Biodegradable polyesters

Abstract

Disclosed are biodegradable polyesters prepared from bio sourced materials and methods for their production. The polyesters comprise a plurality of adducts of two dicarboxylates or anhydrides with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring. wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates and the composition contains pendant carboxylate groups.

Description

BIODEGRADABLE POLYESTERSFIELD

[0001] Disclosed are biodegradable polyesters which may be prepared from bio sourced materials, which can be waterborne and have high performance properties as coatings or discrete films. Disclosed are methods for production of the polyesters and structures prepared from such polyesters.BACKGROUND

[0002] Polyester polymers have proven to be versatile materials with a wide range of uses. Polyesters based on petroleum-derived aromatic monomers are among the most widely utilized polymers, for example polyethylene terephthalate (PET) is produced on massive scale for the production of water bottles, textiles and other consumer goods. PET is not biodegradable and has become a major contributor to the growing problem of environmental contamination by residual post-consumer plastic wastes, including damage to marine ecosystems. Some polyesters can be used in coating and. / or film applications. There is a desire to develop polymer systems which are water-soluble, or which form stable water dispersions that can be utilized in a number of coating and film applications. This facilitates the application of coatings and films using water as the carrier. In recent years there has been increasing interest in biodegradable polyesters, examples include polylactic acid (PLA) and poly-3-hydroxyalkanoates (PHA). These polymers’ high cost and properties have made it difficult to serve large volume applications to displace incumbent high- volume polymers. There remains a need for high performance biodegradable polyesters and methods of making such polymers from flexible feedstock sources that allow manufacturers to balance the cost and sustainability profiles of their products.

[0003] Polyester polyols have been developed which can be made from bio sourced materials that can be utilized to prepare polyurethanes, US 10,941 ,240, incorporated herein by reference, in its’ entirety for all purposes. The preparation of polyurethanes and dispersions of such polyurethanes using the disclosed polyester polyols demonstrate good properties.

[0004] High performance polyesters which are soluble or dispersible in water are desired to facilitate environmentally friendly processing of the polyesters into desired products. What are needed are polyesters which are biodegradable, which can be partially or entirely prepared from bio sourced materials, which have premium properties, and which can be dissolved or dispersed in water. What are needed are such systems which provide good coating properties in a variety of coating applications. What are needed are such systems which provide good films and film properties.SUMMARY

[0005] Disclosed are compositions comprising a plurality of adducts of two dicarboxylates or anhydrides, having two carboxyl groups which form carboxylate groups, with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates or formed from the anhydrides and the composition contains pendant carboxylate groups. The hydroxyl groups on the compounds having at least two fused ring heterocycles react with the carboxylate groups of the dicarboxylates or formed from the anhydrides to form ester linking groups. The dicarboxylates or anhydrides utilized to form the adducts may the same or different. Each of the dicarboxylates and anhydrides contain a hydrocarbylene group between the carboxylate groups or carboxyl groups, wherein the hydrocarbylene groups may be the same or different and may contain a heteroatom of oxygen or sulfur and may contain one or more double bonds. The carboxylate groups may be in the form of carboxylate esters or carboxylic acids. Each of the dicarboxylates or anhydrides may contain a bivalent aliphatic group between the carboxyl groups. The fused rings of the compounds having at least two fused ring heterocycles, may contain heteroatoms of oxygen. The fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

[0006] The adduct may be reacted with any polyols which can react with the adducts to form polymers. The polyols can chain extend and or branch the polymer formed. The polyols may be alkylene diols or alkylene oxide based diols. The alkylene groups can be C2.alkylene groups. The polyols can be diols and polyols having more than two hydroxyl groups on average. If polyols having more than two hydroxyl groups on average are utilized, they may be utilized with diols. The amount of polyols having more than two hydroxyl groups on average may be chosen to introduce a desired amount of branching in the polyester formed. The polyols having more than two hydroxyl groups on average may be triols or tetrols.

[0007] One of the polyols reacted with the adducts are one or more aliphatic diols containing a pendant carboxylate group. The one or more aliphatic diols containing a pendant carboxylate group may be selected such that the pendant carboxylate group does not react with the hydroxyl groups of the polyols during formation of the polymer. It is desired that the pendant carboxylate groups remain substantially unreacted in the formation of the polymers. The carboxylate groups may be in the form of carboxylate esters or carboxylic acids. The one or more aliphatic diolscontaining a pendant carboxylate group may comprise one or more dimethylol alkanoic acids. The one or more aliphatic diols containing a pendant carboxylate group may be present in the formed polymer in a sufficient amount to form a water-soluble or dispersible polymer where converted to a salt or to react with other compounds to crosslink the polymers and / or form other polymeric systems.

[0008] Disclosed are compositions as disclosed herein which are soluble or forms a stable dispersion in water. Disclosed are compositions as disclosed herein dissolved in or dispersed in water. The polymers disclosed herein may be converted to water-soluble salts by contacting the pendant groups with one or more compounds which form a cationic group which forms a salt with pendant carboxylate groups, wherein the formed salt is water-soluble or dispersible. Such salts may be formed when the hydrogens or hydrocarbyl groups on the pendant carboxylate groups are replaced with cations formed from one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as ammonia or a nitrogen containing compound or ammonia or a compound a tertiary nitrogen containing compound. The polymers may contain the residue of disclosed ingredients in the following mole ratios. The fused ring compounds may be present in a mole ratio to the one or more dicarboxylates or anhydrides of about 1 :1 to about 1 :5. The one or more alkylene diols or polyoxyalkylene diols may be present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.5:1 to about 5:1 . The one or more aliphatic diols containing a pendant carboxylate group may be present in a mole ratio to the one or more dicarboxylates or anhydrides of about 1 :20 to about 1 :1 . The polyol having more than two hydroxyl groups on average may be present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.05:1 to about 0.75:1.

[0009] Disclosed are polymerizable compositions comprising: a) one or more dicarboxylates or anhydrides; b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring, wherein the fused ring compounds may be present in a mole ratio to the one or more dicarboxylates or anhydrides of about 1 :1 to about 1 :5; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.5:1 to about 5:1 ; and d) the one or more aliphatic diols containing a pendant carboxylate group, wherein the aliphatic diols containing a pendant carboxylate group are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 1 :20 to about 1 :1. The disclosed composition may be utilized to prepare the disclosed polymers. The polymerizable composition may further comprise e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups. The one or more compounds capable of forming a cationic moietywhich can form a salt with the pendant carboxylate groups comprise one or more of nitrogen containing compounds or ammonia, or tertiary nitrogen containing compounds or ammonia. The polymerizable composition may comprise any of the choices for each component as disclosed herein.

[0010] Disclosed are compositions as disclosed herein wherein the compositions are crosslinked by reaction of the pendant carboxylate groups with a compound having two or more electrophilic groups or a compound which forms ionic groups with the carboxylate groups or salts thereof. Disclosed are coatings prepared from the compositions as disclosed herein. Disclosed are articles comprising a substrate having a coating as disclosed herein applied to a surface or a portion of a surface of the substrate. Disclosed are films prepared from a composition as disclosed herein.

[0011] Disclosed is a method of preparing a composition as disclosed herein comprising adding the compound having at least two fused ring heterocycles to a reaction vessel, heating the reaction vessel to a temperature at which the compound having at least two fused ring heterocycles melts, adding the dicarboxylates or anhydrides to the reaction vessel at a mole ratio of about 2 to 1 or greater, heating the reaction mixture formed to a temperature at which the dicarboxylates or anhydrides and the compound having at least two fused ring heterocycles form an adduct, removing water or the alcohol formed as a result of the adduct formation and contacting the adduct formed with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols under conditions such that the hydroxyl groups of the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols react with the carboxylate groups at the end of the adducts to form a composition having a number average molecular weight of from 1 ,000 to about 5,000,000 atomic mass units, about 1 ,000 to about 500,000 atomic mass units, about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards. The polymer composition formed may have a number average molecular weight of from 1 ,000 to about 5,000,000 atomic mass units, 5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards. The polymer composition formed may be contacted with water and one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, nitrogen containing compounds or ammonia, or tertiary nitrogen containing compounds or ammonia , under conditions such that the carboxylate groups pendant from the composition form a salt with the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as nitrogen containingcompounds or ammonia, or tertiary nitrogen containing compounds or ammonia , to form a composition which is water-soluble or which forms a stable dispersion in water. The polymer composition formed may be contacted with a compound having two or more electrophilic groups or a compound which forms ionic groups with the carboxylate groups, or salts thereof under conditions such that the composition is crosslinked through the pendant carboxylate groups, or salts thereof. The polymer composition formed may be applied to the surface of a substrate and cured to form a coating. The composition formed may be used to form a film.

[0012] The polymers prepared as disclosed herein can be prepared from bio sourced materials, either partially or completely. The polymers disclosed may contain 50 weight percent or greater of biologically sourced materials, 75 weight percent or greater of biologically sourced materials, or 100 weight percent of biologically sourced materials. The disclosed polymers are biodegradable. The disclosed polymers may exhibit a viscosity of about 100 cP to about 100,000 cP, about 500 cPs to about 50,000 cP or about 1 ,000 cP to about 10,000 cP. The disclosed polymers when neutralized in water may exhibit has a pH of about 7.0 to about 8.0. Coatings from the disclosed polymers exhibit excellent adhesion to substrates including stainless steel and excellent flexibility when bent or flexed.DETAILED DESCRIPTION OF THE INVENTION

[0013] While the disclosure has been described in connection with certain embodiments, it is to be understood that the disclosure is not to be limited to the disclosed embodiments and is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be accorded the broadest interpretation to encompass all such modifications and equivalent structures as is permitted under the law.

