Biodegradable polyesters useful as adhesives

Abstract

Disclosed are biodegradable polyesters. Methods for their production and adhesives prepared therefrom. The polyesters comprise a plurality of adducts of two dicarboxylates or anhydrides with a compound having at least two fused ring heterocycles containing a heteroatom and a hydroxyl group pendant from each ring, the adducts are linked by the 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. 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, wherein the composition contains two dicarboxylates, a first dicarboxylate or an anhydride containing between the carboxylate or carboxyl groups a C1-8 hydrocarbylene group and a second dicarboxylate containing between the carboxylate groups a C9-60 hydrocarbylene group.

Description

Attorney Docket: DASC-101 -B-WO PATENTBIODEGRADABLE POLYESTERS USEFUL AS ADHESIVESFIELD

[0001] Disclosed are biodegradable polyesters which may be prepared from bio sourced materials, which can be waterborne and have high performance properties as adhesives. 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 adhesive 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 adhesive applications. This facilitates the application of adhesives using water and 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 adhesive properties in a variety of adhesive applications.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, wherein the composition contains two dicarboxylates, a first dicarboxylate or an anhydride containing between the carboxylate groups or carboxyl groups, a C i-8hydrocarbylene group and a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group. 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 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. The mole ratio of the first dicarboxylate to second dicarboxylate is from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1.

[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 C 2-4 alkylene groups. The polyols can be diols and polyols having more that 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 diols containing 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 carboxylate groups with one or more compounds which forms a cationic group which forms 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) two or more dicarboxylates or anhydrides comprising: i) a first dicarboxylate containing between the carboxylate groups a C 1 - 8 hydrocarbylene group or is an anhydride, and, ii) a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group; 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 ringcompounds may be present in a mole ratio to the two 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 two 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 two 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 moiety which can form a salt with the pendant carboxylate groups comprise one or more of. 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 or salts thereof 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 adhesive prepared from the compositions as disclosed herein. Disclosed are articles comprising a substrate having a coating or adhesives as disclosed herein applied to a surface or a portion of a surface of the substrate. Disclosed are laminates prepared from a composition as disclosed herein. The adhesives may be in the form of a film.

[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 two dicarboxylates or anhydrides to the reaction vessel at a mole ratio of the two dicarboxylates or anhydrides to the fused ring heterocycles 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, 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 determinedby 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, such as 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, nitrogen containing compounds 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. The composition formed may be used to form a film having adhesive properties. The polymer composition formed may be utilized to bond one substrate to a second substrate or to another surface.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 500 cP to about 50,000 cP, 1 ,000 cP 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. The disclosed polymers may be utilized as an adhesive and exhibit good adhesive properties.DETAILED DESCRIPTION OF THE INVENTION

[0012] 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.

[0013] 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 ormore 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. Valence as used herein means a covalent bond between a 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 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 and commercially available software to calculate the molecular weight. 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.

[0014] Disclosed are compositions comprising a plurality of adducts prepared from a) two of two 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 dicarboxylates comprise a first dicarboxylate containing between the carboxylate groups a C 1 -8 hydrocarbylene group or is an anhydride and a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group. The mole ratio of the first dicarboxylate to second dicarboxylate may be from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1. 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 ormore 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 thereof 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 form a salt with the pendant carboxylate group. 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 compositions comprising 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.

[0015] The adducts may be formed from a) two of the two 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 composition contains two dicarboxylates, a first dicarboxylate containing between the carboxylate groups a C 1-8 hydrocarbylene group or is an anhydride and a second dicarboxylate containing between the carboxylate groups a C 9.60 hydrocarbylene group. 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 i-6o hydrocarbylene group which may contain a heteroatom of oxygen or sulfur or one or more double bonds. The bivalent aliphatic group between the carboxylate groups of the first dicarboxylate is a C 1-8 bivalent aliphatic or cycloaliphatic group, a C 2-6 bivalent aliphatic group, or a C 2-4 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. The bivalent aliphatic group between thecarboxylate groups of the second dicarboxylate is a C 9-60 bivalent aliphatic group, a C 9-40 bivalent aliphatic group, or a C 1240 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms 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. The dicarboxylate thereof may correspond to one of the formulas 1 or 1 A: 0 0 0 0R - O - C - R1— C - O - R i or H - O - C - R1— C - O - H IA, 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.

