof. In one embodiment, the surfactant is about 0.25 to 3.0% by weight of the prepolymer composition.

Accordingly, the present invention may provide a foam composition comprising a polyurethane polymer of or prepared by the process of the present invention, or a polyisocyanurate polymer of or prepared by the process of the present invention, and a blowing agent, and, optionally, a surfactant. As mentioned above, the foam comprising the polymer may be formed by: the liquid or semi-liquid prepolymer composition as a polymer precursor is foamed, after which the prepolymer composition components are coagulated to produce a solid foam material. The blowing agent that produces the foam in, for example, a viscous liquid prepolymer composition can be any suitable volatile material. For example, the blowing agent may comprise a hydrocarbon having 3 to 7 carbon atoms, a hydrofluorocarbon, water, carbon dioxide, or mixtures thereof. More specifically, the hydrofluorocarbon blowing agent may be 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa), 1, 1, 1, 2-tetrafluoroethane (HCF-134a), 1, 1-dichloro-1-fluoroethane (HCFC141-B), chlorodifluoromethane (HCFC R-22), 1, 1, 1, 3, 3-pentafluorobutane (HFC-365mfc), or combinations thereof. More specifically, the hydrocarbon blowing agent can be any of butane, n-pentane, isopentane, cyclopentane, hexane, cyclohexane, olefin analogs thereof, or combinations thereof.

Alternatively, the blowing agent may comprise two or more blowing agents (e.g., blowing agents, co-blowing agents, etc.). For example, the blowing agent can be 1, 1, 1, 3, 3-pentafluoropropane and the co-blowing agent can be water, where the 1, 1, 1, 3, 3-pentafluoropropane can be about 60 to 99 weight percent of the blowing agent and the water can be about 1 to 40 weight percent of the blowing agent.

The total amount of blowing agent or agents can range from about 5 to 25 weight percent or from about 8 to 15 weight percent of the prepolymer composition.

Accordingly, the present invention may provide a process for preparing a foam composition comprising mixing a polyol of the present invention, a polyfunctional isocyanate and a blowing agent to produce a prepolymer composition comprising a blowing agent which foams and coagulates to produce a foam formed of a solid polymeric material. The mixture may be sprayed, foamed in place, or otherwise applied in any suitable manner in which a foam is desired.

Catalysts may be used in preparing the foam compositions of the present invention. The catalyst may comprise a metal-based catalyst, an amine-based catalyst, or a mixture thereof. The metal-based catalyst may include, but is not limited to, organomercury, organolead, organoiron, organotin, organobismuth, organozinc catalysts (e.g., tin octoate and dibutyltin dilaurate), and combinations thereof. Amine-based catalysts may include, but are not limited to, triethylenediamine, N-methylmorpholine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-monomethyl-propylamine, N-ethylmorpholine, diethylethanolamine, N-cocoalkylmorpholine, N-dimethyl-N ', N' -dimethylisopropyl-propylenediamine, N-diethyl-3-diethylaminopropylamine, dimethyl-benzylamine, triethanolamine, triisopropanolamine, or any combination thereof. The catalyst may be present at about 0.001 to 10 wt% of the prepolymer composition.

In a variety of applications, the prepolymer compositions comprising the polyols of the present invention and a coreactant, such as a polyfunctional isocyanate, may comprise a solvent, e.g., for coating applications, cement applications, adhesivesAnd applying a binding agent. In one embodiment, the solvent may be one or more substances that are liquid at the use temperature and are capable of dissolving the prepolymer composition. The solvent may be a non-reactive solvent that does not react with the isocyanate, or a reactive solvent that reacts with the isocyanate and is incorporated into the polyurethane. The use of reactive solvents can help reduce Volatile Organic Compound (VOC) emissions during use of the prepolymer composition. Suitable solvents may include, but are not limited to, toluene, xylene, and other aromatic solvents, including high boiling mixtures such as aromatic 150 (e.g., Solvesso from Exxon Mobil Chemical)) Limonene and other unsaturated hydrocarbons, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, t-butyl acetate, methyl glycolate, ethyl glycolate, propyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diisobutyl succinate, diisobutyl glutarate, diisobutyl adipate, methyl 6-hydroxycaproate, methyl 5-hydroxypentanoate, methyl 4-hydroxybutyrate, methyl levulinate, ethyl levulinate, butyrolactone, valerolactone, 3-ethoxyethyl propionate (EEP), esters derived from natural fats and oils such as methyl soyate, esters derived from other biobased materials such as isosorbide or biosuccinate, carbonates such as dimethyl carbonate or propylene carbonate, esters, Ethers such as tetrahydrofuran and dimethyl isosorbide, ketones such as acetone, 2-butanone, methyl isobutyl ketone, diisobutyl ketone, and isophorone, amides such as Dimethylformamide (DMF) or Dimethylacetamide (DMAC), glycol ethers such as ethylene glycol butyl Ether (EB), diethylene glycol butyl ether, and tripropylene glycol methyl ether, glycol esters such as ethylene glycol diacetate and propylene glycol diacetate, glycol ether esters such as propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, halogenated solvents such as methylene chloride and p-chlorotrifluoromethylene, and others, including dimethyl sulfoxide (DMSO), N-methyl pyridinePyrrolidone (NMP), and the like. In the united states, certain solvents may be preferred over others because they are considered VOC free or because they have low photochemical reactivity. VOC free solvents are listed in United States Code of Federal Regulations, Title40, part 51.100 and include acetone, methyl acetate, dimethyl carbonate, methylene chloride, t-butyl acetate, propylene carbonate, and p-chlorotrifluoromethylene, and the like. Low photochemical reactivity refers to the tendency of a solvent to participate in photochemical reactions that contribute to ground level ozone and "smog". One measure of photochemical reactivity is the Maximum Incremental Reactivity (MIR) as described in professor William p.l. Carter et al; see, for example, the Journal of the Air and waste management Association (the Journal of Air and Water management Association), volume 44, page 881 899, William P.P. Carter, published on 20.1.1994, Development of ozone reactivity scales for volatile organic compounds (Development of ozone reactivity scales). Dimethyl succinate and dimethyl glutarate are two examples of solvents with the desired low MIR values of 0.23 and 0.42, respectively.

Prepolymer compositions, for example, prepolymer compositions for foaming applications, can be prepared by methods known to those skilled in the art. For example, the resin blend composition of the present invention may be added to a blend tank and mixed with the coreactant and catalyst (if used) under ambient conditions, and, if the blend tank is pressure rated, the blowing agent may be added last and all of the compositions mixed for a predetermined period of time until a homogeneous mixture results. When the composition is dispensed and the pressure is released, foaming of the prepolymer composition occurs to provide a foamed polymer upon coagulation.

As noted above, embodiments of the present disclosure include compositions for coatings, adhesives, sealants, elastomers, and cements comprising the reaction product of the polyol composition or polyol-containing resin blend of the present invention and a polyfunctional isocyanate. Embodiments of the present disclosure also include in situ pour foam compositions, appliance foam compositions, spray foam compositions, polyisocyanurate foam compositions comprising the reaction product of a polyol composition and a polyfunctional isocyanate. The polyol composition may include any of the polyol compositions described herein.

For example, the polyfunctional isocyanate may include any isocyanate having an average functionality of at least 2, which may be used to form suitable polyurethane and/or polyisocyanurate foams.

As described above, the present disclosure may provide a polymer foam comprising a polyurethane and/or polyisocyanurate foam. The PU and/or PIR foam may comprise an aliphatic polyester polyol composition, a coreactant polyisocyanate, a catalyst, a surfactant, and a blowing agent. The aliphatic polyester polyol composition can comprise any of the aliphatic polyester polyol compositions described herein. Further, the catalyst, surfactant, and blowing agent can be any of the catalysts, surfactants, and blowing agents described herein.

The prepolymer composition may be used to prepare polyurethane and/or polyisocyanurate foams having an NCO index in the range of about 100 to 400 for spray or other types of applications. In one embodiment, the aliphatic polyester polyol blend composition for this use may have an average functionality of at least about 1.5 and a total hydroxyl number of at least about 120.

PU and/or PIR foams may be prepared in a variety of volume ratios of polyol composition and polyisocyanate to achieve a particular isocyanate index. This ratio is commonly referred to as a: B, where "a" (or a-side component) is a polyisocyanate and "B" (or B-side component) is a polyol composition, according to the usual usage in the united states, although the a-side and B-side may have other meanings in other parts of the world (e.g., in europe). In one embodiment, the ratio may be about 1: 1 to 4: 1.

The a-side component may be a polyisocyanate of the formulations disclosed herein, which may incorporate a polymeric mdi (pmdi). As known to those skilled in the art, typically used is that from Bayer CorporationMR Lite and from Huntsman CorporationAnd M. However, the a-side components are not intended to be limited to only those specifically exemplified herein. For example, the a-side component of the formulations of the present disclosure may be selected from organic polyisocyanates, modified polyisocyanates, isocyanate-based prepolymers, and mixtures thereof. This option may also include aliphatic and cycloaliphatic isocyanates, but aromatic and especially polyfunctional aromatic isocyanates are particularly useful.

The present invention may also provide a sealant, adhesive or bonding agent comprising a polyurethane polymer of the present invention or prepared by the process of the present invention, or a polyisocyanurate polymer of the present invention or prepared by the process of the present invention. For example, the present invention may provide a polyurethane polymer comprising or prepared by the process of the present invention, or a polyisocyanurate polymer of or prepared by the process of the present invention; and a fiber-reinforced composite of a cellulosic material. More specifically, the cellulosic material may include wood fibers, as described in more detail in the examples below. The prepolymer composition of the invention is provided comprising a polyol of the invention, a co-reactant, and optionally a catalyst, and optionally a solvent. Such prepolymer compositions can be used in a variety of sealant and adhesive applications as desired.