[0014] One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Hydrocarbyl as used herein refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to one skilled in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and / or triple bonds. Included hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. Alkynylene refers to an aliphatic group containing a triple bond. Valence as used herein means a covalent bond betweena hydrocarbyl or hydrocarbylene group and another group such as a carbonyl, oxygen, nitrogen or sulfur containing group or atom, or the referenced base compound. Carboxyl groups mean a a carbonyl group bonded to an oxygen. Carboxylate is a general term referring to a carboxylic acid group or an ester of a carboxylic acid. The portion of monomers that is incorporated into the backbone of a polymer can be referred to as the residue of the monomer or material. As used herein percent by weight or parts by weight refer to, or are based on, the weight of the compositions unless otherwise specified. Tg is the temperature or temperature range at which a polymeric material shows an abrupt change in its physical properties, including, for example, mechanical strength. Tg can be determined by differential scanning calorimetry (DSC) according to ASTM D3418-15. The molecular weight in this disclosure is determined by gel permeation chromatography using polystyrene standards. Bio sourced means compounds that are produced from biologically sourced materials, such as biomass. Most compounds that can be bio sourced can also be prepared from petroleum feed stocks.

[0015] Disclosed are compositions comprising a plurality of adducts prepared from a) two of one or more dicarboxylates or anhydrides with b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from the ring. The adducts contain carboxylate groups at each end of the adducts. The plurality of adducts are reacted with one or more polyols and one or more diols containing pendant carboxylate groups. The hydroxyl groups of the polyols and one or more diols containing pendant carboxylate groups react with the carboxylate groups at each end of the adducts to form ester groups. A portion of the polyols and one or more diols containing pendant carboxylate groups connect the plurality of adducts to form a polymer having ester linkages. The polyols may be diols or a mixture of diols and compounds containing more than two on average hydroxyl groups. The terminal end of the polymer may contain hydroxyl groups, carboxylate groups or both. The terminal end of the polymer may contain hydroxyl groups. The hydroxyl groups of the polyols and one or more diols containing pendant carboxylate groups preferentially react with the carboxylate groups at each end of the adducts over the pendant carboxylate groups. The pendant carboxylate groups may be carboxylic acid groups or carboxylate ester groups. The pendant carboxylate groups may be carboxylic acid groups. The formed composition may be used for a variety of uses as disclosed herein. The formed composition may be contacted with a compound capable of forming a cationic species. The cationic species can from a salt with the pendant carboxylate groups. Examples of such a compound capable of forming a cationic species include nitrogen containing compounds or ammonia, or tertiary nitrogen containing compounds or ammonia, and the like. The salts of the formed composition may be soluble in or dispersible in water. Disclosed are compositionscomprising the aforementioned salts in water. The formed salts may be dissolved in water or may be in the form of a stable dispersion in water.

[0016] The adducts may be formed from a) two of one or more dicarboxylates or anhydrides with b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from the ring. The two or more dicarboxylates or anhydrides may be any dicarboxylates or anhydrides which are capable of reacting with the hydroxyl groups of the one or more compounds having at least two fused ring heterocycles. The dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxyl groups, wherein the hydrocarbylene groups may be the same or different and may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds. Each of the dicarboxylates or anhydrides may contain a bivalent aliphatic group between the carboxyl groups wherein the bivalent group may contain one or more heteroatoms of oxygen or sulfur. The hydrocarbylene group may be a C 1-40 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur or one or more double bonds. The bivalent aliphatic group between the carboxyl groups may be a C 1-40 bivalent aliphatic group, a C 2-35 bivalent aliphatic group, or a C 2-10 bivalent aliphatic group wherein such aliphatic groups may contain a heteroatom of oxygen or sulfur and / or one or more double bonds. The hydrocarbylene groups and bivalent groups may contain heteroatoms of oxygen. The hydrocarbylene groups and bivalent groups may not contain any heteroatoms.

[0017] The dicarboxylate thereof may correspond to one of the formulas 1 or 1 A:wherein: R is independently in each occurrence hydrogen of a hydrocarbyl group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds; andR1is independently in each occurrence a hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

[0018] Exemplary dicarboxylic acids may be bio sourced or derived from petroleum based feed stocks. Exemplary dicarboxylic acids derived from petroleum based feed stocks include adipic, azelaic acid, dodecanedioic acid, isophthalic acid, terephthalic acid or a short chained fatty acid. Exemplary bio sourced dicarboxylic acids include succinic acid, sebacic acid, furan dicarboxylic acid, itaconic acid, dimerized fatty acids, such as C36 dimer acid (dimer of oleic acid), hydrogenated dimerized fatty acids, such as C36 dimer acid, citric acid, maleic acid, fumaric acid. Any of the disclosed dicarboxylic acids can be used in the esterified form. Exemplary dicarboxylate esters include dialkyl terephthalates, such as dimethyl terephthalates.

[0019] The adducts may be formed from anhydrides. Any anhydride which reacts with the one or more compounds having at least two fused ring heterocycles and which forms an adduct with an end carboxylate, carboxylic acid, groups may be utilized in preparing the adducts. The anhydride may be a cyclic anhydride. Exemplary cyclic anhydrides include those which correspond to the formula:, wherein R 1 as defined herein. Exemplary anhydrides may be bio sourced or derived from petroleum based feed stocks. Exemplary bio sourced anhydrides include phthalic anhydride, succinic anhydride, maleic anhydride and hexa-hydro phthalic anhydride.

[0020] The one or more compounds having at least two fused ring heterocycles may be compounds wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring. Any compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from the ring, which form an adduct with two or more of dicarboxylates or anhydrides may be utilized to prepare the adducts. The fused rings of the compound having at least two fused ring heterocycles, may be C 5-6 rings or C 5 rings. The hetero atoms in the fused rings may be oxygen or sulfur, or oxygen. The fused rings of the compound having at least two fused ring heterocycles, may have one hydroxyl group pendant from each of the rings. The compound having two fused ring heterocycles may correspond to formula 2:2, wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and x is independently in each occurrence an integer of from 2 to 4. Exemplary compounds having at least two fused ring heterocycles may be such compounds wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from the ring include isosorbide, isomanide or isoidide. Exemplary bio sourced compounds having at least two fused ring heterocycles include isosorbide, isomanide and isoidide.

[0021] The adducts are reacted with certain polyols to form polyester polymer chains. Polyols comprising diols function to chain extend the polymers. Polyols having on average greater than two hydroxyls may be present to branch the formed polymer chains, such polyols may have 3 or more or 4 or more hydroxyl groups. Such polyols may have 3 to 4 hydroxyl groups. The polyols having on average greater than two hydroxyls may be present in a sufficient amount to formpolymer chains with the desired amount of branching. A mixture of diols and polyols having on average greater than two hydroxyls may be used to chain extend and branch the polymer chains. The diols may be one or more diols of alkylene diols or polyoxyalkylene diols or alkylene diols. The one or more diols may comprise alkylene diols which contain C 2-6 alkylene or C 6-8 cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups. The diols may be based on ethylene, propylene or butylene diols, or propylene diols. The one or more alkylene diols orH - O - R3-HO - R3-j-0 - H polyoxyalkylene diols may correspond to formula 4: ' , 4 wherein R3is independently in each occurrence C 2-6 alkylene groups, C 6-8 cycloalkylene diol; and y is independently in each occurrence an integer of 0 to 20. Exemplary petroleum-based diols include diethylene glycol, ethylene glycol, polyethylene glycol, neopentyl glycol, methyl propane diol (1 ,3 butylene diol), hexane diol, cyclohexane dimethanol, 1 ,4 butane diol, dipropylene glycol, propylene glycol, hydroxypivalic acid neopentylglycolester. Exemplary bio sourced based diols include 1 ,5-pentane diols, 1 ,3 propane diol and 1 ,4 butane diol. Exemplary polyols having on average greater than two hydroxyls comprise glycerin, trimethyolpropane and pentaerythritol. Exemplary biosourced polyols having on average greater than two hydroxyls include glycerin.

[0022] A portion of the diols used to form the polymer chains are one or more aliphatic diols containing a pendant carboxylate group, such as a carboxylic acid. The one or more aliphatic diols containing a pendant carboxylate group may be any compounds which function to chain extend the polymer chains wherein the carboxylate groups do not significantly react with the hydroxyl groups of the other compounds present when forming the polymers. What is meant by do not significantly react means less than 5 percent of the pendant carboxylate groups react with the other hydroxyl groups present, 2 percent or less, 1 percent or less or 0.5 percent or less. The amount of the one or more aliphatic diols containing a pendant carboxylate group present is that amount that provides sufficient carboxylate groups to crosslink the polymers or to form water- soluble or dispersible polymers as discussed herein. The one or more aliphatic diols containing a pendant carboxylate group comprise one or more C 210 aliphatic diols containing a pendant carboxylate group or one or more C 2-4 aliphatic diols containing a pendant carboxylate group. The pendant carboxylate group may be a carboxylate ester or a carboxylic acid. The one or more aliphatic diols containing a pendant carboxylate group may be one or more dimethylol alkanoic acids, or dimethylol propanoic acid The one or more aliphatic diols containing a pendantcarboxylate group may correspond to formulawherein R is as defined herein and R2is independently in each occurrence one or more C 2-10 aliphatic groups. Exemplary aliphatic diols containing a pendant carboxylate group may correspond to formula 3A;

[0023] The polymers prepared comprise a plurality of adducts of two dicarboxylates and / or anhydrides with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from the ring wherein the plurality of adducts are linked by a plurality of residues of one or more polyols such as diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates and / or anhydrides and the composition contains pendant carboxylate groups. The polyols may comprise one or more polyols having greater than 2 hydroxyl groups on average to introduce branching into the polymer formed. The polymer formed may have the pendant carboxylate groups converted to salts by reaction with a cation containing group. The salts may be soluble in or form stable dispersions in water. Disclosed are the polymer salts dissolved in or dispersed in water. The formed polymers may be further branched or crosslinked by the reaction of the pendant carboxylate groups or salts thereof with one or more compounds having two or more electrophilic groups which react with the carboxylate groups, such as carboxylic acids or salts thereof. The pendant carboxylate groups may be reacted with a compound that forms ionomeric bonds with the pendant carboxylate group, such as carboxylic acid groups or salts thereof. Where there is excess dicarboxylates and / or anhydrides present in the reaction mixture of the adduct and the one or more polyols such as diols of alkylene diols or polyoxyalkylene diols and the one or more aliphatic diols containing a pendant carboxylate group, the polymer may have units derived from the dicarboxylates and / or anhydrides and one or both of the one or more polyols such as diols of alkylene diols or polyoxyalkylene diols and the one or more aliphatic diols containing a pendant carboxylate group.