[0016] Exemplary dicarboxylates may be bio sourced or derived from petroleum based feed stocks. Exemplary dicarboxylates may be dicarboxylic acids or esters thereof. Exemplary first dicarboxylates may be one or more of oxalic acid, malonic, succinic acid, glutaric acid, furan dicarboxylic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, 1 ,4-cyclohexane dicarboxylic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, dimethyl terephthalate, Terephthalic acid and esters thereof. Exemplary second dicarboxylates may be the second dicarboxylates comprise one or more of sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, docosanedioic acid, triacontanedioic acid, 2-decenedioic acid, dodec-2-enedioic acid, glutinic acid (Allene-1 ,3- dicarboxylic acid), citraconic acid, mesaconic acid, a C 20-60 dimer acid, hydrogenated C 20-60 dimer acid, or esters thereof. Exemplary cyclic anhydrides include succinic anhydride, maleic anhydride hexa-hydro phthalic anhydride, phthalic anhydride. Exemplary dicarboxylic acids derived from petroleum based feed stocks include adipic, azelaic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, maleic acid and phthalic 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, and citric acid. Any of the disclosed dicarboxylic acids can be used in the esterified form. Exemplary dicarboxylate esters include dialkyl terephalates, such as dimethyl terephthalates.

[0017] The adducts may be formed form anhydrides. Any anhydride which reacts with the one or more compounds having at least two fused ring heterocycles and which forms an adduct withan 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 is 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, hexahydro phthalic anhydride.

[0018] The one or more 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 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 at least 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.

[0019] 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 form polymer chains with the desired amount of branching. A mixture of diols and polyols having onaverage 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-F-O - R3-j-O - H polyoxyalkylene diols may correspond to formula 4: ' 4 , 4 wherein R3 is 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 and 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.

[0020] 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 2-10 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 apendant carboxylate group may correspond to formulawherein R is as defined herein and R2 is independently in each occurrence one or more C 2-10 aliphatic groups. Exemplary aliphatic diols containing a pendant carboxylate group corresponds to formula

[0021] 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 composition contains two dicarboxylates, a first dicarboxylate containing between the carboxylate groups a C i-8hydrocarbylene group or is an anhydride and a second dicarboxylate containing between the carboxylate groups a C 9.60 hydrocarbylene group. 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 with one or more compounds having two or more electrophilic groups which react with the carboxylate groups, such as carboxylic acids. The pendant carboxylate groups may be reacted with a compound that forms ionomeric bonds with the pendant carboxylate group, such as carboxylic acid groups.

[0022] 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.

[0023] 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.

[0024] 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 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 1-4 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.

[0025] R1may be separately in each occurrence a hydrocarbylene group may contain one or more double bonds, may be optionally a heteroatom or a heteroatom containing functional group. R1may be separately in each occurrence a C 1 20 hydrocarbylene group 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 group. With respect to the first dicarboxylate, R1may be separately in each occurrence a C 1-8 bivalent aliphatic or cycloaliphatic group, a C 2-6 bivalent aliphatic group, or a C 2-4 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. With respect to the second dicarboxylate, R1 may be separately in each occurrence a C 9.60 bivalent aliphatic group, a C 9-40 bivalent aliphatic group, or a C 12-40 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms of oxygen or sulfur and / or one or more double bonds.

[0026] 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-s 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 eachoccurrence 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 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.

[0027] 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 500 atomic mass units or greater, about 1 ,000 atomic mass units or greater, about 5,000 atomic mass units or greater, 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 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 by 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. 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 titled, Determintion of Total acid number according to ASTM 664 available from SI Analytics.

[0028] 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 that the nitrogen compounds or salts may come into contact with.Exemplary nitrogen containing compound include tertiary amines guanidines, imidazolines, pyridines, pyrrolidines or piperdines and the like. The nitrogen containing compounds may be trihydrocarbyl 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.

