Copolymers of glycolaldehyde dimers and method of making same

Abstract

Polymer and copolymers and compositions containing one or more of such polymers and copolymers. Polymers and copolymers comprise, two or more structurally different glycolaldehyde dimers as monomer units. Exemplary dimers are 2,5-dihydroxy-1,4-dioxane; (1,2-hydroxyethoxy) acetaldehyde; 2-(hydroxymethyl)-1,3-dioxolan-4-ol; 1,1'-oxydi(ethane-1,2-diol); 2,2'-oxydi(ethane-1,1-diol); (1,3-dioxetane-2,4-diyl)dimethanol; and 2,2'-oxydiacetaldehyde). Copolymers containing two or more glycolaldehyde dimers have improved optical and mechanical properties.

Description

[0001] COPOLYMERS OF GLYCOLALDEHYDE DIMERS AND METHOD OF MAKING SAME

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the priority benefit of U.S. provisional application 63 / 433,570, filed December 19, 2022 and U.S. provisional application 63 / 500,659, filed May 8, 2023, each of which is incorporated by reference herein in its entirety.

[0004] BACKGROUND

[0005] This invention relates to polymers, particularly copolymers, that comprise one or more dimer of glycolaldehyde as one of the comonomers. More specifically, the invention relates to polymers and copolymers that comprise two or more dimers of glycolaldehyde as comonomers. The invention also relates to resins, coatings, foams, adhesives, interpenetrating networks and elastomers comprising such polymers and copolymers or made from such polymers and copolymers. The invention also relates to methods for making such polymers and copolymers and related materials.

[0006] There is a significant need to replace or supplement polymeric materials currently generated from petroleum materials with polymers or portions thereof generated from renewable resources. Renewable polymers which exhibit commercially useful properties are of particular interest. The present invention relates to copolymeric materials generated at least in part from glycolaldehyde (also called hydroxyacetaldehyde) which can be generated in high yield at relatively low cost from renewable resources (e.g., plant-based biomass).

[0007] U.S. patent 5,397,582 reports a pyrolysis process employing sugar and or starch feedstock to produce a water soluble pyrolysis liquid which contains glycolaldehyde.

[0008] U.S. patent 7,094, 932 reports a process for making glycolaldehyde by hydrous thermolysis of aqueous sugar (e.g., glucose) solutions.

[0009] U.S. published patent application 20200392061 reports a large scale, energy efficient process for production of oxygenates from sugar feedstock. The process involves thermolytic fragmentation of a sugar solution in a fragmentation reactor in which the sugar solution is carried in a fluidized bed with heat carrying particles. Thermolytic fragmentation of a glucose solution is reported to provide a high yield of glycolaldehyde.

[0010] U.S. 9,040,635 reports polymers made from renewable resources based on polymerization of a-hydroxycarbonyl compounds (a-hydroxyaldehdyes and a-hydroxyketones) and particularly glycolaldehyde. Polymers and copolymers are made by a method comprising a step of reacting the cyclic dimer of glycolaldehyde (2,5-dihydroxy-1 ,4-dioxane) with trimethylsilyltrifluoromethane sulfonate. More generally, a method is reported that comprises dehydrating a cyclic dimer of one or more a-hydroxycarbonyl compounds. End capped polymers in which prepared polymers are reacted with an end capping reagent are also reported.

[0011] The present invention provides copolymers prepared at least in part from renewable resources that greatly expand the physical and optical properties of previously available polymeric material from renewable resources. Polymers of this invention, for example, have improved optical clarity, and improved flexibility in thin film form.