[0024] The polymer formed may have a polymer backbone which corresponds to formula 5;Wherein R, R1, R2, R3, and y are as described herein; z is a real number such that the molecular weight of the polymer formed is from 1 ,000 to about 5,000,000 atomic mass units, 5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined as disclosed herein; and, a and b in each unit are zero or 1 and the sum of a and b is 1 . In the polymers, R may be a cationic group which forms a salt with anion formed by abstraction of the hydrogen or hydrocarbyl group, a salt forming cation.

[0025] The polymer formed may have a polymer backbone which corresponds to formula 5A;R, R1, R2, R3, a, b, x y and z are as described herein.

[0026] R may be separately in each occurrence hydrogen or a C 1-20 alkyl group which may contain one or more double bonds which may be optionally substituted a heteroatom or a heteroatom containing functional group, a C 5-20 aryl group which may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group, or a C 5-20 cycloalkyl group which may contain one or more double bonds, may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group. R may be separately in each occurrence hydrogen or a C 1-12 alkyl group which may contain one or more double bonds which may be optionally substituted a heteroatom or a heteroatom containing functional group, a C 5-15 aryl group which may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group, or a C 5-10 cycloalkyl group which may contain one or more doublebonds, may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group. R may be separately in each occurrence hydrogen or a C 1-4 alkyl group which may contain one or more double bonds, a C 5-12 aryl group which may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group, or a C 5-10 cycloalkyl group which may contain one or more double bonds, may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group. R may be separately in each occurrence hydrogen, methyl, ethyl, phenyl, benzyl or cyclohexyl group. In the polymer backbone illustrated, R may be a salt forming cation, such as a cation formed from a nitrogen containing compound or ammonia.

[0027] R1may be separately in each occurrence a hydrocarbylene group which may contain one or more double bonds, and / or a heteroatom or a heteroatom containing functional group. R1may be separately in each occurrence a C 1-20 hydrocarbylene group which may contain one or more double bonds, may be optionally substituted with an alkyl group, heteroatom or a heteroatom containing functional group. R1may be separately in each occurrence a bivalent aliphatic group which may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds. R1may be separately in each occurrence C 1.40 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds. R1may be separately in each occurrence a C 1-40 bivalent aliphatic group, a C 2-35 bivalent aliphatic group, a C 2-10 bivalent aliphatic group or a C 2-5 bivalent aliphatic group.

[0028] R2may be separately in each occurrence a bivalent aliphatic group which may contain one or more double bonds. R2may be separately in each occurrence a bivalent C 2-10 aliphatic group which may contain one or more double bonds. R2may be separately in each occurrence a bivalent C 2-4 aliphatic group. R3may be separately in each occurrence an alkylene group. R3may be separately in each occurrence a C 2-6 alkylene or C6-8 cycloalkylene group, a C 2-4 alkylene groups or a C 2-3 alkylene group. D may be independently in each occurrence two C 5-6 fused ring structures each containing a heteroatom. D may be independently in each occurrence two C 5 fused ring structures each containing a heteroatom. The variable x is an integer of 2 to 4, or 2. The variable y may be independently in each occurrence an integer of 0 to 20 or an integer of 0 to 10 or 0. The variable z is a real number such that the molecular weight of the polymer formed is from 1 ,000 to about 5,000,000 atomic mass units, about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units. The variable z may be a real number of 3 to 15,000 or 15 to 300.

[0029] The polymer formed may have a number average molecular weight which provides for the properties needed in the desired application. The number average molecular weight of the polymer may be about 1 ,000 atomic mass units or greater, about 5,000 atomic mass units orgreater, or about 10,000 atomic mass units or greater. The number average molecular weight of the polymer may be about 5,000,000 atomic mass units or less, about 500,000 atomic mass units or less, about 100,000 atomic mass units or less, or about 70,000 atomic mass units or less. The number average molecular weight of the polymer may be from about 1 ,000 to about 5,000,000 atomic mass units, about 5,000 to about 100,000 atomic mass units, or about to about 70,000 atomic mass units. In the recited ranges the intermediate numbers are included in the disclosure. The number average molecular weight is determined as disclosed herein. Where the pendant carboxylates are carboxylic acids, the polymers formed may have an acid number. The acid number may be about 10 mg KOH / gram or greater, about 15 mg KOH / gram or greater, about 20 mg KOH / gram or greater or about 40 mg KOH / gram or greater. The acid number may be about 60 mg KOH / gram or less, about 50 mg KOH / gram or less or about 40 mg KOH / gram or less. The acid number may be calculated using the test method TAN ASTM 664, the results are reported as the mg of potassium hydroxide per gram of sample tested required to neutralize the sample. The method is described in SI Analytics paper, Determination of Total acid number according to ASTM 664 available from SI Analytics.

[0030] The pendant carboxylate groups, such as carboxylic acid groups, may be contacted with any compound capable of forming a cationic moiety which can form a salt with the carboxylate group. The compound capable of forming a cationic moiety which can form a salt with the carboxylate group can be a nitrogen containing compound or ammonia, or a tertiary nitrogen containing compounds or ammonia capable of forming a cationic moiety which forms a salt with the pendant carboxylate group. Any nitrogen containing compound which can react with a carboxylate, such as a carboxylic acid, to form a water-soluble salt may be used. Nitrogen compounds with tertiary nitrogen atoms are frequently utilized because they are less reactive with other materials in that the nitrogen compounds or salts may come into contact with. Exemplary nitrogen containing compounds include tertiary amines, guanidines, imidazolines, pyridines, pyrrolidines or piperdines and the like. The nitrogen containing compounds may be tri hydrocarbyl amines, such as trialkyl amines. The hydrocarbyl groups may be alkyl groups, aryl groups, alkaryl groups, cycloalkyl groups or mixtures thereof. The hydrocarbyl groups may be alkyl groups, benzyl groups, phenyl groups, cycloalkyl groups or mixtures thereof. The hydrocarbyl groups may be C 1-4 alkyl groups. All or a portion of the carboxylate groups may be converted to salts. The amount of the salt forming compounds forming salts with the polymers can be any amount which renders the polymers water-soluble or capable of forming stable dispersions in water. The salt forming compounds may neutralize any acid groups present. After contacting the polymers with the salt forming compounds, the polymers may have a pH of near neutral. The polymers contacted with the salt forming compounds may have a pH of about 7 or greater, or about 7.1 or greater.The polymers contacted with the salt forming compounds may have a pH of about 8 or less or about 7.9 or less.

[0031] The relative amounts of the recited components are chosen to prepare a polymer having the desired molecular weights, acid numbers, water solubility or dispersibility, hydroxyl number, pH and other desired properties, such as good coating properties. The relative amounts of ingredients can be expressed as mole ratios of each ingredient as compared to dicarboxylate and / or anhydride. The mole ratios of the other ingredients is expressed relative to the 100 moles of the dicarboxylates and / or anhydrides. In forming the adduct, the mole ratio of the compound having at least two fused ring heterocycles to of the dicarboxylates and / or anhydrides is about 1 :5 (0.2:1) or greater, about 1 :3 (0.33:1) or greater or about 1 :2 (0.5:1 ) greater. In forming the adduct, the mole ratio of the compound having at least two fused ring heterocycles to the dicarboxylates and / or anhydrides is about 1 :1 or less, about 1 :2 (0.5:1) or less or about 1 :2.5 (0.4:1 ) or less. In forming the polymer, the mole ratio of the diols of alkylene diols or polyoxyalkylene diols to the dicarboxylates and / or anhydrides is about 0.5:1 or greater, about 1 :1 or greater or about 1 :1 .1 (0.9:1) or greater. In forming the polymer, the mole ratio of the diols of alkylene diols or polyoxyalkylene diols to the dicarboxylates and / or anhydrides is about 5:1 or less, about 2:1 :100 or less or about 1.1 :1 less. In forming the polymer, the mole ratio of the aliphatic diols containing a pendant carboxylate group to the dicarboxylates and or anhydrides is from about0.05:1 or greater, about 0.21 or greater or about 0.3:1 or greater. In forming the polymer, the mole ratio of the aliphatic diols containing a pendant carboxylate group to the dicarboxylates and or anhydrides is from about 1 :1 or less, about 0.5:1 or less or about 0.4:1 or less. In forming the polymer, the mole ratio of the polyols having more than two hydroxyl groups or to the dicarboxylates and / or anhydrides is from about 0.005:1 or greater, about 0.01 :1 or greater or about 0.05:1 or greater. In forming the polymer, the mole ratio of the polyols having more than two hydroxyl groups to the dicarboxylates and / or anhydrides is about 0.1 :100 or less, or about 0.075:100 or less.

[0032] The polymers may be crosslinked through the pendant carboxylate groups, such as carboxylic groups, by contacting the polymer with one or more compounds having two or more electrophilic groups which form a covalent bond with the pendant carboxylate groups, such as carboxylic acid groups. The electrophilic groups may be one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate, and isothiocyanate groups or mixtures thereof. The electrophilic groups may be isocyanate epoxide groups or melamine groups. All or a portion of the pendant carboxylate groups or salts thereof may be reacted with the compound having as least two electrophilic groups. The number of the pendant carboxylate groups reacted with electrophilic groups is chosen to provide the desired properties of thecrosslinked polymers.