[0029] 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.

[0030] The relative amounts of the recited components are chosen to prepare a polymer having the desired molecular weights, acid numbers, water solubility or dispersibility, and other desired properties, such as good adhesion properties. The relative amounts of ingredients can be expressed as mole ratios of each ingredient as compared to dicarboxylate and / or anhydride. 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, about0.21 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.

[0031] 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, melamine and isothiocyanate groups or mixtures thereof. The electrophilic groups may be isocyanate, epoxide groups, and melamine groups. All or a portion of the pendant carboxylate groups or slats 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 the crosslinked polymers.

[0032] The polymers may be crosslinked by ionomeric groups by contacting the pendant carboxylate groups or salt 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, or salts thereof. 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.

[0033] Disclosed are compositions that can be utilized to prepare the polyester polymers disclosed herein. The disclosed compositions may be characterized as polymerizable composition. Such compositions when reacted as described herein may form the disclosed polyester polymers. Disclosed is a composition comprising; a) two or more dicarboxylates or anhydrides comprising: i) a first dicarboxylate containing between the carboxylate groups a C 1 - 8 hydrocarbylene group or is an anhydride, and, ii) a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group; 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 ringcompounds are present in a mole ratio to the two or more dicarboxylates or anhydrides of about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1 .; 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 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 moles. 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 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, which may be present in a sufficient amount to form branched polymeric chains. The one or more polyols having more than two hydroxyl groups may comprise one or more compounds containing one or more hydrocarbylene groups having three or more 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.

[0034] 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 pendantcarboxylate 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 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 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, 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 using 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 reactionmay 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. 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 monitored as described above. 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.

[0036] The composition formed may contacted with water and one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups, 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 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 or a combination thereof. 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. 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 stabledispersion 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 be utilized. 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 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. 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.

[0040] 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 asdisclosed 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.

[0041] Adhesives and films prepared from the water soluble or dispersible polymers disclosed may include additives common for adhesives, Examples of such additives include, but are not limited to, adhesion promoters, 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; antiskinning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; drying agents; catalysts; fillers or coalescing agents.

[0042] The polymers may be utilized as adhesives. The polymers may be applied to a substrate allowed to form discreet coating on the surface of the substrate. Alternatively, the polymers, such as in the 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, as disclosed hereinbefore.

[0043] 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 ofcarbon 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.

[0044] 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.

[0045] 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).