[0012] SUMMARY OF THE INVENTION

[0013] In one aspect, this invention provides a polymer composition (a copolymer composition) that comprises, consists essentially of, or consists of two or more structurally different glycolaldehyde dimers (as monomer units). In embodiments, the dimers are selected from the group consisting of 2, 5-dihydroxy-1 ,4-dioxane; (1 ,2-dihydroxyethoxy)acetaldehyde; 2- (hydroxymethyl)-l ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2-diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'-oxydiacetaldehyde (see Scheme 1). Note that a given glycolaldehyde dimer may form structurally different repeating units on polymerization. Copolymers containing two or more glycolaldehyde dimers have improved properties compared to homopolymers that contain repeating units that are substantially derived from the six-member ring form of the glycolaldehyde dimer (i.e., monomer 2,5-dihydroxy-1 ,4- dioxane). The copolymers herein comprising, consisting essentially of or consisting of two or more different glycolaldehyde dimers exhibit improved optical clarity and thin film flexibility compared to homopolymers comprising, consisting essentially of or consisting of only or substantially only 2,5-dihydroxy-1 ,4-dioxane repeating units. In embodiments, the copolymers comprising, consisting essentially of or consisting of two or more structurally different glycolaldehyde dimers have from 0.1% to 25% by weight of monomers other than 2,5-dihydroxy-1 ,4-dioxane. In embodiments, the copolymers comprising, consisting essentially of or consisting of two or more structurally different glycolaldehyde dimers have from 0.5%-10% by weight of monomers other than 2,5-dihydroxy-1 ,4-dioxane. In other embodiments, the copolymers comprising, consisting essentially of or consisting of two or more structurally different glycolaldehyde dimers have from 1%-5% by weight of monomers other than 2,5-dihydroxy-1 ,4-dioxane. The term substantially all with respect to repeating units and monomers refers to greater than 99.9% by weight.

[0014] In embodiments, the copolymer of two or more glycoaldehdye dimers has Structure 1 , where Q, M, L, K, J, I, H and G are divalent glycolaldehdye dimer species as illustrated and g, h, i, j, k, I, m and n are integers from zero to 10 million, wherein at least two of g, h, i, j, k, I, m and n are different from zero and p is an integer ranging from 1-10 million. Each Ri, R2and 3 of Structure 1 is independently selected from the group consisting of hydrogen (-H), deuterium (-D), an halogen atom ( — F, — Cl, — Br, — I), a hydroxyl group ( — OH), an amino group ( — NH2), an alkylamino group ( — NHR9), a (bisalkylamino) group [ — N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an aminoalkylene group, an (alkylamino)alkylene group, a (bisalkylamino)alkylene group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an alkyl carbonate group, an acrylate group, a methacrylate group, a group comprising an oxirane ring, a glycidyl group, a thiol group (— SH), alkylthio (— SR9), a nitro group ( — NO2), a cyano group ( — CEN), a isocyanate group ( — N=C=O), a azide group ( — N3), a cyanate group ( — O=C=N), a nitroso group (—NO), a phosphine group [ — P(R9)2], a phosphate group [ — OP(O)(OR9)2], a phosphonate group [ — P(O)(ORg)2], a sulfate group ( — O — SO3Rg), a sulfonate group ( — SO3R9), a thiocyanate group (— S=C=N), a iso thiocyanate group ( — N=C=S), a — COR9group, a — COORg group, a — CON(R9)2group, a — CSR9group, a — CS — OR9group, a — N(R9)2group, a — CO — O — CO — R9, a — CO — NRg — CO — R9, a — N=C(R9)2, and a — CR9=NR9; where each Rg is independently, a hydrogen, deuterium, an alkyl, an aryl, an alkenyl or an alkynyl group, and each of which R9is optionally substituted with one or more halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, or thiocyanate group.

[0015] In additional embodiments, each Ri , R2and R3is independently optionally oligomeric, prepolymeric or polymeric in nature and selected from the group consisting of end-capped or uncapped polyethers, poly(fluoroethers), polyglycols, polyacetals, polyolefins, polystyrene, polyfluoroolefins, polyoxides, polychlorolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyols, polyalcohols, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitriles, polybutadiene, alkyds, polyurethanes, epoxies, cellulose and its derivatives, starch and its derivatives, polypeptides, and copolymers thereof.

[0016] In embodiments, one or both of R3is independently optionally oligomeric, pre-polymeric or polymeric. In embodiments, one or both of R3is independently oligomeric, pre-polymeric or polymeric and each of Ri and R2is non-oligomeric, not pre-polymeric or non-polymeric. In embodiments, Ri, R2and R3are non-oligomeric. In embodiments, Ri, R2and R3are not pre-polymeric. In embodiments, Ri, R2and R3are non-polymeric.