The prepolymer compositions of the present invention may also be used to coat fertilizers to provide PU/PIR polymer coated granular fertilizers that may have extended or controlled release properties under field conditions. Accordingly, the present invention may provide a particulate fertilizer composition comprising a fertilizer material in particulate form having a coating comprising a polyurethane polymer of the present invention or prepared by the process of the present invention, or a polyisocyanurate polymer of the present invention or prepared by the process of the present invention. The fertilizer material incorporated herein may be urea, such as prill urea or granular urea. As shown in fig. 1, and described in more detail in the examples below, different degrees of delay in fertilizer release under field conditions can be obtained using different coating formulations. For example, fig. 1 shows that PU compositions containing higher levels of aryl groups derived from the third component as described above may achieve a more extended release period than PU compositions containing lower levels of aryl groups. The coating, which may be decomposed by physical or by biological processes, or both, may be biodegradable.

The polymeric coating may be applied to the particulate fertilizer material according to a variety of methods that produce a prepolymer coating on the fertilizer particles. For example, the resin blend of the present invention may be mixed with a coreactant polyfunctional isocyanate, optionally with a catalyst, solvent, etc. as described above, wherein the resulting prepolymer is then applied to the fertilizer particles while still in fluid condition. Alternatively, the prepolymer composition may be formed in situ on the fertilizer particle by: the B-side resin blend and the a-side isocyanate are separately coated, either simultaneously or sequentially, such that the prepolymer is formed in situ and then coagulated to provide a polymeric coating on the fertilizer particle.

The coated fertilizer of the present invention may further comprise a herbicide, insecticide or fungicide, or any combination thereof, such as in a polyurethane coating or in the particles themselves. The coated fertilizer particles may also contain micronutrients, for example in a polyurethane coating, for controlled release with urea or nitrogen of other N-containing fertilizers incorporated into the granular fertilizer, or other elements such as P or K.

Granular fertilizers prepared using polyols in the form of prepolymer compositions, wherein the third component thereof comprises a polyfunctional aromatic acid, or anhydride thereof, or ester thereof, or mixtures thereof, added in the preparation of the polyol composition, can exhibit unexpectedly advantageous controlled release properties. As shown in fig. 1, and described in more detail in the examples below, polyol compositions comprising aromatic functional groups (which include polyfunctional aromatic acids, esters thereof, or anhydrides thereof, or mixtures thereof) when incorporated into PU polymer coatings for particulate urea fertilizers exhibit slower release profiles under field conditions than comparable compositions having lower levels of aromatic functional groups. In fig. 1, formulations 1-5 were prepared according to the methods described herein to provide samples having the indicated levels of aromatic, aliphatic, and hydrophobic components.

In fig. 1, the relative content of each type of component, i.e. aromatic, aliphatic and hydrophobic components, is given and the data are given for 1 day and 3 day fertilizer release results, which are expressed as relative release curves ranging from 0 to 20 for 3-4% coating. Figure 1 shows a high correlation between the content of aromatic material in the composition and the release delay of the fertilizer content. As can be seen, in formulations 1 and 2, at a ratio of aromatic constituents of 70%, the relative release profile is the same despite varying the aliphatic and hydrophobic ratios; however, as the aromatic content decreased and the aliphatic content increased, in formulation 3, the relative release profile rate increased, and the increase in the hydrophobic fraction in formulations 4 and 5 resulted in still higher relative release profiles. Thus, the present invention may provide a method of preparing a coated fertilizer comprising applying the prepolymer composition of the present invention to a particulate fertilizer material, such as prill urea or granular urea, wherein the relative release profile may be adjusted by varying the relative proportions of aromatic, aliphatic and hydrophobic components in the polyol composition prepared according to the methods disclosed and claimed herein.

The polyol composition used in the formation of the polyurethane coating for the granular fertilizer can be adjusted to provide a solution to a variety of problems involved in the preparation of coated fertilizer particles. Table 3 below shows some adjustments that may be made when evidence of the problem is observed.

Table 3: indication of adjustment of polyol component for PU polymer coatings

The present invention can also provide a fiber-reinforced composite comprising the polyurethane polymer of the present invention, or the polyisocyanurate polymer of the present invention and a fibrous material. The fibrous material may be cellulose, such as wood fiber. The present invention may also provide a method of preparing a fibre-reinforced composite, the method comprising contacting a fibrous material with the prepolymer composition of the invention, and thereafter maintaining the prepolymer composition in contact with the fibrous material under conditions suitable for the prepolymer composition to form the solid PU or PIR polymeric material of the invention. Examples are provided below.

Examples

Analysis of NVR, COP acids and polyester polyols

As noted elsewhere herein, NVR and COP acids contain mono-and polyfunctional molecules with alcohol and carboxylic acid functional groups that can react with each other, forming ester linkages by well-known condensation reactions. When two or more such monomer molecules are linked by the formation of an ester bond, the resulting larger molecule is referred to as an ester oligomer. When at least one monomer molecule is multifunctional, 3 or more monomer molecules may be linked through an ester bond to form an ester oligomer. Ester oligomers, especially higher molecular weight oligomers, cannot be subjected to Gas Chromatography (GC) analysis because they are not sufficiently volatile or stable. Thus, GC analysis of NVR "as is" may give an incomplete image of the composition. For example, some of the adipic acid contained in NVR exists as free adipic acid, but some of the ester oligomers also formed by reaction of adipic acid with the hydroxyl compounds present in NVR exist in bound form. An example of such an ester oligomer would be an ester oligomer formed from adipic acid and 6-hydroxycaproic acid. NVR can be derivatized prior to analysis by treatment with common derivatization reagents such as bis (trifluoromethyl) trifluoroacetamide (BSTFA), but even after such treatment, direct analysis of NVR only shows the amount of free adipic acid, which represents only a fraction of the total adipic acid contained in the free and bound or ester oligomer state.

It was found that NVR can be analyzed by a methanolysis process, wherein NVR is allowed to react with excess methanol in the presence of an esterification catalyst such as sulfuric acid. Transesterification of the oligoester with excess methanol forms the monomeric methyl ester which is readily analyzed by GC. The benefit of this assay is that it provides an assay for the presence of the monomer species contained, whether they be as monomers or ester oligomers.

Methanolysis analysis was performed by refluxing 1g of the sample and 0.125g of an internal suberic acid standard with 10g of 10% sulfuric acid in methanol. The resulting mixture was diluted with 50mL of deionized water and extracted with three 20-mL portions of dichloromethane. The dichloromethane extract was analyzed by gas chromatography on an HP-FFAP column using a method calibrated by using authentic materials of known composition. Table 4 below summarizes the results of the analysis from several different samples of NVR and COP acids obtained using the methanolysis process. The table below also shows "free adipic acid" as determined by BSTFA derivatization and GC analysis, for comparison with "total adipic acid" as determined by the methanolysis method.

The exact composition of cyclohexane oxidation by-products such as water washes, COP acid, and NVR can vary, but both the characteristic difunctional components adipic acid and 6-hydroxyhexanoic acid are typically present in the free and/or bound (i.e., esterified) state. Characteristic monofunctional components include, but are not limited to, butyric acid, valeric acid, and caproic acid. These monofunctional components may be at least partially removed to form a refined mixture prior to and/or during the completion of the formation of the polyester polyol of the present invention.

Table 4: partial composition of NVR and COP acids

Components	NVR-A	NVR-B	NVR-C	NVR-D	NVR-E	COP
							Water (W)	22.0	27.8	23.6	19.6	23.6	38
All butyric acid	1.6	0.5	2.0	1.0	1.7	0.08
							All valeric acid	11.0	4.6	11.4	7.4	11.7	0.6
All hexanoic acid	4.0	2.5	3.6	3.5	4.4	0.03
							All succinic acid	0.5	0.6	0.4	0.4	0.4	0.7
All glutaric acid	2.1	1.5	1.5	1.4	1.9	2.1
							All adipic acid	12.4	15.3	9.3	12.1	11.3	18.9
(free adipic acid)	3.1	3.9	2.7	3.0	2.9	NT
							All HCA	14.5	22.0	16.0	19.1	12.0	20.4

HCA = hydroxycaproic acid; COP = COP acid; NT = not tested.

Procedure for applying a coating to a fertilizer

Typically, the coating comprises a part a and a part B capable of reacting with each other to form a polyurethane polymer. Part B may be a prepolymer composition comprising at least one polyol and optionally other components as described above. In particular, the other components may comprise other isocyanate-reactive compounds such as chain extenders or crosslinkers, one or more catalysts, and one or more solvents. Part a comprises at least one isocyanate and optionally one or more solvents. The relative amounts of reactants are calculated to produce a polyurethane having the desired isocyanate index, where the isocyanate index is calculated as the molar ratio of isocyanate to isocyanate-reactive groups. As noted above, the isocyanate index may be expressed as a percentage, where 100 refers to a molar ratio of isocyanate to isocyanate-reactive groups of 100%. The isocyanate index may also be expressed as a simple ratio rather than a percentage, and both expressions are equivalent: for example, an isocyanate index of 1 is equivalent to an index of 100% and refers to an equimolar number of isocyanate and isocyanate-reactive groups, whereas an isocyanate index of 1.05 is equivalent to 105% and refers to a 5% molar excess of isocyanate over isocyanate-reactive groups.