[0046] Embodiments1 . A composition 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, wherein the composition contains two dicarboxylates, a first dicarboxylate or is an anhydride which forms two carboxylate groups containing between the carboxylate groups a C i-8hydrocarbylene group and a second dicarboxylate containing between the carboxylate groups a C 9.60 hydrocarbylene group.2. A composition according to Embodiment 1 , wherein the first dicarboxylate and second dicarboxylate are present in a mole ratio of from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1.3. A composition according to Embodiment 1 , wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate groups or carboxyl groups, wherein the hydrocarbylene groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.4. A composition according to Embodiment 1 or 2, wherein the hydrocarbylene group is a C 1-60 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.5. A composition according to anyone of the preceding Embodiments, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic or cycloaliphatic group between the carboxylate or carboxyl groups wherein the bivalent aliphatic or cycloaliphatic group 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 Embodiments wherein, the bivalent aliphatic group between the carboxylate or carboxyl groups of the first dicarboxylate or anhydride is a C i s bivalent aliphatic or cycloaliphatic group, a C2-6bivalent aliphatic group, or a C 2-4 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.7. A composition according to anyone of the preceding Embodiments wherein, the bivalent aliphatic group between the carboxylate groups of the second dicarboxylate is a C 9-60 bivalent aliphatic group, a C 9.40 bivalent aliphatic group, or a C 12-40 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms of oxygen or sulfur and / or one or more double bonds.8. A composition according to anyone of the preceding Embodiments wherein, the first dicarboxylates, including anhydrides comprise one or more of oxalic acid, malonic, succinic acid, glutaric acid, , furan dicarboxylic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, 1 ,4- cyclohexane dicarboxylic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, succinic anhydride, maleic anhydride hexa-hydro phthalic anhydride, phthalic anhydride, dimethyl terephthalate, terephthalic acid and esters thereof.9. A composition according to anyone of the preceding Embodiments wherein, the second dicarboxylates comprise one or more of sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, docosanedioic acid, triacontanedioic acid, 2-Decenedioic acid2Dodec-2-enedioic acid, Glutinic acid (Allene-1 ,3- dicarboxylic acid), Citraconic acid, Mesaconic acid, Dodecanedioic acid, a C20-60 - dimer acid, hydrogenated C20-60 dimer acid, or esters thereof,.10. 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.1 1. 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.12. 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.13. 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 or isoidide.14. A composition according to any one of the preceding Embodiments, wherein the carboxylate groups are carboxylic acids.15. A composition according to any one of the preceding Embodiments, wherein the anhydride is a cyclic anhydride.16. A composition according to anyone of the preceding Embodiments, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2-6 alkylene groups or C 6-8 cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.17. 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.18. 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.19. 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.20. A composition according to anyone of the preceding Embodiments, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise dimethylol propanoic acids.21 . 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.22. A composition according to any one of the preceding Embodiments, wherein the one or more polyols having three or more hydroxyl groups comprise one or more compounds containing one or more hydrocarbylene groups having three or more hydroxyl groups.23. A composition according to any one of the preceding Embodiments, which has an acid value of about 10 to about 40 determined according to methods disclosed herein.24. A composition according to any one of the preceding Embodiments, wherein the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with a cationic moiety which forms a salt with the pendant carboxylate group.25. A composition according to any one of the preceding Embodiments, wherein the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with cations derived from ammonia or tertiary amines.26. A composition according to Embodiment 24 or 25, which is soluble in or forms a stable dispersion in water.27. A composition according to any one of Embodiments 24 to 26 wherein the composition is dissolved or dispersed in water.28. A composition according to any one of Embodiments 24 to 27 wherein the composition has a pH of about 7.0 to about 8.0 when determined in water.29. A composition according to any one of Embodiments 20 to 23 wherein the composition exhibits a viscosity of about 500 cP to about 50,000 cP, or about 1000 cP to about 50,000 cPs.30. 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.31. A composition according to any one of the preceding Embodiments, wherein the composition contains 50 mole percent or greater of biologically sourced materials, 75 mole percent or greater of biologically sourced materials, or 100 mole percent of biologically sourced materials.32. 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 formulaand 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 for the first dicarboxylate is a C i-8hydrocarbylene group and for the second dicarboxylate a C 9-60 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 20.33. A composition according to any one of the preceding Embodiments, comprising a polymer having a polymer backbone which 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 wherein for the first dicarboxylate the hydrocarbylene groups is a C i-8hydrocarbylene group and for the second dicarboxylate a C 9-60 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 has a number average molecular weight 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 .34. A composition according to any one of the preceding Embodiments, wherein the composition is 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.35. A composition comprising: a) two or more dicarboxylates or anhydrides, having two carboxyl groups which form two carboxylate groups, comprising: i) a first dicarboxylate or anhydride containing between the carboxylate or carboxyl groups a C 1-8 hydrocarbylene group, and, ii) a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group; 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 two or more dicarboxylates or anhydrides of about 1 :1 to about 5:1 moles; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the two 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 