[0017] In specific embodiments of the copolymer of Structure 1 , each Ri and each R2are independently selected from H, D, optionally substituted alkyl groups having 1-3 carbon atoms, and optionally substituted aryl groups, particularly optionally substituted phenyl or benzyl groups. In specific embodiments, each R3independently is hydrogen, deuterium, alkyl, acyl, acrylic, methacrylic, aminoalkylene, (alkylamino)alkylene, (bisalkylamino)alkylene, glycidyl, in particular RgCO-, where 9 is optionally substituted alkyl, optionally substituted alkenyl or optionally substituted aryl (for example, optionally substituted phenyl or benzyl).

[0018] In specific embodiments of the copolymer of structure 1 , each Ri and each R2are hydrogen and R3is hydrogen, alkyl or acyl.

[0019] In embodiments, I-3groups include hydrogen, methyl, ethyl, n-butyl, acetyl (CH3CO-), phenyl, and benzoyl groups each of which is optionally substituted in embodiments with one or more halogen, an alkyl having 1-3 carbon atoms or an alkoxy having 1-3 carbon atoms.

[0020] In specific embodiments, (n+m+l) x p ranges from 10 to 200,000. In specific embodiments, (n+m+l) x p ranges from 10 to 100,000. In specific embodiments, (n+m+l) x p ranges from 10 to 50,000. In specific embodiments, (n+m+l) x p ranges from 10 to 20,000. In specific embodiments, (n+m+l) x p ranges from 10 to 1 ,000. In specific embodiments, (n+m+l+k+j+i+h+g) x p ranges from 2 to 200,000. In specific embodiments, (n+m+l+k+j+i+h+g) x p ranges from 10 to 1500. In specific embodiments, (n+m+l+k+j+i+h+g) x p ranges from 20 to 120.

[0021] SCHEME 1 : Glycolaldehyde Dimers

[0022] In embodiments of Structure 1 , at least two of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , three of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least four of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least five of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least six of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least seven of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at all of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , 1, m, and n are non-zero. In embodiments of Structure 1 , I, m, and n are non-zero and g, h, I, j, and k are zero. In embodiments of Structure 1 , I, m, and n are non-zero and (g+h+l+j+k) / (n+m+l+k+j+i+h+g) is less than 0.1. In embodiments of Structure 1 , 1, m, and n are non-zero and (g+h+l+j+k) / (n+m+l+k+j+i+h+g) is less than 0.2. In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.5.

[0023] In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.8. In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.9. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.8. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.9. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.95. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.99.

[0024] In further embodiments, Structure 1 has (l+k+j+i+h+g) / (n+m+l+k+j+i+h+g)<0.1 , m / (n+m+l+k+j+i+h+g)<0.4 and n / (n+m+l+k+j+i+h+g)>0.5. In further embodiments, Structure 1 has (l+j+h+g) / (n+m+l+k+j+i+h+g)<0.4, (i+m+k)+ / (n+m+l+k+j+i+h+g)<0.1 , and n / (n+m+l+k+j+i+h+g)>0.5.

[0025] In a related aspect, the invention also provides a method of making copolymers that comprise, consist essentially of or consist of two or more different glycolaldehyde dimers by polymerization of a mixture comprising two or more glycolaldehyde dimers in the presence of a Lewis acid catalyst.

[0026] Lewis acid catalysts include, among others, salts of iron, boron, aluminum, copper, zinc, scandium, lanthanum, yttrium, ytterbium with anions selected from the group of fluoride, chloride, bromide, iodide, triflate (CF3SO3), and bistriflidamide ([(CF3SO2)2N]_, perchlorate, chlorate, nitrate, tetrafluoro borate, hexaflurophosphate, tetrachloraluminate, and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. In some embodiments the Lewis acid catalyst is ZnCI2, BF3, SnCI4, AICI3, or MeAICI2.

[0027] In some embodiments the catalysts is selected from the group of scandium triflate SC(OSO2CF3)3, lanthanum triflate La(OSO2CF3)3, zinc triflate Zn(OSO2CF3)2, aluminum triflate AI(OSO2CF3)3, iron triflate Fe(OSO2CF3)3and copper triflate Cu(OSO2CF3)2.