Coating procedure A

The Buchi R-210 rotary evaporator is equipped with a dry ice-cooled condenser. 1/4 "length of PTFE tubing was connected to the liquid inlet and extended to the upper neck region of the evaporator flask. The water bath is preheated to the curing temperature, typically 60-80 ℃.

A1 l, pear-shaped, Buchi rotary evaporator flask was charged with 150.0g of fertilizer and connected to a Buchi R-210 rotary evaporator. The apparatus was evacuated to 50-60mm Hg and the fertilizer was preheated to the curing temperature. The evaporator flask was initially rotated at a setting of "2" on B ü chi, corresponding to-45 rpm.

The buchi flask is lifted from the water bath and the reactants (or mixture or reactants, optionally including solvent) are allowed to enter through the liquid inlet, vacuum is used to draw the reactants through the liquid inlet and PTFE tube into the buchi apparatus onto the fertilizer in the rotary evaporator flask. A small amount of solvent may be used as a "chaser" to flush reactants adhering to the liquid inlet and PTFE tube onto the fertilizer.

The rotary buchi flask was lowered into the water bath and heating/rotation continued for a time sufficient to coat the one or more reactants onto the fertilizer. The rotation speed was adjusted as needed to impart a tumbling motion to the flask contents.

Steps 3 and 4 are repeated as necessary to add all of the reactants necessary to form a single coating at a time.

After receiving all of the reactants necessary to form a single coating at a time, heating and rotation are continued for a time sufficient to cure the coating.

Steps 3 to 6 are repeated as required to form as many additional coatings as required.

Coating procedure B

Coating procedure B was the same as coating procedure a except that a modified version of step 3 was used to minimize solvent usage. In step 3 of the variation, the rotary evaporator inlet is not used. Instead, the buchi flask was removed from the rotary evaporator and the reaction was added directly to the buchi flask. No solvent "repellents" are required or used. The flask was shaken by hand for-30 seconds to disperse the liquid reactant onto the urea. The flask was then connected to a rotary evaporator and the procedure was completed as in coating procedure a above.

Coating weight measurement

The weight and weight percentage of the polymer coating applied to the urea fertilizer was determined using the following procedure.

Approximately 5g of coated urea fertilizer was weighed into a mortar and the coated sample ground to a powder using a pestle to break the coating

The pulverized sample was transferred to a 150mL flask and stirred with-50 mL deionized water for 10 minutes to dissolve the water soluble portion of the sample (i.e., urea). The coating remained undissolved.

The vacuum filtration apparatus was assembled using a tared sheet of vacuum flask, 70mm Buchner funnel and Whatman #42 filter paper. The contents of the flask were poured through a filter assembly to collect the undissolved coating on filter paper. The flask was rinsed with 50mL additional deionized water to transfer all of the coating to a tared filter paper.

The filter paper with the coating was dried in an oven at 100 ℃ for 1 hour, cooled and weighed. The hide weight was subtracted and the paint weight was calculated. The weight percent of the coating was calculated based on the initial weight of the fertilizer used in step 1.

Controlled release fertilizer test

The following laboratory tests were used to measure the relative release rate of the coated urea fertilizer. This test does not measure the release rate in actual use, but provides a relative measure of the effectiveness of the coating to slow the dissolution of urea in water. The test period may be any desired period of time to show the difference in performance between samples of interest. Too short a test period may not distinguish well whether very little release is observed for all test samples. An excessively long test period may not make a good distinction as to whether virtually complete release is observed for all test samples. We found that a 68 hour test period distinguished the performance of some commercial controlled release urea fertilizers from the controlled release fertilizers prepared using the present invention.

A20 mL scintillation vial was loaded with 2.0g of coated fertilizer and 8.0g of deionized water.

The scintillation vial was securely capped and attached (using an elastic band) to a rotating horizontal shaft so that it would be flipped upside down at-7 rpm. The start time is recorded.

After the desired test period, — 5mL of liquid was passed through a 0.45 μm syringe filter and the filtrate was collected in a tared aluminum foil weighing dish. The gross weight was recorded and the net weight of the filtrate was calculated.

The aluminum pan containing the filtrate was placed in a nitrogen purged oven at 100 ℃ until all water evaporated. The dry hair weight was recorded and the weight of the dried residue was calculated.

The percent solids (solids content) of the filtrate was calculated from the weight of the dried residue from step 4 and the net weight of the filtrate measured in step 3.

The maximum percent solids is expected if the coating weight from the coated fertilizer weight in step 1 is subtracted and divided by the total weight of fertilizer and water (10g) to calculate that the dissolved coated fertilizer sample contains 100% urea.

Percent release was calculated by dividing the result of step 5 by the result of step 6.

Polyol example 1

A polyol having a hydroxyl number of 168 was prepared using NVR-D and diethylene glycol as follows.

A3-liter round bottom flask was charged with 565g NVR-D (see Table) and 225g diethylene glycol. The flask was equipped with a distillation draw, condenser, and distillate receiver, vacuum connector, electromagnetic stirrer, and an immersion tube (bubbler) to admit nitrogen below the liquid surface. The mixture was heated and bubbled with nitrogen while reducing the pressure to-300 mm Hg. The distillate was collected in a distillate receiver. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen and the mixture was allowed to cool to <100 ℃. The collected distillate was removed and found to weigh 153 g. Analysis of the distillate showed that it contained monofunctional components including cyclohexanol, butyric acid, valeric acid and caproic acid, but no desired bifunctional species including adipic acid and 6-hydroxycaproic acid were detected. The nitrogen bubbler was removed, 0.15g of titanium tetraisopropoxide was added, and the mixture was heated under vacuum. The temperature was raised to 196 ℃ and the pressure was reduced to 142mm over a period of-1 hour. The pressure was further reduced to 42mm Hg over the course of an additional 2.6 hours while maintaining the temperature in the range of 196 ℃ and 200 ℃. The heat was removed and the mixture was allowed to cool under nitrogen.

The reaction mixture was analyzed for hydroxyl number. The hydroxyl number was found to be 158mg KOH/g. Diethylene glycol (4.56g) was added and the reaction mixture was heated to 180 ℃ for 1 hour to re-equilibrate the polyol with the addition of diethylene glycol. The product polyol had a hydroxyl number of 168mg KOH/g, a viscosity of 324cSt at 23 ℃, and a weight of 464 g.

Both the NVR-D raw material and the polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid in the NVR-D feed was found to be 0.61 and only 0.32 in the polyol product, indicating that the polyol product contained only 52% monofunctional valeric acid relative to adipic acid as present in the NVR-D starting material. As noted above, analysis of the condensate showed that the monofunctional component was at least partially removed with the condensate, thereby accounting for the reduction found in the polyol product. The weight ratio of adipic acid to 6-hydroxyhexanoic acid was 0.63 in NVR-D starting material and 0.66 in polyol product, indicating that the relative amounts of these two desired difunctional molecules were not substantially altered by the polyol preparation.

Polyol example 2

A polyol having a hydroxyl number of 168 was prepared using NVR-E, terephthalic acid and diethylene glycol as follows.

A500-mL round bottom flask was charged with 113g NVR-E (see Table) and 13.5g terephthalic acid. The flask was equipped with a distillation draw, condenser and distillate receiver, vacuum connection, electromagnetic stirrer and immersion tube (bubbler) to admit nitrogen below the liquid surface. The mixture was heated to 154 ℃ and bubbled with nitrogen while reducing the pressure to-143 mm Hg. The distillate was collected in a distillate receiver. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen. The mixture was allowed to cool to 91 ℃ after which 0.02g of titanium tetraisopropoxide was added. The mixture was heated to 159 ℃ and bubbled with nitrogen while reducing the pressure to 148mm Hg. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen. The distillate was removed and found to weigh 32.4 g. Diethylene glycol (70g) was added and the reaction mixture was heated to 156 ℃ and bubbled with nitrogen while the pressure was reduced to 283mm Hg. After 3 hours, 0.02g additional titanium tetraisopropoxide was added, the nitrogen sparge was removed, and the mixture was heated under vacuum. The temperature was maintained in the range of 174 ℃ to 208 ℃ while the pressure was reduced to 41mm Hg. After 7.5 hours under these conditions, 57.9g of distillate was collected. The reaction mixture weighed 104.8g and analysis showed an acid value of 0.21mg KOH/g and a hydroxyl value of 131mg KOH/g. Diethylene glycol (4.23g) was added and the reaction mixture was heated to 180 ℃ for 1 hour to equilibrate. The heating was removed and the mixture was allowed to cool under nitrogen. The final product had a weight of 109.1g, an acid number of 0.80mg KOH/g, a hydroxyl number of 168mg KOH/g and a viscosity of 947cSt at 23 ℃.

Both the NVR-E starting material and the polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid was found to be 1.04 in the NVR-E feed and only 0.53 in the polyol product, showing that the polyol product contained only 51% monofunctional valeric acid relative to adipic acid as present in the NVR-E raw material.

Polyol example 3

A polyol having a hydroxyl number of 168 was prepared using NVR-D and neopentyl glycol as follows.