two or more dicarboxylates or anhydrides of about 1 :20 to about 1 :1 .36. A composition according to Embodiment 35, wherein the mole ratio of the first dicarboxylate to second dicarboxylate is from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1.37. A composition according to Embodiment 35 or 36 which forms a composition comprising a plurality of adducts of two of the first dicarboxylates or anhydrides and second dicarboxylates 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.38. A composition according to any one of Embodiments 35 to 37 comprising: e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups.39. A composition according to Embodiment 38, 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.40. A composition according to Embodiment 38, 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.41 . A composition according to Embodiment 35 or 40, 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 composition when in water exhibits a pH of from about 7.0 to about 8.0.42. A composition according to any one of Embodiments 35 to 41 , 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 polymeric chains.43. A composition according to any one of Embodiments 35 to 42, 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.44. A composition according to any one of Embodiments 35 to 43, wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate groups, wherein the hydrocarbylene groups 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 Embodiments 35 to 44, wherein the hydrocarbylene group is a C 1-60 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.46. A composition according to any one of Embodiments 35 to 45, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic or cycloaliphatic group between the carboxylate groups wherein the bivalent aliphatic or cycloaliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.47. A composition according to anyone of Embodiments 35 to 46, the bivalent aliphatic group between the carboxylate groups of the first dicarboxylate is a C i-8bivalent aliphatic or cycloaliphatic group, a C2.6bivalent aliphatic group, or a C2.4bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.48. A composition according to anyone of Embodiments 35 to 47 wherein, the bivalent aliphatic group between the carboxylate groups of the second dicarboxylate is a C 9 eo bivalent aliphatic group, a C 9-40 bivalent aliphatic group, or a C i2.o bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms of oxygen or sulfur and / or one or more double bonds.49. A composition according to any one of Embodiments 35 to 48 wherein, the first dicarboxylates, including anhydrides comprise one or more of oxalic acid, malonic, succinic acid, glutaric acid, furan dicarboxylic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, 1 ,4- cyclohexane dicarboxylic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, succinic anhydride, maleic anhydride hexa-hydro phthalic anhydride, phthalic anhydride, terephthalic acid and esters thereof.50. A composition according to anyone of Embodiments 35 to 49 wherein, the second dicarboxylates comprise one or more of sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, docosanedioic acid, triacontanedioic acid, 2-Decenedioic acid, Dodec-2-enedioic acid, Glutinic acid (Allene-1 ,3- dicarboxylic acid), Citraconic acid, Mesaconic acid, a C20-60 - dimer acid, hydrogenated C20-60 dimer acid, or esters thereof.51. A composition according to any one of Embodiments 35 to 50, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C5 rings.52. A composition according to any one of Embodiments 35 to 51 , wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.53. A composition according to any one of Embodiments 35 to 52, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.54. A composition according to any one of Embodiments 35 to 53, wherein the fused rings of the compound having at least two fused ring heterocycles comprise a residue of isosorbide, isomanide, or isoidide.55. A composition according to any one of Embodiments 35 to 54, wherein the carboxylate groups are carboxylic acids.56. A composition according to any one of Embodiments 35 to 55, wherein the anhydride is a cyclic anhydride.57. A composition according to any one of Embodiments 35 to 56, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C2.6alkylene groups or C6-s cycloalkylene groups, C2.4alkylene groups or C 2-3 alkylene groups.58. A composition according to any one of Embodiments 35 to 57, 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.59. A composition according to any one of Embodiments 35 to 58, 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.60. A composition according to any one of Embodiments 35 to 59, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.61 . A composition according to any one of Embodiments 35 to 60, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise dimethylol propanoic acids.62. A composition according to any one of Embodiments 35 to 61 , 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 formulaand 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 for the first dicarboxylate is a C 1 8 hydrocarbylene group and for the second dicarboxylate a C 9-60 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 20.63. A method of preparing a composition according to any one of Embodiments 1 to 34 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 two dicarboxylates or anhydrides to the reaction vessel at a mole ratio of about 2 to 1 or greater, heating the reaction vessel 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 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 the carboxylate groups at an end of the adducts to form a composition having a number average molecular weight of from 1 ,000 to about5,000,000 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.64. A method according to Embodiment 63 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.65. A method according to Embodiment 63 or 64, wherein the compound having at least two fused ring heterocycles and the dicarboxylates or anhydrides are reacted until the formation of byproducts slows down.66. A method according to any one of Embodiments 63 to 65, 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 reacted until the formation of byproduct slows.67. A method according to any one of Embodiments 63 to 66 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 tertiary amine, 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 ammonia or a tertiary amine, to form a composition which is water soluble or which forms a stable dispersion in water.68. A method according to any one of Embodiments 60 to 64, 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 :1.69. A method according to any one of Claims 62 to 69 wherein the composition formed is contacted with a compound having two or more electrophilic groups or a compound which forms ionic groups with carboxylate groups, such as carboxylic acids, under conditions such that the composition is crosslinked through the pendant carboxylate groups, such as carboxylic acids.Examples