[0028] In embodiments, the polymerization to form Structure 1 is carried out in a solvent. In embodiments, the solvent is a polar aprotic solvent. In embodiments the solvent is an ionic liquid. In embodiments, the solvent is a mixture of polar aprotic solvent and an ionic liquid. In embodiments, the solvent is selected from acetonitrile, propionitrile, butyronitrile, 3- methoxypropionitrile, chloroform, dimethyl carbonate, ethylene carbonate, propylene, carbonate, dimethyl sulfoxide, dimethyl formamide, methylene chloride or mixtures thereof. In embodiments, the polar aprotic solvent is anhydrous. In specific embodiments, as illustrated in Example 1 D, the polar aprotic solvent contains water, e.g., a minimum of 10% by volume water. In embodiments the polymerization is carried out in the absence of solvents either for its entire duration or a portion of it.

[0029] In embodiments, the reaction is carried out either in the solid state or in solution and various methods are used to remove the byproduct of the reaction, which may include water or methanol. Methods of removing byproducts include running the reaction under reduced pressure, the use of dehydrating reagents, or by using reactors that allows the condensation of water or other solvent away from the reaction mixture, such as a Dean-Stark trap.

[0030] In general, the polymerization can be conducted at temperatures ranging from -78 °C to 120 °C, dependent upon the solvent, reagents and reactants used. More specifically, the reaction is conducted at temperatures ranging from 0 °C to 80 °C, yet more specifically from 5 °C to 55 °C and even more specifically from 30 °C to 45 °C. The polymerization reaction is optionally carried out under reduced pressure most generally from 4 mtorr to 200 mtorr, and more specifically from 60 mtorr to 120 mtorr. The polymerization reaction can generally be carried out for any convenient time that provides desired product. It is however preferred to minimize the reaction time to achieve desired product. Generally, the reaction can be conducted from 0.5 h to 3 days, although shorter reaction times may be beneficial, In embodiments, the polymerization is carried out from 1 h to 3 days or from 6 h to 18 h or from 1 h to 6 h.

[0031] In embodiments, the polymerization reaction to prepare the polymer of Structure 1 is carried out to generated an oligomer of Structure 1 or a pre-polymer of Structure 1 which is then used as a starting material in further polymerizations as illustrated in the Examples.

[0032] In another aspect, this invention provides a copolymer composition comprising one or more monomers that are optionally substituted 2,5-dihydroxy-1 ,4-dioxanes in combination with a second monomer.

[0033] The second monomer is selected from any monomer that can react with a OH group to form the desired polymer. Non limiting examples of molecules that can be used as the second monomer include: monosaccharides, disaccharides, oligosaccharides, polysaccharides, diols, polyols, compounds containing one, two or more carboxylic acid groups, hydroxyacids, aminoacids, compounds containing one, two or more carboxylic acid ester groups, compounds containing one, two or more acyl chloride groups, compounds containing one, two or more acyl bromide groups, compounds containing one, two or more isocyanate groups, compounds containing one, two or more oxirane groups, compounds containing one, two or more isothiocyanate groups, compounds containing one, two or more nitrile groups, compounds containing one, two or more azide groups, phosgene, dialkyl carbonates, dialkyl dichlorosilanes, and diaryldichlorosilanes. In embodiments, the second monomer is other than a dimer of an alpha-hydroxycarbonyl compound. In embodiments, the second monomer is other than a dimer of an alpha-hydroxyaldehdye or an alphahydroxyketone. In embodiments, the second monomer is an alpha-hydroxycarbony. In specific embodiments, the second monomer is an alpha-hydroxyketone. In specific embodiments, the second monomer is hydoxyacetone. In specific embodiments, the second monomer is lactaldehyde.

[0034] In embodiments, the copolymer comprises the repeating unit of structure M3 or M4:

[0035] Structure M3 Structure M4 where -R- is bivalent and is selected from a single bond, -O-, -NH-, -NR10-, -S-, -SO-, -SO2-, -PR10-, -0-PO(ORio)-0-, a linear or branched bivalent organic radical including, but not limited to -CH2-, -(CH2)X-, a linear or branched bivalent alkyl radical, a bivalent aromatic radical, a bivalent heteroaromatic aromatic radical, a bivalent oligomeric radical, or a bivalent polymeric radical, wherein x is an integer number ranging from 1 to 100 and Ri0is monovalent organic radical. In embodiments, R is an optionally substituted alkyl, alkenyl, or aryl group. CH2groups of R are optionally substituted. In embodiments, optional substitution of R and Rio include substitution with one or more halogen, alkyl, alkenyl, aryl or alkoxy.