[0033] The polymers may be crosslinked by ionomeric groups by contacting the pendant carboxylate groups or salts thereof with a compound that forms an ionomeric links with the carboxylate groups or salts thereof, such as carboxylic acids or salts thereof. One or more metal salts and / or metal oxides of a metal having a valence of 2 or greater may form ionomeric groups with the pendant carboxylate groups. The metal may be any metal that is capable of forming 2 or more cationic groups that will form an ionic bond with anions formed from the carboxylate groups or complexing with two carboxylate groups. The metal may be one or more of transition metals, post transition metals, metalloids or an alkaline earth metals. The metal may be one or more of zinc, zirconium, aluminum, magnesium and calcium. The metal may be one or more of zinc and / or zirconium. The metal may be zinc. The metal is used in the form of a salt or oxide. Any salt or oxide may be used which can form cations under heat and or shear conditions. The metal may be present in the form of a metal carbonate, metal acetate, metal bicarbonate, metal oxide, metal hydroxide, metal carboxylate, metal acetylacetonate, metal salt of a fatty acid or mixtures thereof. Exemplary metal salts or metal oxides include zinc acetate, zinc oxide, zinc carbonate, zinc hydroxide, zinc stearate, zinc citrate, zirconium acetate, zirconium oxide, aluminum acetate, calcium carbonate, calcium stearate and the like.

[0034] Disclosed are compositions that can be utilized to prepare the polyester polymers disclosed herein. The disclosed compositions may be characterized as polymerizable compositions. Such compositions when reacted as described herein may form the disclosed polyester polymers. Disclosed is a composition comprising: a) one or more dicarboxylates or anhydrides; b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring, wherein such fused ring compounds are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 1 :1 to about 1 :5; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.5:1 to about 5:1 and d) one or more aliphatic diols containing a pendant carboxylate group, wherein the aliphatic diols containing a pendant carboxylate group are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.05:1 moles to about 1 :1 . Any of the mole ratios discussed previously may be used to prepare the disclosed compositions. Any of the disclosed variations of the disclosed ingredients may be utilized in these compositions. The disclosed composition may comprise e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups. The one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups are as disclosed herein. The one ormore compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups may be present in a sufficient amount such that the composition when in water exhibits a pH of from about 7.0 to about 8.0. The amount of the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups that can be used can be determined by calculating the acid number of the polymer that the composition would form and determining the amount of the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups needed to prepare a salt having the desired pH. This calculation may utilize the following formula as disclosed in this document. To introduce branching into the polymer, a portion of the one or more diols of alkylene diols or polyoxyalkylene diols may be replaced with f) one or more polyols having more than two hydroxyl groups, present in a sufficient amount to form branched polymeric chains. The one or more polyols having more than two hydroxyl groups comprise one or more compounds containing one or more hydrocarbylene groups having more than two hydroxyl groups, may be present in a sufficient amount to form branched polymeric chains. One skilled in the art can calculate the desired amount of such polyols. The mole ratio of the polyols having more than two hydroxyl groups or to the dicarboxylates and / or anhydrides is from about 0.005:1 to about 0.075: or less. The polymerizable compositions may have any of the mole ratios of ingredients as disclosed herein. The polymers are prepared by first preparing an adduct of two dicarboxylates and / or anhydrides with the compound having at least two fused ring heterocycles. After formation of the adducts, the adducts are reacted with a plurality one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group to form the polymer. The water-soluble version of the polymer may be formed by contacting the polymer formed and a compound that forms a salt with the pendant carboxylate groups in water. The method of preparing the disclosed composition comprises adding the compound having at least two fused ring heterocycles to a reaction vessel, heating the reaction vessel to a temperature at which the compound having at least two fused ring heterocycles melts, adding the dicarboxylates or anhydrides to the reaction vessel at a mole ratio as disclosed herein, heating the reaction mixture formed to a temperature at which the dicarboxylates or anhydrides and the compound having at least two fused ring heterocycles form an adduct, removing water or the alcohol formed as a result of the adduct formation, cooling the formed adduct to about 1200C to 130 ° C and contacting the adduct formed with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols under conditions such that the hydroxyl groups of the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols react with the carboxylate groups at the end of the adducts to form a composition having a numberaverage molecular weight of from 1 ,000 to about 5,000,000 atomic mass units, 5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined as disclosed herein.

[0035] To form the adduct the compound having at least two fused ring heterocycles is heated to a temperature at which the compound is melted. The temperature for this step is based on the melting temperature of the compound having at least two fused ring heterocycles. The temperature can be determined by determining a temperature at which the compound having at least two fused ring heterocycles melts. The dicarboxylates and / or anhydrides are added to the melted compound having at least two fused ring heterocycles with agitation. The temperature of the reaction mixture formed is raised to a temperature at which the dicarboxylic acids or esters thereof or anhydrides will react with the hydroxyl groups of the compound having at least two fused ring heterocycles. The temperature for such reaction may about 150 °C or greater, about 170 °C or greater or about 210 °C or greater. The temperature may be about 250 °C or less, about 240 °C or less or about 210 °C or less. The by-product formed by the reaction of the dicarboxylates and / or anhydrides with the hydroxyl groups of the compound having at least two fused ring heterocycles is removed. The removal of the byproducts may be accomplished by application of any known method of removing volatile materials such as through the use of a vacuum, and the like. When the formation of the byproduct slows down the temperature of the reaction mixture is adjusted to a temperature at which the which the one or more diols of alkylene diols or polyoxyalkylene diols and one or more aliphatic diols containing a pendant carboxylate group, and optionally the polyols having on average more than two hydroxyl groups, react with the terminal carboxylates of the adducts. The temperature for such reaction may be about 150 °C or greater, about 175 °C or greater or about 205 °C or greater. The temperature of such reaction may be about 250 °C or less, about 225 °C or less or about 215 °C or less. This step is performed with agitation and the byproduct from the reaction of the hydroxyl groups and the carboxylate groups is removed from the reaction mixture. The by product is water when the carboxylate is a carboxylic acid or anhydride and an alcohol where the carboxylate is an ester. The adduct and with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are reacted until the formation of byproduct slows. When the formation of the byproduct slows the reaction mixture is held at the reaction temperature and the acid number of the polymer formed is monitored. The heating continues until the target acid number is reached. The acid number is as described above. The adduct and the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are reacted until the formation of byproduct slows.

[0036] The composition formed may be contacted with water and one or more compoundscapable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such that the carboxylate groups pendant from the composition form a salt with the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups to form a composition which is water-soluble, or which forms a stable dispersion in water.

[0037] Once the polymer formed has reached the target acid number it can be let down into water. The formed polymer may be cooled before being contacted with water or it may be contacted with water that is cooler than the polymer when formed in the previous reaction step. Cooling is not necessary but is desirable as control of reaction with the compound capable of forming a salt can be better controlled and by-product formation can be minimized. Cooling to any temperature at which these goals can be achieved is desired. Water can be added to the reaction vessel, or the polymer can be transferred to a vessel containing water. The formed polymer is contacted with a compound which forms a salt with the polymer in water. The polymer and compound which forms a salt may be added to water in any sequence. They may be added at the same time or the compound which forms the salt may be in the water when the polymer is added. The amount of water and polymer is chosen to provide the desired solids content and to form a solution or stable dispersion. The solids level may be about 20 percent by weight in water or greater based on the weight of the polymer and the compound capable of forming a salt, 30 percent by weight or greater, of about 40 percent by weight or greater or about 45 percent by weight or greater. The solids level may be about 70 percent by weight in water or less based on the weight of the polymer and the compound capable of forming a salt, about 60 percent by weight or less, about 55 percent by weight or less or about 50 percent by weight or less. The formation of the salt may be performed at any temperature at which a solution or stable dispersion forms at the desired solids level. Such temperature may be from about 20 °C to about 90 °C.

[0038] A stable dispersion of the polymer formed may formed as disclosed herein. Stable dispersion as used herein means the polymer remains suspended in water for up to about 3 months, up to about 6 months, up to about 9 months or up to about a year or more. Stable emulsions can be formed from polymers having a combination of an acid level as disclosed herein and a solids level in water as disclosed herein. Dispersions that may be stable for extended periods of time may have a combination of an acid level of about 40 mg KOH / gram or greater to about 60 mg KOH / gram or less and a solids level of about 45 percent by weight or greater to about 55 percent by weight or less.

[0039] A surfactant may be added to the polymer and the salt forming compound to aid in stabilizing the mixture in water and to aid in the formation of a stable dispersion. Any known surfactants which stabilize the mixture and / or the water-soluble or dispersible polymer may beutilized. A surfactant may be added after forming the salt of the polymer to stabilize the polymer salt in water. The formed polymer salt maybe transported and used in the form of a solution or dispersion in water, which may contain a surfactant. Any surfactant which stabilizes the solution or the dispersion may be used such as an anionic surfactant, a cationic surfactant or a nonionic surfactant. A nonionic surfactant may be used. Exemplary types of nonionic surfactants include fatty alcohols ethoxylates, alkyl phenol ethoxylates, fatty acid alkoxylates, polyglycerol alkyl ethers, glucosyl dialkyl ethers, crown ethers, ester-linked surfactants, polyoxyethylene alkyl ethers, sorbitan esters and polysorbates. Exemplary nonionic surfactants include (polyoxyethylene(20)sorbitan monolaurate. The surfactants may be utilized in a sufficient amount to stabilize the solutions or dispersions in water. During formation of the adducts, polymers or polymer salts additives may be added, for instance biocides, bactericides, heat stabilizers, dispersing agents, surfactants, and the like. The polymer salts in water may contain additives such as those disclosed herein. Useful additive types and additives include those utilized in the examples of this document.