[0047] 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;Dimer fatty acid - hydrogenated C 36 dimerdicarboxylic acid, Biosourced Propylene diol, biosourced;Dimethylolpropionic Acid;Ammonia 50 percent v / v in water;Biocide 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; non-ionic surfactant poly(oxyethylene)n-sorbitan-monolaurate, Tween 20 from RocheThe 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 and dimer fatty 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. 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 with the spindle chosen based on the observed thickness of the sample. pH is determined by using a standard pH meter.

[0048] Example 3 Sublimation too bad to allow for powder submission, added only PDO to wash down sublimation and subsequently added DMPA.Example 7 and 7B units in water let down are in pounds except for the dispersant which is in grams.

[0049] The following conclusions can be gleaned from the examples, A biodegradable, biosourced adhesive can be synthesized that is effective as an adhesive for lamination or other purposes. Furthermore, the adhesive will bio-degrade over time.

Claims

Claims1 . A composition 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, wherein the composition contains two dicarboxylates, a first dicarboxylate or is an anhydride which forms two carboxylate groups containing between the carboxylate groups a C i-8hydrocarbylene group and a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group.

2. A composition according to Claim 1 , wherein the first dicarboxylate and second dicarboxylate are present in a mole ratio of from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1.

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

4. A composition according to Claim 1 or 2, wherein the hydrocarbylene group is a C i-6o hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

5. A composition according to anyone of the preceding claims, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic or cycloaliphatic group between the carboxylate or carboxyl groups wherein the bivalent aliphatic or cycloaliphatic group 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 bivalent aliphatic group between the carboxylate or carboxyl groups of the first dicarboxylate or anhydride is a C 1-8 bivalent aliphatic or cycloaliphatic group, a C2-e bivalent aliphatic group, or a C 2-4 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.

7. A composition according to anyone of the preceding claims wherein, the bivalent aliphatic group between the carboxylate groups of the second dicarboxylate is a C 960 bivalent aliphatic group, a C 9-40 bivalent aliphatic group, or a C 12-40 bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms of oxygen or sulfur and / or one or more double bonds.

8. A composition according to anyone of the preceding claims wherein, the first dicarboxylates, including anhydrides comprise one or more of oxalic acid, malonic, succinic acid, glutaric acid, , furan dicarboxylic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, 1 ,4- cyclohexane dicarboxylic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, succinic anhydride, maleic anhydride hexa-hydro phthalic anhydride, phthalic anhydride, dimethyl terephthalate, terephthalic acid and esters thereof.

9. A composition according to anyone of the preceding claims wherein, the second dicarboxylates comprise one or more of sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, docosanedioic acid, triacontanedioic acid, 2-Decenedioic acid2Dodec-2-enedioic acid, Glutinic acid (Allene-1 ,3- dicarboxylic acid), Citraconic acid, Mesaconic acid, Dodecanedioic acid, a C20-60 - dimer acid, hydrogenated C20-60 dimer acid, or esters thereof,.

10. 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.1 1. 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.

12. 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.

13. 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.

14. A composition according to any one of the preceding claims, wherein the carboxylate groups are carboxylic acids.

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

16. A composition according to anyone of the preceding claims, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C 2-6 alkylene groups or C6-s cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

17. A composition according to anyone of the preceding claims, wherein the one or more diols comprise alkylene diols which contain C2-6alkylene groups, C2-4alkylene groups or C2.3alkylene groups.

18. 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 C2- aliphatic diols containing a pendant carboxylic acid group or one or more C2.4aliphatic diols containing a pendant carboxylic acid group.