A500-mL round bottom flask was charged with 113g NVR-D (see Table) and 68.3g neopentyl glycol. The flask was equipped with a distillation draw, condenser, and distillate receiver, vacuum connector, electromagnetic stirrer, and an immersion tube (bubbler) to admit nitrogen below the liquid surface. The mixture was heated to 151 ℃ and bubbled with nitrogen while reducing the pressure to 298mm Hg. The distillate was collected in a distillate receiver. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen and the mixture was allowed to cool to <100 ℃. The weight of the distillate collected was 32.9 g. The nitrogen bubbler was removed, 0.03g of titanium tetraisopropoxide was added, and the mixture was heated and maintained at the 173-202 ℃ range while reducing the pressure to 40mm Hg. The heat was removed and the mixture was allowed to cool under nitrogen.

The reaction mixture was analyzed for acid value and hydroxyl value. The acid value was found to be 0.41mg KOH/g. The hydroxyl number was found to be 142mg KOH/g. Neopentyl glycol (2.50g) was added and the reaction mixture was heated to 180 ℃ for 1 hour to reequilibrate the polyol with the added neopentyl glycol. The product polyol had an acid number of 0.68mg KOH/g, a hydroxyl number of 167mg KOH/g, a viscosity of 667cSt at 23 ℃ and a weight of 89.6 g.

Both NVR-D raw material and polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid in the NVR-D feed was found to be 0.61 and only 0.33 in the polyol product, indicating that the polyol product contained only 54% monofunctional valeric acid relative to adipic acid as present in the NVR-D starting material.

Polyol example 4

A polyol having a hydroxyl number of 169 was prepared using NVR-D, terephthalic acid and diethylene glycol as follows.

A2L round bottom flask was charged with 508.5g of NVR-D (see Table) and 60.75g of terephthalic acid. The flask was equipped with a distillation draw, condenser and distillate receiver, vacuum connection, electromagnetic stirrer, immersion tube (bubbler) to admit nitrogen below the liquid surface. The mixture was heated and bubbled with nitrogen while reducing the pressure to-150 mm Hg. Water and low boiling components of NVR were top distilled and collected in a distillate receiver. When no more distillate was observed coming out of the top, the vacuum was broken with nitrogen, the mixture was allowed to cool to 118 ℃, and 0.1g of titanium tetraisopropoxide was added. The reaction mixture was bubbled with nitrogen and heated to 160 ℃ while reducing the pressure to 300mm Hg. When no more distillate was seen coming out, the vacuum was broken with nitrogen and the mixture was allowed to cool to 69 ℃. The accumulated distillate was discharged from the distillate receiver and found to weigh 143.1 g. Analysis of the distillate showed that it contained monofunctional components including cyclohexanol, butyric acid, valeric acid and caproic acid, but no desired bifunctional species including adipic acid and 6-hydroxycaproic acid were detected. Diethylene glycol (315g) was added to the reaction mixture. The reaction mixture was bubbled with nitrogen and heated to 160 ℃ while reducing the pressure to 300mm Hg. After 3 hours, the nitrogen sparge was removed and 0.1g of titanium tetraisopropoxide was added. The reaction mixture was heated to 200 ℃ while reducing the pressure to 150mm Hg. After 1 hour, the pressure was reduced to 40mmHg and held for 4.5 hours. The heat was removed and the mixture was allowed to cool under nitrogen.

The reaction mixture was analyzed for hydroxyl number. The hydroxyl number was found to be 148mg KOH/g. Diethylene glycol (10.6g) was added and the reaction mixture was heated to 180 ℃ for 1 hour to re-equilibrate the polyol with additional diethylene glycol. The product polyol weighed 515g and had an acid value of 0.43mg KOH/g, a hydroxyl value of 169mg KOH/g, and a viscosity at 23 ℃ of 773 cSt.

Both the NVR-D starting material and the polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid in the NVR-D feed was found to be 0.61 and only 0.31 in the polyol product, indicating that the polyol product contained only 51% monofunctional valeric acid relative to adipic acid as present in the NVR-D starting material. As noted above, analysis of the condensate showed that the monofunctional component was at least partially removed with the condensate, accounting for the reduction found in the polyol product.

Polyol example 5

A polyol having a hydroxyl number of 168 was prepared using COP acid and diethylene glycol as follows:

a500 mL round bottom flask was charged with 150g COP acid (see Table). The flask was equipped with a short path distillation head with a condenser, a vacuum connector, an electromagnetic stirrer, and a nitrogen inlet tube to admit nitrogen below the surface of the liquid. The pressure was reduced to 300mm Hg and the mixture was heated to 150 ℃ while bubbling with a slow flow of nitrogen. After-3 hours, 0.03g of titanium tetraisopropoxide was added, the nitrogen inlet tube was removed, the pressure was reduced to 40mm Hg, and the mixture was heated to 200 ℃ and held for an additional-3 hours. The mixture was cooled and 45.0g of diethylene glycol was added. The pressure was reduced to 40mm and the mixture was heated to 200 ℃ for 3.5 hours. The mixture was cooled and the acid number was found to be 9.3mg KOH/g. An additional 0.02g of titanium tetraisopropoxide was added, the pressure was reduced to 40mm Hg, and the mixture was heated to 200 ℃ for an additional 2 hours. The acid value was measured and found to be 0.63mg KOH/g. The hydroxyl number was measured and found to be 145mg KOH/g. An additional 2.89g of diethylene glycol was added and the mixture was heated to 180 ℃ under atmospheric pressure and held for 1 hour. The weight of the product was found to be 119 g. The acid value was found to be 1.01mg KOH/g, the hydroxyl value was found to be 168mg KOH/g, the water content was found to be 0.06% by weight, and the viscosity was found to be 542cSt at 21 ℃.

Both COP acid starting material and polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid was found to be 0.0372 in COP acid feed and only 0.015 in the polyol product, showing that the polyol product contained only 40% monofunctional valeric acid relative to adipic acid as present in COP acid starting material. The weight ratio of adipic acid to 6-hydroxycaproic acid was 0.96 in both the starting material and the product, indicating that the relative amounts of these two desired bifunctional molecules were unchanged by the polyol preparation.

Polyol example 6

A polyol having a hydroxyl number of 188 was prepared using NVR-D, glycerol, and diethylene glycol as follows.

A500 mL round bottom flask was charged with 113g NVR-D (see Table). The flask was equipped with a distillation draw, condenser, and distillate receiver, vacuum connector, electromagnetic stirrer, and an immersion tube (bubbler) to admit nitrogen below the liquid surface. The mixture was bubbled with nitrogen while reducing the pressure to-300 mm Hg and the contents were heated to 150 ℃. The distillate was collected in a distillate receiver. After 4.5 hours, no more distillate was observed coming out of the top, the vacuum was broken with nitrogen and the mixture was allowed to cool. The collected distillate was removed and found to weigh 30.2 g. The nitrogen bubbler was removed, 0.3g titanium tetraisopropoxide, 10.0g glycerol and 28g diethylene glycol were added, and the mixture was heated to 185 ℃ while reducing the pressure to 40mm Hg. After 7 hours, the mixture was cooled. The acid value was found to be 1.76mg KOH/g. About 0.03g of titanium tetraisopropoxide was added and the temperature was raised to 200 ℃ while the pressure was reduced to 40mm Hg. After 1 hour, an acid number of 0.90mg KOH/g and a hydroxyl number of 223mg KOH/g were found. The collected distillate was removed and found to weigh 20.3 g. The reaction mixture was heated again and maintained at 200-212 ℃ and 40mmHg until an additional 6.7g of distillate was collected. The heating was removed and the mixture was allowed to cool under nitrogen. The product was found to weigh 88.6g and had an acid value of 0.25mg KOH/g, a hydroxyl value of 188mg KOH/g, and a viscosity of 725cSt at 23 ℃.

Both the NVR-D starting material and the polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid in the NVR-D feed was found to be 0.61 and only 0.38 in the polyol product, indicating that the polyol product contained only 62% monofunctional valeric acid relative to adipic acid as present in the NVR-D starting material.

Polyol example 7

1500 grams of COP acid from a adipic acid manufacturing plant containing 40% water were charged to a 2 liter glass reactor equipped with a stirrer, reflux condenser, separation column, overhead receiver, and thermocouple. The physical water contained is boiled off at temperatures up to 160 ℃. After dehydration to less than 1% water, 630 grams of diethylene glycol and one or more esterification catalysts were added. The reaction mixture was heated under constant stirring at atmospheric pressure to a maximum temperature of 235 ℃ until the theoretical top product was obtained. The acid number of the resulting mixture was reduced to the target specification of <2mg KOH/gram of sample (AN). The final product was analyzed as follows: OH value =190mg KOH/gram sample, AN =1.5mg KOH/gram sample, viscosity = 1390cps at 25 ℃. During the COP dehydration and esterification steps, monofunctional components are removed and found to be present in the water by-product.

Polyol example 8

1200 grams of COP acid containing 40% water from a adipic acid manufacturing plant was charged. Water was removed from COP acid using the same reaction equipment as described in polyol example 7. Subsequently, 648 g of diethylene glycol, 200 g of tall oil fatty acid and one or more catalysts were added and reacted using the same reaction conditions as in polyol example 7. The final product was analyzed as follows: OH value =190mg KOH/gram sample gram, AN = <2mg KOH/gram sample, viscosity = 250cps at 25 ℃.

Polyol example 9

821 g of COP acid containing 40% water from the adipic acid manufacturing plant were charged to a one liter reactor and dehydrated using the same reaction equipment as described in polyol example 7. After dehydration to < 1% water, 168 grams of diethylene glycol, 32 grams of ethylene glycol and 16 grams of pentaerythritol were added and reacted using the same reaction conditions as in polyol example 7. The final product was analyzed as follows: OH value =199mg KOH/gram sample gram, AN =2.8mg KOH/gram sample, viscosity = 1080cps at 25 ℃.