[0040] The molecular weight of the polymers formed may be increased by a process of solid state polymerization. Solid -state polymerization may be carried out by heating the polymer at temperatures below its melting point but above its glass transition temperature. Post condensation occurs and the condensation byproducts can be removed by applying vacuum or inert gas. This can be performed before letting the polymer down into water to form the salt from or may be performed after formation of the polymer salt.

[0041] Films may be formed from the water-soluble or dispersible polymers disclosed by applying the polymers in water to a surface, removing the water by evaporation and allowing the polymers to form a film on the surface. The polymers may be contacted with a curing agent as disclosed in this document and cured. The film may be removed from the surface to which it was originally applied. The formed films upon removal may be discrete films that are self-supporting and can be used as free standing films.

[0042] Coatings and films prepared from the water-soluble or dispersible polymers disclosed may include additives common for coatings, Examples of coating additives include, but are not limited to, leveling, rheology, anti-block, and flow control agents such as silicones, fluorocarbons, urethanes, or cellulosics; extenders; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; drying agents; catalysts; or coalescing agents.

[0043] The polymers may be utilized as coatings. The polymers may be applied to a substratein the form of a melt and allowed to form discreet coating on the surface of the substrate. Alternatively, the polymers, such as in salt form, may be dissolved or dispersed in water may be applied to the surface of the substrate. The water may thereafter be evaporated off leaving the polymer on the surface of the substrate. The coatings may be cross linked with a material that reacts with or forms ionomers with the carboxylates or salts thereof, as disclosed herein.

[0044] The polyesters formed may be fully or partially bio sourced, which means the ingredients used to prepare them are derived from biological sources and not from petroleum based products. Bio sourced monomer content means the percentage by weight of the residue of the monomers in the polyesters derived from biologically based raw materials and not from petroleum based sources. Bio sourced monomers useful with the compositions described herein include monomers containing bio sourced carbon. The term bio sourced carbon means carbon obtained from a biological source rather than a fossil based source. The bio sourced content of a monomer, a copolymer, or a copolymer composition can be determined using a method such as ASTM D6866-08. ASTM D6866-08 provides three different methods for determining the bio sourced content of a solid, liquid, or gaseous composition. For example, the compositions described herein can be dried as a film and tested as a solid. As defined by ASTM D6866-08, bio sourced content is the amount of bio sourced carbon in the material or product as a percent of the weight (mass) of the total organic carbon in the product. In particular, ASTM D6866-08 Method B measures the ratios of 14C / 12C and 13C / 12C in the composition using Accelerator Mass Spectrometry (AMS) and Isotope Ratio Mass Spectrometry (IRMS). Fossil based carbon contains essentially no 14C because its age is much greater than the 5,730 year half-life of 14C. The presence and level of 14C in a composition provides a direct measure of the amount of carbon that originated from a source other than a fossil fuel, i.e., the level of bio sourced carbon in the composition. Carbon based on biological sources is referred to as modern carbon.

[0045] The polymers disclosed may contain 50 weight percent or greater of biologically sourced materials, 75 weight percent or greater of biologically sourced materials, or 100 weight percent of biologically sourced materials. Bio sourced materials include those derived from biomass, for example as a result of preparation via fermentation. The materials used to produce the polymers described herein may have a bio-content of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99%, up to 100%. In certain variations, materials are derived from renewable sources is used. In other variations, at least a portion of the materials used is derived from renewable sources, and at least a portion of the material is derived from non-renewable sources.

[0046] The polyester may have a biodegradability of at least 10%, at least 20%, at least 30%,at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99%, up to 100%. Biodegradable and biodegradability is as defined and determined based on ASTM D5338-15 (Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions, Incorporating Thermophilic Temperatures). Embodiments

[0047] 1. A composition comprising a plurality of adducts of two dicarboxylates or anhydrides, containing two carboxyl groups which form carboxylate groups, with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates or formed from the anhydrides and the composition contains pendant carboxylate groups.

[0048] 2. A composition according to Embodiment 1 , wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate or carboxyl groups, wherein the hydrocarbylene groups may be the same or different and may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0049] 3. A composition according to Embodiment 1 or 2, wherein the hydrocarbylene group of the dicarboxylates or anhydrides is a C 1-40 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

[0050] 4. A composition according to anyone of the preceding Embodiments, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic group between the carboxylate or carboxyl groups wherein the bivalent aliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0051] 5. A composition according to anyone of the preceding Embodiments wherein, the bivalent aliphatic group between the carboxylate or carboxyl groups is a C 1-40 bivalent aliphatic group, a C 2-35 bivalent aliphatic group, or a C 2-10 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0052] 6. A composition according to anyone of the preceding Embodiments wherein, the dicarboxylates or anhydrides comprise one or more of succinic acid, sebacic acid, furan dicarboxylic acid, itaconic acid, a C36 dimer acid, hydrogenated C36 dimer acid, adipic acid, azelaic acid, Dodecanedioic acid, dimethyl terephthalate, hexa-hydro phthalic anhydride, Isophthalic acid, Terephthalic acid or a short chained fatty acid.

[0053] 7. A composition according to anyone of the preceding Embodiments, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C5 rings.

[0054] 8. A composition according to anyone of the preceding Embodiments, wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.

[0055] 9. A composition according to anyone of the preceding Embodiments, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

[0056] 10. A composition according to anyone of the preceding Embodiments, wherein the fused rings of the compound having at least two fused ring heterocycles comprise the residue of isosorbide, isomanide, orjsoidide.

[0057] 11 . A composition according to any one of the preceding Embodiments, wherein the carboxylate groups are carboxylic acids.

[0058] 12. A composition according to any one of the preceding Embodiments, wherein the anhydride is a cyclic anhydride.

[0059] 13. A composition according to anyone of the preceding Embodiments, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2.6alkylene groups or C 6-8 cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

[0060] 14. A composition according to anyone of the preceding Embodiments, wherein the one or more diols comprise alkylene diols which contain C 2-6 alkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

[0061] 15. A composition according to anyone of the preceding Embodiments, wherein the one or more aliphatic diols containing a pendant carboxylate group comprise one or more C 2-10 aliphatic diols containing a pendant carboxylic acid group or one or more C 2-4 aliphatic diols containing a pendant carboxylic acid group.

[0062] 16. A composition according to any one of the preceding Embodiments, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.

[0063] 17. A composition according to anyone of the preceding Embodiments, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprises dimethylol propanoic acid.

[0064] 18. A composition according to any one of the preceding Embodiments, wherein a portion of the one or more diols of alkylene diols or polyoxyalkylene diols are replaced with one or more polyols having more than two hydroxyl groups.

[0065] 19. A composition according to any one of the preceding Embodiments, wherein the one or more polyols having more than two hydroxyl groups comprise one or more compounds containing one or more hydrocarbylene groups having three or more hydroxyl groups.

[0066] 20. A composition according to any one of the preceding Embodiments, which has an acid value of about 10 to about 40.

[0067] 21. A composition according to any one of the preceding Embodiments, wherein an oxygen of the pendant carboxylates is bonded to hydrogens or hydrocarbyl groups and the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with a cationic moiety derived from a compound capable of forming a cationic moiety which can form a salt with the pendant carboxylate group.

[0068] 22. A composition according to any one of the preceding Embodiments, wherein the hydrogens or hydrocarbyl groups on an oxygen of the pendant carboxylates are replaced with cationic moieties derived from ammonia or a nitrogen containing compound.

[0069] 23. A composition according to Embodiment 20 or 21 , which is soluble in or forms a stable dispersion in water.

[0070] 24. A composition according to any one of Embodiments 20 to 22 wherein the composition is dissolved or dispersed in water.

[0071] 25. A composition according to any one of Embodiments 20 to 23 wherein the composition has a pH of about 7.0 to about 7.9 when determined in water.

[0072] 26. A composition according to any one of Embodiments 20 to 23 wherein the composition exhibits a viscosity of about 100 Cp to about 100,000 cP, or about 500 cP to about 50,000 cP.

[0073] 27. A composition according to any one of the preceding Embodiments, having a number average molecular weight of about 1 .000 to about 500,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards.

[0074] 28. A composition according to any one of the preceding Embodiments, wherein the composition contains 50 weight percent or greater of biologically sourced materials, 75 weight percent or greater of biologically sourced materials, or 100 weight percent of biologically sourced materials.

[0075] 29. A composition according to any one of the preceding Embodiments, wherein theO O dicarboxylates correspond to formula 1, the compound having at least two fused ring heterocycles corresponds to formula 2:the one or more aliphatic diols containing a pendant carboxylate group corresponds to formula 3:and the one or more diols of alkylene diols or polyoxyalkylene diols correspond to formula 4:and the one or more anhydrides correspond to Formula 5;wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C2- aliphatic groups;R3is independently in each occurrence C2.6alkylene or C 6-8 cycloalkylene groups; x is independently in each occurrence an integer of from 2 to 4; y is independently in each occurrence an integer of 0 to 20.

[0076] 30. A composition according to any one of the preceding Embodiments, wherein the composition has a polymer with a backbone and the backbone of the composition corresponds to Formula 6:wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group or a salt forming cation;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C 2-10 aliphatic groups;R3is independently in each occurrence C 2-6 alkylene groups; y is independently in each occurrence an integer of 0 to 20; z is a real number such that the polymer formed is has a molecular weight of from 1 ,000 to about 5,000,000 atomic mass units, about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards; and, a and b in each unit are zero or 1 and the sum of a and b is 1 .

[0077] 31. A composition according to any one of the preceding Embodiments, wherein the polymer has an acid level of from about 40 mg KOH / gram or greater to about 60 mg KOH / gram or less and a solids level in an emulsion of about 45 percent by weight or greater to about 55 percent by weight or less.

[0078] 32. A composition according to Embodiment 31 , the polymer remains suspended in water for up to about 3 months, up to about 6 months, up to about 9 months or up to about a year or more.