19. 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.

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

21. 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.

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

23. A composition according to any one of the preceding claims, which has an acid value of about 10 to about 40 determined according to methods disclosed herein.

24. A composition according to any one of the preceding claims, wherein the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with a cationic moiety which forms a salt with the pendant carboxylate group.

25. A composition according to any one of the preceding claims, wherein the hydrogens or hydrocarbyl groups on the pendant carboxylates are replaced with cations derived from ammonia or tertiary amines.

26. A composition according to Claim 24 or 25, which is soluble in or forms a stable dispersion in water.

27. A composition according to any one of Claims 24 to 26 wherein the composition is dissolved or dispersed in water.

28. A composition according to any one of Claims 24 to 27 wherein the composition has a pH of about 7.0 to about 8.0 when determined in water.

29. A composition according to any one of Claims 20 to 23 wherein the composition exhibits a viscosity of about 500 cP to about 50,000 cP, or about 1000 cP to about 50,000 cPs.

30. 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.

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

32. 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 to formulaand 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 for the first dicarboxylate is a C i-8hydrocarbylene group and for the second dicarboxylate a C 9.60 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.

33. A composition according to any one of the preceding claims, comprising a polymer having a polymer backbone which 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 wherein for the first dicarboxylate the hydrocarbylene groups is a C 1-8 hydrocarbylene group and for the second dicarboxylate a C 9 _6o 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 has a number average molecular weight 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 .

34. A composition according to any one of the preceding claims, wherein the composition is 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.

35. A composition comprising: a) two or more dicarboxylates or anhydrides, having two carboxyl groups which form two carboxylate groups, comprising: i) a first dicarboxylate or anhydride containing between the carboxylate or carboxylgroups a C i-8hydrocarbylene group, and, ii) a second dicarboxylate containing between the carboxylate groups a C 9-60 hydrocarbylene group; 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 two or more dicarboxylates or anhydrides of about 1 :1 to about 5:1 moles; c) one or more alkylene diols or polyoxyalkylene diols, wherein the alkylene diols or polyoxyalkylene diols are present in a mole ratio to the two 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 two or more dicarboxylates or anhydrides of about 1 :20 to about 1 :1 .

36. A composition according to Claim 35, wherein the mole ratio of the first dicarboxylate to second dicarboxylate is from about 3:1 to about 9:1 or about 4.8:1 to about 6.7:1 .

37. A composition according to Claim 35 or 36 which forms a composition comprising a plurality of adducts of two of the first dicarboxylates or anhydrides and second dicarboxylates 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.

38. A composition according to any one of Claims 35 to 37 comprising: e) one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups.

39. A composition according to Claim 38, 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.

40. A composition according to Claim 38, 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.41 . A composition according to Claim 35 or 40, wherein the one or more compounds capable of forming a cationic moiety which can form a salt with the pendant carboxylate groups arepresent is a sufficient amount such that the composition when in water exhibits a pH of from about 7.0 to about 8.0.

42. A composition according to any one of Claims 35 to 41 , 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 polymeric chains.

43. A composition according to any one of Claims 35 to 42, 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.

44. A composition according to any one of Claims 35 to 43, wherein each of the dicarboxylates or anhydrides contain a hydrocarbylene group between the carboxylate groups, wherein the hydrocarbylene groups 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 35 to 44, wherein the hydrocarbylene group is a C 1-60 hydrocarbylene group which may contain a heteroatom of oxygen or sulfur and / or one or more double bonds.

46. A composition according to any one of Claims 35 to 45, wherein each of the dicarboxylates or anhydrides contain a bivalent aliphatic or cycloaliphatic group between the carboxylate groups wherein the bivalent aliphatic or cycloaliphatic group may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

47. A composition according to anyone of Claims 35 to 46, the bivalent aliphatic group between the carboxylate groups of the first dicarboxylate is a C 1-8 bivalent aliphatic or cycloaliphatic group, a C2.6bivalent aliphatic group, or a C2.4bivalent aliphatic group and the bivalent aliphatic groups may contain one or more heteroatoms of oxygen or sulfur and / or one or more double bonds.