Polyol syrupExample 10

A polyol having a hydroxyl number of 163 was prepared using NVR-E, terephthalic acid and diethylene glycol as follows.

A500-mL round bottom flask was charged with 113g NVR-E (see Table) and 27g terephthalic acid. The flask was equipped with a distillation draw, a condenser and distillate receiver, a vacuum connector, an electromagnetic stirrer, and an immersion tube (bubbler) to admit nitrogen below the surface of the liquid. The mixture was heated to 154 ℃ and bubbled with nitrogen while reducing the pressure to-156 mm Hg. The distillate was collected in a distillate receiver. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen. The mixture was allowed to cool to 122 ℃ before 0.02g of titanium tetraisopropoxide was added. The mixture was heated to 154 ℃ and bubbled with nitrogen while reducing the pressure to 153mm Hg. When no more distillate was observed to come out of the top, the vacuum was broken with nitrogen. Diethylene glycol (70g) was added and the reaction mixture was heated to 150 ℃ and bubbled with nitrogen while reducing the pressure to 295mm Hg. After 4 hours, the mixture was allowed to cool. The distillate was removed and found to weigh 33.2 g. An additional 0.02g of additional titanium tetraisopropoxide was added, nitrogen bubbling was removed, and the mixture was heated under vacuum. The temperature was maintained in the range 184-202 ℃ while the pressure was reduced to 40mm Hg. After 6.5 hours, 36g of distillate was collected.

The reaction mixture weighed 138.8g and analysis showed an acid number of 0.53mg KOH/g, a hydroxyl number of 163mg KOH/g and a viscosity of 1181cSt at 23 ℃.

Both NVR-E raw material and polyol product were analyzed using the methanolysis method described above. The weight ratio of valeric acid to adipic acid was found to be 1.04 in the NVR-E feed and only 0.69 in the polyol product, indicating that the polyol product contained only 66% monofunctional valeric acid relative to adipic acid as present in the NVR-E starting material.

Polyol for rigid foam applications example 11

A hand-mixed rigid polyurethane foam is prepared after the preparation of the aliphatic polyester polyol as described above. The polyol resin (B-side) for the control was prepared using the ingredients of the polyurethane foam as used in appliance applications, such as select polyethers, catalysts, surfactants, water, and 245 fa. A different polyol (B-side) similar to the control was prepared in which a portion of the polyether was replaced by polyol example 9, as shown in table 5 below. In both runs, the MDI used and the B-side were pre-cooled to 15 ℃ before manual mixing foaming to enable handling of the blowing agent in the laboratory. Polyurethane foams containing aliphatic polyester polyols exhibit properties equivalent to PUR foams from all polyether formulations.

Table 5: examples of polyols for rigid foam applications

B side component	Foam examples	Control foam
			Polyol example 9	30	0
Amine initiated polyether polyols (OH =800)	35	50
			Sucrose-glycerol initiated polyether polyol (OH =360)	35	50
Siloxane surfactants	2	2
			Catalyst and process for preparing same	2	2
Water (W)	2	3
			HFC245-fa	17	20
Index (I)	1.10	1.10
			Reactivity, second
Cream	11	10
			Gel	35	38
T.F.	45	50
			E.R.	45	44
Foam properties
			Measurement of Density, pcf	2.06	2.07
Factor K, initial:	0.139	0.140
			freeze test, 28D, volume% Change	-0.7％	-0.5％
Humidity aging, 28D, volume% Change	2％	2％
			Compression, parallel, psi	36	44
Vertical, psi	19	21

Urea coating comparative example a-castor oil based coating on urea

This example describes the preparation of coated urea using castor oil using coating procedure a as described above.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution of part B to a total of 42g was prepared from 4.20g of Vertellus DB castor oil (available from HallStar Company, hydroxyl number 165mg KOH/g) and 0.49g triethanolamine in dry toluene. A solution of part A was prepared from 3.30g of polymeric methylene diphenyl diisocyanate (PMDI, Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to a total of 42 g. The amounts of castor oil polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.14 wt%. The release rate was measured using the procedure described above and was found to be 55% in 68 hours.

Urea coated comparative example B

29-0-4 fertilizers were purchased from Lowe's. The label indicated that the product contained 29% urea nitrogen, of which 4.5% was a slow release of N from coated urea. The exact nature of the coating employed is not disclosed. Visual observation showed white uncoated urea and green-band coated urea. The urea particles of the green band coating were physically separated for analysis and release testing.

The coating weight was measured using the procedure described above and found to be 3.1 wt%. The release rate was measured using the procedure described above and was found to be 72% in 68 hours.

Urea coated comparative example C

Purchased from Harrell's, manufactured by Agrium Advanced Technologies43-0-0 controlled-release fertilizer. According to the literature of the products,43-0-0 is 100% polymer coated, controlled release urea, no uncoated, immediate release urea. The exact nature of the coating employed is not disclosed. Visual observation showed that all particles were green-band coated urea.

The coating weight was measured using the procedure described above and found to be 6.0 wt%. The release rate was measured using the procedure described above and was found to be 3% in 68 hours.

Urea coated comparative example D

The Agrium Duration75 coated urea was tested as above and found to have 4.38 wt% coating and 12% release in 68 hours.

Urea coated comparative example E

The Agrium XCU43-0-0 coated urea was tested as above and found to have 6.36 wt% coating and a release of 64% in 68 hours.

Urea coated comparative example F

Shore lawn Food (Shaw's Turf Food), SurfCote36-0-6 Fertilizer from Knox Fertilizer was observed as a mixture of blue-coated urea and brown irregular particles. The blue coated urea was physically separated from the brown particles, tested as above, and found to have 4.37 wt% coating and 78% release in 68 hours.

Urea coated comparative example G

This example describes the use of predominantly aromatic polyols, obtainable from INVISTA258 to produce coated urea using coating procedure a described above.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). Preparation of solution B containing 3.60g of a 50/50 mixture of anhydrous toluene and anhydrous Tetrahydrofuran (THF)258 polyol (1NVISTA, hydroxyl number 256 mgKOH/g) and 0.49g triethanolamine to make a total of 42 g. Solution A was prepared containing 3.91g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of castor oil polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.80 wt%. The release rate was measured using the procedure described above and was found to be 16% in 68 hours.

Urea coating example 1

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution B was prepared comprising 4.20g of the polyol of example 1 and 0.49g of triethanolamine in dry toluene to make up a total of 42 g. Solution A was prepared containing 3.34g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of polyol and isocyanate were calculated to give 8 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.37 wt%. The release rate was measured using the procedure described above and was found to be 65% in 68 hours.

Urea coating example 2

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). A solution B was prepared comprising 3.86g of the polyol of example 1 and 0.49g of triethanolamine in dry toluene to make up a total of 12 g. Solution A was prepared containing 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 12 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added to the coating flask as described in procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50-55 minutes. Five additional coats were then added, allowing 50-55 minutes cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.40 wt%. The release rate was measured using the procedure described above and was found to be 28% in 68 hours.

Urea coating example 3

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol example 1 polyol 3.86g and triethanolamine 0.49g were dissolved in anhydrous toluene to make up a total of 6g, to prepare solution B. Solution A was prepared by dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 6 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 80 ℃ for 30 minutes. Five additional coats were then added in the same manner, allowing 30 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 80 ℃ for a total of 2 hours.

The coating weight was measured using the procedure described above and found to be 3.38 wt%. The release rate was measured using the procedure described above and was found to be 56% in 68 hours.

Urea coating example 4

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 139g of coated urea from the above urea coating example 2. Polyol example 1 polyol 3.86g and triethanolamine 0.49g were dissolved in anhydrous toluene to make up a total of 12g, to prepare solution B. Solution A was prepared by dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make up a total of 12 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 50 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours. Since the coated urea from urea coating example 2 already has 6 coatings, the product of this example has a total of 12 coatings.

The coating weight was measured using the procedure described above and found to be 7.24 wt%. The release rate was measured using the procedure described above and was found to be 5% in 68 hours.

Urea coating example 5

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). Solution B was prepared comprising 3, 85g of the polyol of example 6 and 0.49g of triethanolamine in anhydrous toluene to make up a total of 42 g. Solution A was prepared containing 3.63g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 1.15. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately fed to a coating apparatus as described in coating procedure a above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.46 wt%. The release rate was measured using the procedure described above and was found to be 35% in 68 hours.

Urea coating example 6

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution B was prepared comprising 5.35g of the polyol of example 1 and 0.10g of DABCO in dry tolueneCatalysts (Air Products) to make up a total of 42 g. Solution A was prepared containing 2.53g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. Calculating the amount of polyol (including DABCO)Hydroxyl content of the catalyst) and the amount of isocyanate to give 8 grams of polyol, polyol,And the total weight of the isocyanates and the isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ and 55mm Hg for 45 minutes. Five additional coats were then added in the same manner, allowing 45-55 minutes cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.45 wt%. The release rate was measured using the procedure described above and was found to be 86% in 68 hours.

Urea coating example 7

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B and toluene solvent described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol 3.92g of the polyol of example 7 and 0.49g of triethanolamine were dissolved in anhydrous toluene to make up a total of 9g, to prepare solution B. Solution A was prepared by dissolving 3.09g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 9 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 50 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.40 wt%. The release rate was measured using the procedure described above and was found to be 11% in 68 hours.