[0079] 33. A composition according to any one of the preceding Embodiments, wherein the composition is crosslinked by reaction of the pendant carboxylate groups or salts thereof with a compound having two or more electrophilic groups or a compound which forms ionic groups with the pendant carboxylate groups or salts thereof.

[0080] 34. A composition comprising: a) one or more dicarboxylates or anhydrides; b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendantfrom each ring, wherein the fused ring compounds are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.2:1 to about 1 :1 ; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about mole 0.5:1 to about 5:1 ; and d) one or more aliphatic diols containing a pendant carboxylate group, wherein the aliphatic diols containing a pendant carboxylate group are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.05:1 to about 1 :1.

[0081] 35. A composition according to Embodiment 34 which forms a composition comprising a plurality of adducts of two dicarboxylates or anhydrides with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates and the composition contains pendant carboxylate groups.

[0082] 36. A composition according to Embodiment 34 or 35 comprising: e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups.

[0083] 37. A composition according to Embodiment 36, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups comprise one or more of ammonia or a nitrogen containing compound.

[0084] 38. A composition according to Embodiment 36, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups comprise one or more of ammonia or a compound containing a tertiary nitrogen.

[0085] 39. A composition according to Embodiment 37 or 38, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups are present is a sufficient amount such that the polymer formed exhibits a pH of from about 7.0 to about 8.0 in water.

[0086] 40. A composition according to any one of Embodiments 34 to 39, wherein a portion of the one or more diols of alkylene diols or polyoxyalkylene diols are replaced with f) one or more polyols having more than two hydroxyl groups, present in a sufficient amount to form branched polymer chains.

[0087] 41 . A composition according to any one of Embodiments 34 to 39, wherein the one or more polyols having more than two hydroxyl groups comprise one or more compounds containingone or more hydrocarbylene groups having three or more hydroxyl groups, present in a sufficient amount to form branched polymeric chains.

[0088] 42. A composition according to any one of Embodiments 34 to 41 , wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate groups, wherein the hydrocarbylene groups may be the same or different and may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0089] 43. A composition according to any one of Embodiments 34 to 42, wherein the hydrocarbylene group between the carboxylate groups of the dicarboxylates or anhydrides is a C i-4o hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

[0090] 44. A composition according to any one of Embodiments 34 to 42, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic group between the carboxylate groups wherein the bivalent aliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0091] 45. A composition according to any one of Embodiments 34 to 44, wherein the bivalent aliphatic group between the carboxylate groups of the dicarboxylates or anhydrides is a C 1-40 bivalent aliphatic group, a C 2-35 bivalent aliphatic group, or a C 2-10 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0092] 46. A composition according to any one of Embodiments 34 to 45, wherein the dicarboxylates or anhydrides comprise one or more of succinic acid, sebacic acid, furan dicarboxylic acid, itaconic acid, a C36 dimer acid, hydrogenated C36 dimer acid, adipic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate, hexa-hydro phthalic anhydride, Isophthalic acid, terephthalic acid or a short chained fatty acid.

[0093] 47. A composition according to any one of Embodiments 34 to 46, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C 5 rings.

[0094] 48. A composition according to any one of Embodiments 34 to 46, wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.

[0095] 49. A composition according to any one of Embodiments 34 to 48, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

[0096] 50. A composition according to any one of Embodiments 34 to 49, wherein the fused rings of the compound having at least two fused ring heterocycles comprise a residue of isosorbide, isomanide or isoidide.

[0097] 51 . A composition according to any one of Embodiments 34 to 50, wherein the carboxylate groups are carboxylic acids.

[0098] 52. A composition according to any one of Embodiments 34 to 51 , wherein the anhydride is a cyclic anhydride.

[0099] 53. A composition according to any one of Embodiments 34 to 52, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2.6alkylene groups or C 6-8 cycloalkylene groups, C2.alkylene groups or C2.3alkylene groups.

[0100] 54. A composition according to any one of Embodiments 34 to 53, wherein the one or more diols comprise alkylene diols which contain C2-6 alkylene groups, C2-4 alkylene groups or C2-3 alkylene groups.

[0101] 55. A composition according to any one of Embodiments 34 to 54, wherein the one or more aliphatic diols containing a pendant carboxylate group comprise one or more C 2-10 aliphatic diols containing a pendant carboxylic acid group or one or more C2-4 aliphatic diols containing a pendant carboxylic acid group.

[0102] 56. A composition according to any one of Embodiments 34 to 55, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.

[0103] 57. A composition according to any one of Embodiments 34 to 56, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprises dimethylol propanoic acid.

[0104] 58. A composition according to any one of Embodiments 34 to 57, wherein theO O dicarboxylates correspond to formula 1, the compound having at least two fused ring heterocycles corresponds to formula 2:the one or more aliphatic diols containing a pendant carboxylate group corresponds to formula 3:and the one or more diols of alkylene diols or polyoxyalkylene diols correspond to formula 4:and the one or more anhydrides correspond to Formula 5;wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C2- aliphatic groups;R3is independently in each occurrence C2.6alkylene or C 6-8 cycloalkylene groups; x is independently in each occurrence an integer of from 2 to 4; y is independently in each occurrence an integer of 0 to 20.

[0105] 59. A coating comprising a composition according to any one of Embodiments 1 to 33.

[0106] 60. An article comprising a substrate having a coating according to Embodiment 59 applied to a surface or a portion of a surface of the substrate.

[0107] 61. An article comprising a film prepared from a composition according to any one of Embodiments 1 to 33.

[0108] 62. A method of preparing a composition according to any one of Embodiments 1 to 33 comprising adding the compound having at least two fused ring heterocycles to a reaction vessel, heating the reaction vessel to a temperature at which the compound having at least two fused ring heterocycles melts, adding the dicarboxylates or anhydrides to the reaction vessel at a weight ratio of about 2 to 1 or greater, heating a reaction mixture formed to a temperature at which the dicarboxylates or anhydrides and the compound having at least two fused ring heterocycles form an adduct, removing water or an alcohol formed as a result of adduct formation, cooling the formed adduct to about 120 ° C to 130 ° C and contacting the adduct formed with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols under conditions such that the hydroxyl groups of the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols react with carboxylate groups at the end of the adduct to form a composition having a number average weight of from 1 ,000 to about 5,000,000 atomic mass units,5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards.

[0109] 63. A method according to Embodiment 62 wherein the adduct and the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are contacted and heated to a temperature of from about 1500C to 215 ° C.

[0110] 64. A method according to Embodiment 62 or 63, wherein the compound having at least two fused ring heterocycles and the dicarboxylates or anhydrides are reacted until the formation of byproducts slows down.

[0111] 65. A method according to any one of Embodiments 62 to 64, wherein the adduct and with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are reacted until the formation of byproduct slows.

[0112] 66. A method according to any one of Embodiments 62 to 65 wherein the composition formed is contacted with water and one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as ammonia or a nitrogen containing compound, under conditions such that the carboxylate groups pendant from the composition form a salt with a cationic moiety formed from one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as ammonia or a nitrogen containing compound, to form a composition which is water-soluble or which forms a stable dispersion in water.

[0113] 67. A method according to any one of Embodiments 62 to 66, wherein the fused ring compounds are present in a weight ratio to the one or more dicarboxylates or anhydrides of about weight 1 :5 to 1 :1 ; the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.5:1 to 5:1 and the aliphatic diols containing a pendant carboxylate group are present in a mole ratio of the aliphatic diols containing a pendant carboxylate group to the one or more dicarboxylates or anhydrides of about 0.05:1 to about 1 :1 .

[0114] 68. A method according to any one of Embodiments 62 to 67 wherein the composition formed is contacted with a compound having two or more electrophilic groups or a compound which forms ionic groups with the carboxylate groups, such as carboxylic acids, under conditions such that the composition is crosslinked through the pendant carboxylate groups or salts thereof.

[0115] 69. A method according to any one of Embodiments 62 to 68 wherein the composition formed is applied to a surface of a substrate and cured to form a coating.

[0116] 70. A method according to any one of Embodiments 60 to 69 wherein the composition formed is used to form a film.EXAMPLES

[0117] The following examples are provided to illustrate the invention but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated. IngredientsIsosorblde, biosourced;Succinic Acid , biosourced ;Propane diol, biosourced; PDODimethylolpropionic Acid; DMPAAmmonia 50 percent v / v in water;AcetoneBiocide containing 1.856 to 2.436 magnesium nitrate, 1.16 to 1.392 of 5-chloro-2-methyl-4- isophthiaazolin-3-one, and 0.212 nitiric acid copper(2+) salt in a solvent;Bactericide 19.8% aqueous solution of 1 ,2 benzoisothiazol-3(2H)-oneDispersant anionic, polymeric wetting and dispersing additive, Evonik TEGO Dispers755 W; Phosphite stabilizer.Melamine curing agent CYMEL® 303 LF resin having a structure ofCuring Catalyst Amine salt of an aromatic sulfonic acid in ethylene glycol, CYCAT® 4045 catalyst.