48. A composition according to anyone of Claims 35 to 47 wherein, the bivalent aliphatic group between the carboxylate groups of the second dicarboxylate is a C 9-60 bivalent aliphatic group, a C 9.40 bivalent aliphatic group, or a C i2.40bivalent aliphatic group and the bivalent aliphatic groups may contain one or more cycloaliphatic rings, heteroatoms of oxygen or sulfur and / or one or more double bonds.

49. A composition according to any one of Claims 35 to 48 wherein, the first dicarboxylates, including anhydrides comprise one or more of oxalic acid, malonic, succinic acid, glutaric acid, furan dicarboxylic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, 1 ,4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, succinic anhydride, maleic anhydride hexa-hydro phthalic anhydride, phthalic anhydride, terephthalic acid and esters thereof.

50. A composition according to anyone of Claims 35 to 49 wherein, the second dicarboxylates comprise one or more of sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, docosanedioic acid, triacontanedioic acid, 2-Decenedioic acid, Dodec-2-enedioic acid, Glutinic acid (Allene- 1 ,3- dicarboxylic acid), Citraconic acid, Mesaconic acid, a C20-60 - dimer acid, hydrogenated C20-60 dimer acid, or esters thereof.

51. A composition according to any one of Claims 35 to 50, wherein the fused rings of the compound having at least two fused ring heterocycles, are C 5-6 rings or are C5 rings.

52. A composition according to any one of Claims 35 to 51 , wherein the fused rings of the compound having at least two fused ring heterocycles, contain heteroatoms of oxygen.

53. A composition according to any one of Claims 35 to 52, wherein the fused rings of the compound having at least two fused ring heterocycles, have one hydroxyl group pendant from each of the rings.

54. A composition according to any one of Claims 35 to 53, wherein the fused rings of the compound having at least two fused ring heterocycles comprise a residue of isosorbide, isomanide, or isoidide.

55. A composition according to any one of Claims 35 to 54, wherein the carboxylate groups are carboxylic acids.

56. A composition according to any one of Claims 35 to 55, wherein the anhydride is a cyclic anhydride.

57. A composition according to any one of Claims 35 to 56, wherein the one or more diols of alkylene diols or polyoxyalkylene diols contain C 2-6 alkylene groups or C 6-8 cycloalkylene groups, C 2-4 alkylene groups or C 2-3 alkylene groups.

58. A composition according to any one of Claims 35 to 57, 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.

59. A composition according to any one of Claims 35 to 58, 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.

60. A composition according to any one of Claims 35 to 59, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise one or more dimethylol alkanoic acids.61 . A composition according to any one of Claims 35 to 60, wherein the one or more aliphatic diols containing a pendant carboxylic acid group comprise dimethylol propanoic acids.

62. A composition according to any one of Claims 35 to 61 , 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 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 for the first dicarboxylate is a C 1-8 hydrocarbylene group and for the second dicarboxylate a C 9-60 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.

63. A method of preparing a composition according to any one of Claims 1 to 34 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 two dicarboxylates or anhydrides to the reaction vessel at a mole ratio of about 2 to 1 or greater, heating the reaction vessel 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 alcohol formed as a result of 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 an 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, 5,000 or about 5,000 to about 100,000 atomic mass units, or about 10,000 to about 70,000 atomic mass units.

64. A method according to Claim 63 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.

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

66. A method according to any one of Claims 63 to 65, 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 reacted until the formation of byproduct slows.

67. A method according to any one of Claims 63 to 66 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 tertiary amine, 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 ammonia or a tertiary amine, to form a composition which is water soluble or which forms a stable dispersion in water.

68. A method according to any one of Claims 60 to 64, 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 .

69. A method according to any one of Claims 62 to 69 wherein the composition formed is contacted with a compound having two or more electrophilic groups or a compound which forms ionic groups with carboxylate groups, such as carboxylic acids, under conditions such that the composition is crosslinked through the pendant carboxylate groups, such as carboxylic acids.

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