Urea coating example 8

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above and a tert-butyl acetate solvent.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol 3.86g of the polyol of example 1 and 0.49g of triethanolamine were dissolved in anhydrous t-butyl acetate to make a total of 9g, solution B was prepared. Solution A was prepared by dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous t-butyl acetate to make up a total of 9 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 50 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.52 wt%. The release rate was measured using the procedure described above and was found to be 22% in 68 hours.

Urea coating example 9

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B and toluene solvent described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol example 6 polyol 3.86g and triethanolamine 0.49g were dissolved in anhydrous toluene to make up a total of 9g, to prepare solution B. Solution A was prepared by dissolving 3.26g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 9 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.03. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 50 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.25 wt%. The release rate was measured using the procedure described above and was found to be 27% in 68 hours.

Urea coating example 10

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above and an acetone solvent.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol example 1 polyol 3.86g and triethanolamine 0.49g were dissolved in anhydrous acetone to make a total of 9g, to prepare solution B. Solution A was prepared by dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous acetone to make up a total of 9 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 1.05. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 50 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.25 wt%. The release rate was measured using the procedure described above and was found to be 48% within 68 hours.

Urea coating example 11

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution B was prepared comprising 4.20g of the polyol of example 2 and 0.49g of triethanolamine in anhydrous toluene to make up a total of 42 g. Solution A was prepared containing 3.33g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 4.50 wt%. The release rate was measured using the procedure described above and was found to be 43% in 68 hours.

Urea coating example 12

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol example 1 by dissolving 3.86g of the polyol and 0.49g of triethanolamine in anhydrousTo make a total of 6g in ester, solution B was prepared. By dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous waterTo make a total of 6g in ester, solution A was prepared. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 80 ℃ for 30 minutes. Five additional coats were then added in the same manner, allowing 30 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 80 ℃ for a total of 2 hours.

The coating weight was measured using the procedure described above and found to be 3.29 wt%. The release rate was measured using the procedure described above and was found to be 100% in 68 hours.

Urea coatingLayer example 13

This example describes the preparation of coated urea using NVR-based polyols of the present invention using procedure B described above.

A1 liter pear-shaped Buchi rotavapor flask was charged with 150g of granular urea (Lange-Stegmann Company, St. Louis, Mo.). Polyol 3.86g of the polyol of example 1 and 0.49g of triethanolamine were dissolved in anhydrous propylene carbonate to make a total of 6g, solution B was prepared. Solution A was prepared by dissolving 3.15g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous propylene carbonate to make a total of 6 g. The amounts of polyol and isocyanate were calculated to give 7.5 grams of the combined weight of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solution was immediately added directly to the evaporator flask as described in coating procedure B above for one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added in the same manner, allowing 30 minutes of cure time between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.43 wt%. The release rate was measured using the procedure described above and was found to be 100% in 68 hours.

Urea coating example 14

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution B was prepared comprising 4.00g of the polyol of example 1, 0.10g of DABCO in dry tolueneCatalysts (Air Products) and 0.49g triethanolamine to make up a total of 42 g. Solution A was prepared containing 3.40g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. The final coating was allowed to cure at 60 ℃ for a total of 2.5 hours.

The coating weight was measured using the procedure described above and found to be 3.90 wt%. The release rate was measured using the procedure described above and was found to be 71% in 68 hours.

Urea coating example 15

This example describes the preparation of coated urea according to procedure a described above using NVR-based polyols of the present invention.

A1 liter pear-shaped Buchi rotavapor flask was equipped with 150g urea pellets (Aldrich cat. No. 51460, 99.0% purity). A solution B was prepared comprising 3.95g of the polyol of example 1 and 0.49g of triethanolamine in dry toluene to make up a total of 42 g. Solution A was prepared containing 3.58g of polymeric methylene diphenyl diisocyanate (Sigma Aldrich product number 372986, 30% NCO) in anhydrous toluene to make a total of 42 g. The amounts of polyol and isocyanate were calculated to give a total weight of 8 grams of polyol, triethanolamine and isocyanate and an isocyanate index of 105. Solution A and solution B were each divided into 6 equal parts. One sixth of solution a was combined with one sixth of solution B and the combined solutions were immediately fed to the coating apparatus as described above to perform one coating. The coating was allowed to cure at 60 ℃ for 50 minutes. Five additional coats were then added, with a 50 minute cure time allowed between coats, for a total of 6 identical coats. After the 6 th coat cure, 0.1g of Exxal13 isotridecyl alcohol (ExxonMobil Chemical) in toluene was added and allowed to cure for 2 hours at 60 ℃.

The coating weight was measured using the procedure described above and found to be 4.18 wt%. The release rate was measured using the procedure described above and was found to be 45% in 68 hours.

Table 6: summary of urea coating results

Coating examples	Polyol examples	Weight% coating	Release%
				Comparative example C	--	6.04	3％
Urea coating example 4	1	7.24	5％
				Urea coating example 7	7	3.40	11％

Comparative example D	--	4.38	12％
				Comparative example G	--	3.80	16％
Urea coating example 8	1	3.52	22％
				Urea coating example 9	6	3.25	27％
Urea coating example 2	1	4.40	28％
				Urea coating example 5	6	3.46	35％
Urea coating example 11	2	4.50	43％
				Urea coating example 15	1	4.18	45％
Urea coating example 10	1	4.25	48％
				Comparative example A	--	4.14	55％
Urea coating example 3	1	3.38	56％
				Comparative example E	--	6.36	64％
Urea coating example 1	1	4.37	65％
				Comparative example B	--	3.10	70％
Urea coating example 14	1	3.90	71％
				Comparative example F	--	4.31	78％
Urea coating example 6	1	4.45	86％
				Urea coating example 12	1	3.29	100％
Urea coating example 13	1	3.43	100％

Table 6 above summarizes the coating weight and release test results for the inventive urea coating examples and comparative examples. It is readily apparent from the table that the comparative examples exhibit release rates in a very broad range of 3% up to 78%, and that the urea coating examples of the present invention rely on the composition of the polyol, the composition of the prepolymer composition, the thickness of the coating, and other details of the coating method to span a similar range of release rates. The present invention provides polyols, prepolymer compositions and coatings that can be tailored to achieve a wide range of release rates.

Spray foam extruded fertilizer

Polyurethane-coated slow release fertilizers having a coating based on an isocyanate component and an isocyanate-reactive component including a polyol. The method for preparing such particles comprises: applying an isocyanate-reactive component comprising a polyol to a fertilizer particle to form a coated fertilizer particle, applying an isocyanate component to the coated fertilizer particle; and forming polyurethane-coated fertilizer particles.

Spray foam formulations were prepared by preparing the following "B" side blends: 76.40 wt% of a polyol having a hydroxyl number of 168 prepared from NVR-D and diethylene glycol according to example 1; 5.00% by weight of a polymer composed ofObtained from CorporationRB-79; 1.00% by weight of DABCODC3.00% by weight of a product from Air Products30, of a nitrogen-containing gas; 2.00% by weight of a product obtained from BASF Corporation220, 220; 8.00 wt% Enovate (TM) 3000 from Honeywell (HFC-245 fa); 3.00% by weight of a product from Tosoh Specialty Chemicals USA, IncTRX and 1.60 wt% water. This "B" side blend was blended with a blend made by Huntsman CorpThe "A" -side polyisocyanates obtained under M were sprayed together in a volume ratio of 1: 1 by means of a high-pressure spray foaming machine.

The foam obtained from the sprayer was directed onto a large number of urea pellets (Aldrich cat 51460, 99.0% purity) such that the urea pellets represent about 10% by weight of the total mass of the obtained foam. Without the urea content, the foam would have a density of 1.80 pounds per cubic foot, a compressive strength in the direction parallel to the rise of over 21psig and a closed cell content of greater than 94%. The foams show good adhesion on urea substrates when sprayed at room temperature (72 ° F/> 20% RH).

Alternatively, the "a" side and "B" side blends may be co-linearly directed with a plurality of urea prills conveyed with air using any suitable extrusion means known in the art to provide an extrudate comprising urea dispersed throughout the foam.

The extrudate can be further processed into short sections for use as a urea slow release fertilizer with a coating based on an isocyanate component and an isocyanate-reactive component including a polyol.

Aliphatic polyester polyols for use in wood joining applications

The use of polyurethane cements in the preparation of synthetic panels from cellulosic and/or lignocellulosic materials has been described in the literature, including U.S. patents 4609513, 4752637, 4833182, 4898776, which are incorporated herein by reference in their entirety.

The aliphatic polyester polyols from the by-products of cyclohexane oxidation are used to prepare polyurethane-based cements for use in the preparation of synthetic boards from cellulosic and/or lignocellulosic materials.

The polyols may be prepared in the proportions indicated, with an OH number in the range of 100 to 400, from the following ingredients:

preparation of aliphatic polyester polyols for use in wood joining applications

Amount of component (c)

60-70% of the by-product from the cyclohexane oxidation process as described above

Diethylene glycol 30-40%

Catalyst and process for preparing same

The procedure is as follows:

840 grams of the pre-dried by-product from the cyclohexane oxidation process as described herein and 420 grams of diethylene glycol are charged to a 2 liter 3 neck round bottom flask equipped with a stirrer, thermometer, and a vigreux column. The titanate-based catalyst was added at 150 ℃ and the ingredients were heated to 235 ℃ until all 99.5% of the theoretical water was removed and the following properties were obtained:

acid number <2mg KOH/g sample

Hydroxyl value: 150-180mg KOH/g sample.