[0118] The experiments are performed according to the procedure described. Charge isosorbide to a round bottom-flask equipped with nitrogen sparge and agitation. Melt at 100 °C, start agitation, and then add succinic acid. Heat to a maximum of 225 °C while collecting water off the side through a condenser. When water slows, cool to 175 °C and add DMPA and PDO. Place Vigreaux column, then heat to a maximum of 210 °C. When water slows, remove column. Hold at 210 °C until acid value (AV) is 30 - 35. The formed reaction product is fed to a reaction vessel at ambient temperatures and then heated to 120 to 130 °C. The amount of base needed to neutralize the pendant acid is calculated. A premix of the calculated amount of ammonia, 50 / 50 v / v in water is added to additional water to form a premix. The temperature of the reactor is cooled to 95 °C and ammonia premix is added to the formed product over a time period of 0.5 to 3 hours.The heat is removed and the remainder of the water needed to achieve the desired solids level is added and the mixture is cooled to ambient temperature. The ingredients are reacted in mole ratios based on 100 moles of succinic acid. The isosorbide is reacted at a ratio of 55.6 moles to 100 moles of succinic acid. The propylene diol is reacted at a ratio of 33.0 moles to 100 moles of succinic acid. The dimethylolpropionic acid is reacted at a ratio of 22.2 moles to 100 moles of succinic acid. The formed polymer has a theoretical functionality of 2.0 and theoretical hydroxyl number of 57.1 and theoretical acid value of 57.1 , unless otherwise stated. Table 1 contains data about the polyesters prepared. The acid value is determined by dissolving ~ 1 g sample in 20 - 50 mL of toluene / methanol (80 / 20 by volume) using heat and a magnetic stirrer in a beaker. Cool to ambient temperature, about 23 ° C and add about 0.1 g phenolphthalein indicator. Titrate to a light pink endpoint using 0.1 M KOH in methanol. Acid value is calculated using the formula AV = (ml KOH final - mL KOH start) * 56.1 / sample weight. Viscosity is determined using a Brookfield viscometer using a spindle appropriate for the thickness of the sample and using. pH is determined by using a standard pH meter.

[0119] Table 11 . Material brittle. Example 3 contained 19.5 grams of dispersing agent.The polyester of Example 5 had the hydroxyl number measured at 91 .3.Table 1 Continued2. Mole ratio of isosorbide to succinic acid 60 to 100, Mole ratio of propy ene diol to succinic acid 32 to 100, and Mole ratio of dimethylol propionic acid to succinic acid 10 to 100. Theoretical OH solids 10.8 and pendant Acid Value calculated is 27.0.Examples 3 and 7B contained Biocide in 0.22 and 0.24 g respectively. Example 3 contained 0.05 g of bactericide. Example 3 used 250 g of acetone in the formation of the water dispersion.

[0120] The following conclusions can be gleaned from the examples. A robust composition that is fully dispersible in water is realized. These coating compositions can be applied effectively to a variety of substrates, revealing corrosion resistance, stain resistance and abrasion resistance. Furthermore, the use of toxic solvents is unnecessary.

[0121] Example 18 CoatingsA water-soluble polymer prepared as described in Example 7B at a 40 weight percent solids level is contacted with a melamine curing agent CYMEL 303 LF resin, at a ratio of 15 parts per hundred parts by weight of the water-soluble resin, and a curing catalyst, at a ratio of 1 .5 parts per hundred parts by weight of the water-soluble resin. Portions of the mixture are applied to cold rolled steel panels and cured at 130 °C for one hour. Several of such panels are used for testing of the coatings.

[0122] Dry film thickness is measured at 5 different points and averaged for each panel. Table 2 includes the results for gloss, Kbnig, and pencil hardness. Since gloss and Konig are not destructive tests, the same panels are also used for pencil hardness. Table 3 includes results for the crosshatch, mandrel bend, and impact tests. Tables 4 and 5 include the results for the 1 -hour and 16-hour chemical spot testing.

[0123] Table 2 - Gloss, Konig, and pencil hardness results* Above 125 in- b, cracks are observed where air bubbles were in the film. A coating with no defects may give a better result.Table 4 - 1 hour covered spot test resultsTable 4 - 16 hour covered spot test results

[0124] Test MethodsMandrel bend (conical) -ASTM D522Panels were observed after bending for cracks. The length of the crack from the narrow end toward the wide end of the panel was measured in millimeters. The test was performed in duplicate.Specular Gloss - ASTM D523Gloss was measured in two separate places on duplicate panels. The values for each panel were averaged. The 20°, 60°, and 85° gloss measurements were all recorded.Chemical spot testing (covered) - ASTM D1308Solvents used for spot tests were methanol, MEK, xylene, toluene, acetone, and 20% H2S04. A 1 -hour test and a 16-hour test were performed. The test was performed in duplicate.Impact resistance - ASTM D2794Both intrusion and extrusion tests were performed and were measured on separate panels. Therange of the test is from 6 in-lbs to 160 in-lbs. A failure at 6 or a pass at 160 were denoted as <6 or >160 respectively.Crosshatch adhesion -ASTM D3359Crosshatch adhesion was performed in two separate places on each panel. One panel was tested dry at standard conditions (23 ± 2 °C, 50 ± 5% humidity). A second panel was soaked in room temperature tap water for 18 hours before being blotted dry and immediately tested. Panels were rated on a scale of 0-5 with 0 denoting >65% loss of adhesion and 5 denoting no loss of adhesion. Pencil hardness -ASTM D3363Pencil hardness was performed on duplicate panels. The hardest pencil that glides across the surface of the coating without scratching it is taken as the pencil hardness. The letter B denotes softer pencils, with 9B being the softest. The letter H denotes harder pencils, with 9H being the hardest.Pendulum hardness (Kbnig) - ASTM D4366Pendulum hardness was measured by counts in three separate places on duplicate panels. The period of oscillation was measured on glass and was used to calculate the damping time.

[0125] Example 19A polymer is formed and let down into water as described hereinbefore. In forming the polymer 1620 g of isosorbide, 2182.0 g of succinic, 449.9 grams of Propane diol, biosourced, and 247.8 g of Dimethylolpropionic Acid are reacted. The mole ratios of the ingredients are 60.0, 100.0, 32.0 and 10.0 respectively. The final Acid Value is 51 .0. The charge is 4500 g. The solids level is 3,835 g and theoretical water loss is 665 g.ln the formation of the emulsion, 3800 g of the polymer, 3706.6 water, 207.7 of the ammonia solution, and 902 g of BC 820 bactericide is used. The formed emulsion exhibits a pH of 8.10, a solids level of 50.1 percent, a viscosity of 425,000 cPs at 20 °C using a #4 spindle at 1 rpm. A stable emulsion is formed.

Claims

Claims1 . A composition comprising a plurality of adducts of two dicarboxylates or anhydrides, which have two carboxyl groups which form two dicarboxylate groups, with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates or formed from the anhydrides and the composition contains pendant carboxylate groups.

2. A composition according to Claim 1 , wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate or carboxyl groups, wherein the hydrocarbylene groups may be the same or different and may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

3. A composition according to Claim 1 or 2, wherein the hydrocarbylene group of the dicarboxylates or anhydrides is a C 1-40 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

4. A composition according to anyone of the preceding claims, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic group between the carboxylate or carboxyl groups wherein the bivalent aliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

5. A composition according to anyone of the preceding claims wherein, the bivalent aliphatic group between the carboxylate or carboxyl groups is a C 1-40 bivalent aliphatic group, a C 2- 35 bivalent aliphatic group, or a C 2-10 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

6. A composition according to anyone of the preceding claims wherein, the dicarboxylates or anhydrides comprise one or more of succinic acid, sebacic acid, furan dicarboxylic acid, itaconic acid, a C36 dimer acid, hydrogenated C36 dimer acid, adipic acid, azelaic acid, Dodecanedioic acid, dimethyl terephthalate, hexa-hydro phthalic anhydride, Isophthalic acid, Terephthalic acid or a short chained fatty acid.

7. A composition according to anyone of the preceding claims, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C5 rings.

8. A composition according to anyone of the preceding claims, wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.

9. A composition according to anyone of the preceding claims, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

10. A composition according to anyone of the preceding claims, wherein the fused rings of the compound having at least two fused ring heterocycles comprise the residue of isosorbide, isomanide, or isoidide.1 1. A composition according to any one of the preceding claims, wherein the carboxylate groups are carboxylic acids.

12. A composition according to any one of the preceding claims, wherein the anhydride is a cyclic anhydride.

13. A composition according to anyone of the preceding claims, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2.6alkylene groups or C 6-8 cycloalkylene groups, C2.4alkylene groups or C 2-3 alkylene groups.

14. A composition according to anyone of the preceding claims, wherein the one or more diols comprise alkylene diols which contain C 2-6 alkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

15. A composition according to anyone of the preceding claims, wherein the one or more aliphatic diols containing a pendant carboxylate group comprise one or more C 2-10 aliphatic diols containing a pendant carboxylic acid group or one or more C 2-4 aliphatic diols containing a pendant carboxylic acid group.

16. A composition according to any one of the preceding claims, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.

17. A composition according to anyone of the preceding claims, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprises dimethylol propanoic acid.

18. A composition according to any one of the preceding claims, wherein a portion of the one or more diols of alkylene diols or polyoxyalkylene diols are replaced with one or more polyols having more than two hydroxyl groups.

19. A composition according to any one of the preceding claims, wherein the one or more polyols having more than two hydroxyl groups comprise one or more compounds containing one or more hydrocarbylene groups having three or more hydroxyl groups.

20. A composition according to any one of the preceding claims, which has an acid value of about 10 to about 40.21 . A composition according to any one of the preceding claims, wherein an oxygen of the pendant carboxylates is bonded to hydrogens or hydrocarbyl groups and the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with a cationic moiety derived from a compound capable of forming a cationic moiety which can form a salt with the pendant carboxylate group.

22. A composition according to any one of the preceding claims, wherein the hydrogens or hydrocarbyl groups on an oxygen of the pendant carboxylates are replaced with cationic moieties derived from ammonia or a nitrogen containing compound.

23. A composition according to Claim 20 or 21 , which is soluble in or forms a stable dispersion in water.

24. A composition according to any one of Claims 20 to 22 wherein the composition is dissolved or dispersed in water.

25. A composition according to any one of Claims 20 to 23 wherein the composition has a pH of about 7.0 to about 7.9 when determined in water.

26. A composition according to any one of Claims 20 to 23 wherein the composition exhibits a viscosity of about 100 Cp to about 100,000 cP, or about 500 cP to about 50,000 cP.

27. A composition according to any one of the preceding claims, having a number average molecular weight of about 1.000 to about 500,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards.