Viscosity <1000cps at 25 ℃.

Polyurethane cement composition

Polyurethane cements are made from the reaction of polyol blends with polyisocyanates. The polyol blend may be composed of the aliphatic polyester polyols, aromatic polyester polyols, other polyethers, polyurethane catalysts, and surfactants listed above. The polyisocyanate of the binder system is any organic polyisocyanate compound or mixture of such compounds having at least 2 reactive isocyanate groups per molecule.

The cement composition is as follows:

the

The

Wood bonding method using polyurethane cement having polyester polyol of the present invention

(examples are cited in U.S. patent 4609513, incorporated herein by reference in its entirety.)

The wood fibers are treated sequentially with 1% of the above described polyol blend followed by 3% of a polyisocyanate such as Rubinate M. The treated result was compression molded between untreated steel platens at a pressure of about 500psi and a temperature of about 350 ° F. The operation is repeated 40-50 times and thereafter terminated with the fiberboard still released and finally without stickiness.

While the invention has been described and illustrated in sufficient detail to enable those skilled in the art to make and use it, various alternatives, modifications, and improvements will be apparent to those skilled in the art without departing from the spirit and scope of the claims.

All patents and publications mentioned herein are incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference in its entirety.

The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it will be appreciated that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

Claims (92)

1. A process for preparing a polyol composition, the process comprising:

mixing the byproduct mixture, and one or more polyols, and optionally, a catalyst;

optionally under vacuum, or optionally under bubbling with an inert gas,

to remove the monofunctional components and water by distillation,

the byproduct mixture comprises:

i) an optionally concentrated aqueous extract of the cyclohexane oxidation reaction product; alternatively, the first and second electrodes may be,

ii) optionally concentrated non-volatile residue of cyclohexane oxidation reaction product; or mixtures thereof.

2. The method of claim 1, further comprising the steps of: the by-product mixture is heated, optionally under vacuum, or optionally under sparging with an inert gas, to remove monofunctional components and water prior to addition of the one or more polyhydroxy compounds, after which the resulting mixture continues to be heated after addition of the one or more polyhydroxy compounds.

3. The method of claim 1 or 2, wherein the residual content of the monofunctional compound after the steps of heating and removing it by distillation is about 10% or less, or about 5% or less, or about 2% or less, by weight of the composition.

4. The method of any one of claims 1-3, wherein the monofunctional component comprises a monocarboxylic acid and a monohydric alcohol.

5. The method of any one of claims 1-4, wherein the polyol comprises a diol, triol, tetrol, saccharide, or sugar alcohol, or any combination thereof.

6. The method of any one of claims 1-4, wherein the polyol is ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, pentanediol, hexanediol, glycerol, trimethylolpropane, pentaerythritol, or sorbitol, or a combination thereof.

7. The method of any one of claims 1-6, further comprising adding a third component to the byproduct mixture, the third component comprising a polyfunctional acid, or an activated ester thereof, or a polyfunctional ester thereof, or an anhydride thereof, or a combination thereof, prior to heating and removing monofunctional compounds by distillation.

8. The method of claim 7, wherein the third component comprises a polyfunctional aromatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof, or mixtures thereof.

9. The process of claim 8, wherein the third component comprises terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid; an activated ester thereof, a polyfunctional ester thereof, or an anhydride thereof; or any combination thereof.

10. The method of claim 7, wherein the third component comprises a multifunctional aliphatic acid, or an activated ester thereof, or a multifunctional ester thereof, or an anhydride thereof; or mixtures thereof.

11. The method of claim 10, wherein the third component comprises glycolic acid, citric acid, lactic acid, malic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, or adipic acid; or an activated ester thereof; or a polyfunctional ester thereof; or an anhydride thereof; or mixtures thereof.

12. The process of any one of claims 1-11, further comprising adding a multifunctional crosslinker or chain extender having two or more reactive hydroxyl or amino functional groups to the byproduct mixture.

13. The method of claim 12, wherein the multifunctional crosslinker or chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether, neopentyl glycol, glycerol, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, phenyldiethanolamine, trimethylolpropane, 1, 2, 6-hexanetriol, pentaerythritol, N' -tetrakis- (2-hydroxypropyl) ethylenediamine, diethyltoluenediamine, or dimethylthiotoluenediamine; or any mixture thereof.

14. The method of claim 12, wherein the multifunctional crosslinker or chain extender has more than three reactive hydroxyl or amino functional groups.

15. The method of claim 14, wherein the multifunctional crosslinker or chain extender is glycerol, triethanolamine, trimethylolpropane, 1, 2, 6-hexanetriol, pentaerythritol, or N, N' -tetrakis- (2-hydroxypropyl) ethylenediamine; or any mixture thereof.

16. The method of any one of claims 1-15, comprising adding the catalyst to the byproduct mixture, wherein the catalyst comprises an organometallic compound or a strong acid.

17. The method of claim 16, wherein the organometallic compound comprises an organomercury, organolead, organoiron, organotin, organobismuth, or organozinc compound, or the strong acid comprises toluene sulfonic acid or xylene sulfonic acid.

18. The method of claim 16, wherein the organometallic compound is tetraisopropyl titanate or dibutyltin dilaurate, or the strong acid is toluenesulfonic acid or xylenesulfonic acid.

19. The method of any one of claims 1-18, further comprising adding a hydrophobic material to the byproduct mixture prior to heating and removing monofunctional components by distillation.

20. The method of claim 19, wherein the hydrophobic material comprises a natural oil, a fatty acid or fatty acid ester derived therefrom; or mixtures thereof.

21. The method of claim 19, wherein the hydrophobic material comprises a vegetable oil, a fatty acid or fatty acid ester derived therefrom; or mixtures thereof.

22. The method of claim 19, wherein the hydrophobic material comprises animal oil, fatty acids or fatty acid esters derived therefrom, and mixtures thereof.

23. The method of claim 19, wherein the hydrophobic material comprises one or more of: tallow, tall oil fatty acids, soybean oil, coconut oil, castor oil, linseed oil, inedible vegetable-derived oils, or edible vegetable-derived oils.

24. The method of claim 19, wherein the hydrophobic material comprises a synthetic oil, a synthetic fatty acid, or a synthetic fatty ester.

25. The method of claim 19, wherein the hydrophobic material is an aminated material, a hydroxylated material, or a combination thereof.

26. The method of any one of claims 1-25 wherein the polyol composition has an OH number of about 100 to 500mg KOH/gm sample; or, wherein the composition has an acid number of less than 10mg KOH/gm sample, or less than 5mg KOH/gm sample, or preferably less than 1mg KOH/gm sample; or any combination thereof.

27. The method of any one of claims 1-26, further comprising adding another polyol, solvent, catalyst, chain extender, cross-linker, curing agent, surfactant, blowing agent, filler, flame retardant, plasticizer, light stabilizer, colorant, wax, biocide, mineral, micronutrient, inhibitor, stabilizer, organic or inorganic additive.

28. The method of any one of claims 1-27, wherein the byproduct mixture is a byproduct mixture of an adipic acid manufacturing process, or a byproduct mixture of a caprolactam manufacturing process, or a mixture thereof.

29. A polyol composition prepared by the process of any one of claims 1-28.

30. A resin blend comprising the polyol composition of claim 29, and optionally further comprising a catalyst, chain extender, cross-linker, curing agent, surfactant, blowing agent, filler, flame retardant, plasticizer, light stabilizer, colorant, wax, biocide, mineral, micronutrient, inhibitor, stabilizer, organic or inorganic additive.

31. The resin blend of claim 30, including a catalyst adapted to catalyze the formation of a polyurethane or polyisocyanurate polymer when the resin blend containing the catalyst is contacted with a polyfunctional isocyanate.

32. A method of preparing a polyurethane polymer, the method comprising combining the polyol composition of claim 29 or the resin blend of claim 30, and a polyfunctional isocyanate under conditions suitable to provide a polyurethane polymer.

33. The method of claim 32, wherein the polyfunctional isocyanate comprises monomeric MDI, polymeric MDI, aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, polyfunctional aromatic isocyanates, organic polyisocyanates, modified polyisocyanates, isocyanate-based prepolymers, or mixtures thereof.

34. The method of claim 32, wherein the multifunctional isocyanate comprises more than three isocyanate groups.

35. The method of claim 34, wherein the polyfunctional isocyanate is a polymeric MDI.

36. The method of any one of claims 32-35, further comprising adding a catalyst to the polyol composition and the multifunctional isocyanate.

37. The method of claim 36, wherein the catalyst comprises an amine or metal carboxylate or an organometallic compound.

38. The method of claim 37, wherein the amine comprises triethanolamine or diazobicyclooctane, or wherein the metal carboxylate comprises potassium acetate or potassium octoate.

39. The method of any one of claims 32-38, further comprising adding a solvent to the polyol composition and the multifunctional isocyanate.

40. The method of claim 39, wherein the solvent comprises a hydrocarbon.

41. The method of claim 39, wherein the solvent comprises toluene.

42. A polyurethane polymer prepared by the process of any one of claims 32-41.

43. A method of making a polyisocyanurate polymer, the method comprising mixing the polyol composition of claim 29 or the resin blend of claim 30, and a polyfunctional isocyanate under conditions suitable to provide the polyisocyanurate polymer.