28. A composition according to any one of the preceding claims, wherein the composition contains 50 weight percent or greater of biologically sourced materials, 75 weight percent or greater of biologically sourced materials, or 100 weight percent of biologically sourced materials.

29. A composition according to any one of the preceding claims, wherein the dicarboxylates correspond to formula 1, the compound having at least two fused ring heterocycles corresponds to formula 2:the one or more aliphatic diols containing a pendant carboxylate group corresponds toformulaand the one or more diols of alkylene diols or polyoxyalkylene diols correspond to formulaand the one or more anhydrides correspond to Formula 5;wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C 2-10 aliphatic groups;R3is independently in each occurrence C 2-6 alkylene or C 6-8 cycloalkylene groups; x is independently in each occurrence an integer of from 2 to 4; y is independently in each occurrence an integer of 0 to 20.

30. A composition according to any one of the preceding claims, wherein the composition has a polymer with a backbone and the backbone of the composition corresponds to Formula 6:wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group or a salt forming cation;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C 2-10 aliphatic groups;R3is independently in each occurrence C 2-6 alkylene groups; y is independently in each occurrence an integer of 0 to 20; z is a real number such that the polymer formed is has a molecular weight of from 1 ,000 to about 5,000,000 atomic mass units, about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards; and, a and b in each unit are zero or 1 and the sum of a and b is 1 .

31. A composition according to any one of the preceding claims, wherein the polymer has an acid level of from about 40 mg KOH / gram or greater to about 60 mg KOH / gram or less and a solids level in an emulsion of about 45 percent by weight or greater to about 55 percent by weight or less.

32. A composition according to Claim 31 , the polymer remains suspended in water for up to about 3 months, up to about 6 months, up to about 9 months or up to about a year or more.

33. A composition according to any one of the preceding claims, wherein the composition is crosslinked by reaction of the pendant carboxylate groups or salts thereof with a compound having two or more electrophilic groups or a compound which forms ionic groups with the pendant carboxylate groups or salts thereof.

34. A composition comprising: a) one or more dicarboxylates or anhydrides; b) one or more compounds having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring, wherein the fused ring compounds are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.2:1 to about 1 :1 ; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about mole 0.5:1 to about 5:1 ; and d) one or more aliphatic diols containing a pendant carboxylate group, wherein the aliphatic diols containing a pendant carboxylate group are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.05:1 to about 1 :1.

35. A composition according to Claim 34 which forms a composition comprising a plurality of adducts of two dicarboxylates or anhydrides with a compound having at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur and at least one hydroxyl group pendant from each ring wherein the plurality of adducts are linked by a plurality of residues of one or more diols of alkylene diols or polyoxyalkylene diols and a plurality of one or more aliphatic diols containing a pendant carboxylate group wherein ester groups are formed by reaction of the hydroxyl groups of the fused ring compounds and the diols with the carboxylate groups of the dicarboxylates and the composition contains pendant carboxylate groups.

36. A composition according to Claim 34 or 35 comprising: e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups.

37. A composition according to Claim 36, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups comprise one or more of ammonia or a nitrogen containing compound.

38. A composition according to Claim 36, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups comprise one or more of ammonia or a compound containing a tertiary nitrogen.

39. A composition according to Claim 37 or 38, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups are present is a sufficient amount such that the polymer formed exhibits a pH of from about 7.0 to about 8.0 in water.

40. A composition according to any one of Claims 34 to 39, wherein a portion of the one or more diols of alkylene diols or polyoxyalkylene diols are replaced with f) one or more polyols having more than two hydroxyl groups, present in a sufficient amount to form branched polymer chains.41 . A composition according to any one of Claims 34 to 39, wherein the one or more polyols having more than two hydroxyl groups comprise one or more compounds containing one or more hydrocarbylene groups having three or more hydroxyl groups, present in a sufficient amount to form branched polymeric chains.

42. A composition according to any one of Claims 34 to 41 , wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate groups, wherein the hydrocarbylene groups may be the same or different and may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

43. A composition according to any one of Claims 34 to 42, wherein the hydrocarbylene group between the carboxylate groups of the dicarboxylates or anhydrides is a C 1-40 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

44. A composition according to any one of Claims 34 to 42, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic group between the carboxylate groups wherein the bivalent aliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

45. A composition according to any one of Claims 34 to 44, wherein the bivalent aliphatic group between the carboxylate groups of the dicarboxylates or anhydrides is a C 1-40 bivalent aliphatic group, a C 2-35 bivalent aliphatic group, or a C 2-10 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

46. A composition according to any one of Claims 34 to 45, wherein the dicarboxylates or anhydrides comprise one or more of succinic acid, sebacic acid, furan dicarboxylic acid, itaconic acid, a C36 dimer acid, hydrogenated C36 dimer acid, adipic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate, hexa-hydro phthalic anhydride, Isophthalic acid, terephthalic acid or a short chained fatty acid.

47. A composition according to any one of Claims 34 to 46, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C 5 rings.

48. A composition according to any one of Claims 34 to 46, wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.

49. A composition according to any one of Claims 34 to 48, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

50. A composition according to any one of Claims 34 to 49, wherein the fused rings of the compound having at least two fused ring heterocycles comprise a residue of isosorbide, isomanide or isoidide.51 . A composition according to any one of Claims 34 to 50, wherein the carboxylate groups are carboxylic acids.

52. A composition according to any one of Claims 34 to 51 , wherein the anhydride is a cyclic anhydride.

53. A composition according to any one of Claims 34 to 52, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2-6alkylene groups or C 6-8 cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

54. A composition according to any one of Claims 34 to 53, wherein the one or more diols comprise alkylene diols which contain C 2-6 alkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

55. A composition according to any one of Claims 34 to 54, wherein the one or more aliphatic diols containing a pendant carboxylate group comprise one or more C 2 -10 aliphatic diols containing a pendant carboxylic acid group or one or more C 2-4 aliphatic diols containing a pendant carboxylic acid group.

56. A composition according to any one of Claims 34 to 55, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.

57. A composition according to any one of Claims 34 to 56, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprises dimethylol propanoic acid.

58. A composition according to any one of Claims 34 to 57, wherein the dicarboxylates correspond to formula 1, the compound having at least two fused ring heterocycles corresponds to formula 2:the one or more aliphatic diols containing a pendant carboxylate group corresponds to formulaand the one or more diols of alkylene diols or polyoxyalkylene diols correspond to formulaand the one or more anhydrides correspond to Formula 5;wherein D is independently in each occurrence a structure comprising at least two fused ring heterocycles wherein each heterocycle contains a heteroatom of oxygen or sulfur;R is independently in each occurrence hydrogen or a hydrocarbyl group;R1is independently in each occurrence a hydrocarbylene group;R2is independently in each occurrence one or more C 2-10 aliphatic groups;R3is independently in each occurrence C2.6alkylene or C 6-8 cycloalkylene groups; x is independently in each occurrence an integer of from 2 to 4; y is independently in each occurrence an integer of 0 to 20.

59. A coating comprising a composition according to any one of Claims 1 to 33.

60. An article comprising a substrate having a coating according to Claim 59 applied to a surface or a portion of a surface of the substrate.61 . An article comprising a film prepared from a composition according to any one of Claims 1 to 33.

62. A method of preparing a composition according to any one of Claims 1 to 33 comprising adding the compound having at least two fused ring heterocycles to a reaction vessel, heating the reaction vessel to a temperature at which the compound having at least two fused ring heterocycles melts, adding the dicarboxylates or anhydrides to the reaction vessel at a weight ratio of about 2 to 1 or greater, heating a reaction mixture formed to a temperature at which the dicarboxylates or anhydrides and the compound having at least two fused ring heterocycles form an adduct, removing water or an alcohol formed as a result of adduct formation, cooling the formed adduct to about 1200C to 1300C and contacting the adduct formed with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols under conditions such that the hydroxyl groups of the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols react with carboxylate groups at the end of the adduct to form a composition having a number average weight of from 1 ,000 to about 5,000,000 atomic mass units, 5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units as determined by gel permeation chromatography using polystyrene standards.

63. A method according to Claim 62 wherein the adduct and the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are contacted and heated to a temperature of from about 150 ° C to 215 ° C.

64. A method according to Claim 62 or 63, wherein the compound having at least two fused ring heterocycles and the dicarboxylates or anhydrides are reacted until the formation of byproducts slows down.

65. A method according to any one of Claims 62 to 64, wherein the adduct and with the one or more aliphatic diols containing a pendant carboxylate group and the one or more diols of alkylene diols or polyoxyalkylene diols are reacted until the formation of byproduct slows.

66. A method according to any one of Claims 62 to 65 wherein the composition formed is contacted with water and one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as ammonia or a nitrogen containing compound, under conditions such that the carboxylate groups pendant from the composition form a salt with a cationic moiety formed from one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, such as ammonia or a nitrogen containing compound, to form a composition which is water- soluble or which forms a stable dispersion in water.

67. A method according to any one of Claims 62 to 66, wherein the fused ring compounds are present in a weight ratio to the one or more dicarboxylates or anhydrides of about weight 1 :5 to 1 :1 ; the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the one or more dicarboxylates or anhydrides of about 0.5:1 to 5:1 and the aliphatic diols containing a pendant carboxylate group are present in a mole ratio of the aliphatic diols containing a pendant carboxylate group to the one or more dicarboxylates or anhydrides of about 0.05:1 to about 1 :1.

68. A method according to any one of Claims 62 to 67 wherein the composition formed is contacted with a compound having two or more electrophilic groups or a compound which forms ionic groups with the carboxylate groups, such as carboxylic acids, under conditions such that the composition is crosslinked through the pendant carboxylate groups or salts thereof.

69. A method according to any one of Claims 62 to 68 wherein the composition formed is applied to a surface of a substrate and cured to form a coating.

70. A method according to any one of Claims 60 to 69 wherein the composition formed is used to form a film.

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