44. The method of claim 43, wherein the polyfunctional isocyanate is MDI.

45. The method of any one of claims 43-44, further comprising adding a catalyst to the polyol composition and the multifunctional isocyanate.

46. The method of claim 45, wherein the catalyst comprises an amine, an organometallic compound, or a metal carboxylate.

47. The method of claim 46, wherein the amine comprises triethanolamine or diazobicyclooctane, or the organometallic compound comprises tetraisopropyl titanate or dibutyltin dilaurate, or the metal carboxylate comprises potassium acetate or potassium octoate.

48. A polyisocyanurate polymer prepared by the process of any one of claims 43-47.

49. A method of preparing a prepolymer composition for forming a solid polymer, the method comprising combining the polyol composition of claim 29 or the resin blend of claim 30, with a co-reactant, and optionally, a catalyst, and optionally, a solvent, and optionally, one or more additional ingredients selected from the group consisting of: another polyol, a solvent, a catalyst, a chain extender, a cross-linking agent, a curing agent, a surfactant, a blowing agent, a filler, a flame retardant, a plasticizer, a light stabilizer, a colorant, a wax, a biocide, a mineral, a micronutrient, an inhibitor, a stabilizer, an organic additive, and an inorganic additive.

50. A process as in claim 49, wherein the polymer is a polyurethane or polyisocyanurate polymer, the co-reactant is a polyfunctional isocyanate, and the optional solvent is a non-reactive solvent that does not react with the isocyanate or a reactive solvent that reacts with the isocyanate and is incorporated into the polyurethane or polyisocyanurate.

51. The method of claim 50, wherein the solvent is an aromatic hydrocarbon, an unsaturated hydrocarbon, an ester, a carbonate, an ether, a ketone, an amide, a glycol ether, a glycol ester, a glycol ether ester, a halocarbon, or Dimethylsulfoxide (DMSO); or any mixture thereof.

52. The method of claim 51, wherein the aromatic hydrocarbon is toluene, xylene, or a mixture of high boiling aromatic hydrocarbons; or mixtures thereof.

53. The method of claim 52, wherein the high boiling aromatic hydrocarbon mixture is aromatic 150.

54. The method of claim 51, wherein the unsaturated hydrocarbon is limonene.

55. The method of claim 51, wherein the ester is methyl acetate, ethyl acetate, propyl acetate, butyl acetate, t-butyl acetate, methyl glycolate, ethyl glycolate, propyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diisobutyl succinate, diisobutyl glutarate, diisobutyl adipate, methyl 6-hydroxycaproate, methyl 5-hydroxypentanoate, methyl 4-hydroxybutyrate, methyl levulinate, ethyl levulinate, butyrolactone, valerolactone, 3-ethoxyethyl propionate (EEP), methyl soyate, isosorbide, or bio-succinate; or any mixture thereof.

56. The method of claim 51, wherein the ester is an ester derived from a natural fat or oil, or is an ester derived from a carbohydrate, or is an ester comprising a material derived from fermentation.

57. The method of claim 51, wherein the carbonate is dimethyl carbonate or propylene carbonate; or mixtures thereof.

58. The method of claim 51, wherein the ether is tetrahydrofuran or dimethyl isosorbide; or mixtures thereof.

59. The method of claim 51, wherein the ketone is acetone, 2-butanone, methyl isobutyl ketone, diisobutyl ketone, or isophorone; or mixtures thereof.

60. The method of claim 51, wherein the amide is Dimethylformamide (DMF), Dimethylacetamide (DMAC), or N-methylpyrrolidinone (NMP); or mixtures thereof.

61. The method of claim 51, wherein the glycol ether is ethylene glycol butyl Ether (EB), diethylene glycol butyl ether, or tripropylene glycol methyl ether; or mixtures thereof.

62. The method of claim 51, wherein the glycol ester is ethylene glycol diacetate or propylene glycol diacetate; or mixtures thereof.

63. The process of claim 51, wherein the glycol ether ester is propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, or diethylene glycol butyl ether acetate; or mixtures thereof.

64. The process of claim 51, wherein the halogenated solvent is dichloromethane or p-chlorotrifluoromethylene.

65. The method of any one of claims 51-64, wherein the catalyst is an amine.

66. The method of claim 65, wherein the amine is triethanolamine or diazobicyclooctane, or a mixture thereof.

67. A prepolymer composition prepared by the method of any one of claims 49-66.

68. A foam composition comprising the polyurethane polymer of claim 42, or the polyisocyanurate polymer of claim 48, or the prepolymer composition of claim 67; and a blowing agent, and, optionally, a surfactant.

69. The foam composition of claim 68, wherein the blowing agent comprises a hydrocarbon having 3 to 7 carbon atoms, a hydrofluorocarbon, water, or carbon dioxide; or mixtures thereof.

70. The foam composition of claim 69 wherein the hydrofluorocarbon is 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa), 1, 1, 1, 2-tetrafluoroethane (HCF-134a), 1, 1-dichloro-1-fluoroethane (HCFC141-B), chlorodifluoromethane (HCFC R-22), or 1, 1, 1, 3, 3-pentafluorobutane (HFC-365 mfc); or a combination thereof.

71. The foam composition of claim 69, wherein the hydrocarbon is any of butane, n-pentane, isopentane, cyclopentane, hexane, cyclohexane, or an olefinic analogue thereof; or a combination thereof.

72. A method of making a polymeric foam composition, the method comprising combining the prepolymer composition of claim 67, or the resin blend of claim 30, and a polyfunctional isocyanate; with a blowing agent comprising a hydrocarbon having from 3 to 7 carbon atoms, a hydrofluorocarbon, water or carbon dioxide, or mixtures thereof; and optionally, a surfactant; under conditions suitable for the blowing agent to produce a foamed state in the prepolymer composition prior to the prepolymer composition curing into the solid polymeric material of claim 42 or claim 48.

73. A sealant comprising the polyurethane polymer of claim 42, the polyisocyanurate polymer of claim 48, or the prepolymer composition of claim 67.

74. A method of sealing an object or a void therein, the method comprising applying the prepolymer composition of claim 67 to an object to be sealed, and thereafter maintaining the prepolymer composition on the object under conditions suitable for the prepolymer composition to form the solid polymeric material of claim 42 or 48.

75. An adhesive or bonding agent comprising the polyurethane polymer of claim 42, the polyisocyanurate polymer of claim 48, or the prepolymer composition of claim 67.

76. A method of bonding or joining two or more solid objects, the method comprising applying the prepolymer composition of claim 67 to the two or more solid objects, placing the two or more solid objects adjacent to each other, and maintaining the prepolymer composition on the adjacent objects under conditions suitable for the prepolymer composition to form the solid polymeric material of claim 42 or 48.

77. A coating comprising the polyurethane polymer of claim 42, the polyisocyanurate polymer of claim 48, or the prepolymer composition of claim 67.

78. A method of applying a coating to one or more solid objects, the method comprising applying the prepolymer composition of claim 67 to the solid objects, and thereafter maintaining the prepolymer composition on the objects under conditions suitable for the prepolymer composition to form the solid polymeric material of claim 42 or 48.

79. A coated particulate fertilizer composition comprising a fertilizer material in particulate form having a coating thereon comprising the polyurethane polymer of claim 42 or the polyisocyanurate polymer of claim 48.

80. The coated granular fertilizer composition of claim 79 wherein the fertilizer material is urea.

81. The coated granular fertilizer composition of claim 79 wherein the fertilizer material is prilled or granular urea.

82. The coated granular fertilizer composition of any one of claims 79-81 wherein the coated granular fertilizer is a controlled release or time release fertilizer.

83. The coated granular fertilizer composition of any one of claims 79-82, wherein the coating is biodegradable.

84. The coated granular fertilizer composition of any one of claims 79-83, wherein the composition further comprises a herbicide, an insecticide, or a fungicide, or any combination thereof.

85. The coated particulate fertilizer composition of any one of claims 79-84, wherein the third component of the polyol composition comprises a polyfunctional aromatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof, or mixtures thereof, added in the preparation of the resin composition comprising the polyol.

86. The coated granular fertilizer composition of claim 85 wherein the composition exhibits a release profile under field conditions for a fertilizer that is slower than a comparative composition having a lower content of aromatic functional groups.

87. A method of making the coated particulate fertilizer composition of any one of claims 79-86, the method comprising coating a fertilizer material in particulate form with the prepolymer composition of claim 67, and thereafter maintaining the prepolymer composition on the fertilizer material in particulate form under conditions suitable for the prepolymer composition to form the solid polymeric material of claim 42 or 48.

88. A method of making the composition of claim 85, said method comprising the method of claim 87, wherein said third component of said polyol composition comprises a polyfunctional aromatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof, or mixture thereof; such that there is present an aliphatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof; or a greater proportion of an aromatic acid, or anhydride thereof, or activated ester thereof, or polyfunctional ester thereof, than the hydrophobic material.

89. A fiber-reinforced composite comprising the polyurethane polymer of claim 42 or the polyisocyanurate polymer of claim 48 and a fibrous material.

90. The fiber-reinforced composite of claim 89, wherein the fibrous substance is cellulose.

91. The fiber-reinforced composite of claim 90, wherein the cellulosic substance comprises wood fiber.

92. A method of making a fiber-reinforced composite, the method comprising contacting a fibrous mass with the prepolymer composition of claim 67, followed by maintaining the prepolymer composition in contact with the fibrous mass under conditions suitable for the prepolymer composition to form the solid polymeric material of claim 42 or 48.