[0036] In embodiments, the second monomer is formed by reaction of alkyl diacid, an ester thereof, or an anhydride thereof, or a diacid halide, particularly a diacid chloride thereof. In embodiments, the alkyl diacid or diester monomer has formula M5, M6 or M7. In embodiments, the diacyl halide monomer has formula M8, M9 or M10. In embodiments, the diisocyanate monomer has formula M11, M12 or M13. In embodiments, the second monomer is an isomer, dimer, trimer, biuret or isocyanurate derivative of formula M 11 , M12 or M13.

[0037] M13 where: each R14 is independently hydrogen, an alkyl group, or an aryl group, in M5, M8, M1 1 x is an integer ranging from 1-100 and one or more of the CH2groups is optionally substituted; in M6, M7, M9, M10, M12 and M13, AR is an optionally substituted bivalent aryl, optionally substituted bivalent heteroaryl, including among others bivalent phenyl, bivalent methylphenyl, bivalent dimethyl phenyl, bivalent naphthyl or bivalent furfuryl, bivalent pyridyl; in M7, M 10 and M 13 y and z are 0 or an integer from 1 -6 where at least one o y or z is not zero; where optional substitution is substitution with one or more groups selected from deuterium, halide optionally protected hydroxyl group ( — OH, — OPR9), an amino group ( — NH2), an alkylamino group ( — NHR9), a (dialkylamino) group [ — N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an alkyl carbonate group, a thiol group ( — SH), alkylthio ( — SR9), a nitro group ( — NO2), a cyano group ( — C=N), a isocyanate group ( — N=C=O), a azide group ( — N3), a cyanate group (— O=C=N), a nitroso group ( — NO), a phosphine group [ — P(R9)2], a phosphate group [— OP(O)(OR9)2], a phosphonate group [ — P(O)(OR9)2], a sulfate group ( — O — SO3R9), a sulfonate group ( — SO3R9), a thiocyanate group ( — S=C=N), a iso thiocyanate group ( — N=C=S), a — COR9group, a — COOR9group, a — CON(R9)2group, a — CSR9group, a — CS— OR9group, a — N(R9)2group, a — CO — O — CO — R9, a — CO — NR9— CO—9, a — N=C(R9)2, and a — CR9=NR9, where R9, where each R9is independently, a hydrogen, deuterium, an alkyl, an aryl, an alkenyl or an alkynyl group, and each of which Rg is optionally substituted with one or more halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, or thiocyanate group.

[0038] In another embodiment the second monomer is a di- tri- or poly-isocyanate. Diisocyanates include among others methylenebis(phenyl isocyanate) (MDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis- cyclohexylisocyanate (HMDI)(hydrogenated MDI), and isophorone diisocyanate (IPDI), Tetramethylxylidene diisocyanate (TMXDI ), their isomers, dimers, trimers, biuret and isocyanurate derivatives. In yet another embodiment the second monomer is a reagent that will form a carbonate group upon reaction, including but not limited to phosgene, urea, urea derivatives, a dialkyl carbonate and more specifically dimethyl carbonate, a alkylene carbonate, diphosgene, triphosgene, carbonyl diimidazole, disuccinimidyl carbonate, or carbon monoxide.

[0039] This invention also provides copolymer compositions comprising one or more glycolaldehyde dimer selected from the group of 2,5-dihydroxy-1 ,4-dioxane; (1 ,2- dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2- diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'- oxydiacetaldehyde and a second monomer that is not a glycolaldehyde dimer..

[0040] The second monomer may be selected as described above from any monomer that can react with a OH group to form the desired polymer. Non limiting examples of molecules that can be used as the second monomer include: polysaccharides, monosaccharides, disaccharides, oligosaccharides, polysaccharides, diols, polyols, compounds containing two or more carboxylic acid groups, hydroxyacids, aminoacids, compounds containing two or more carboxylic acid ester groups, compounds containing two or more acyl chloride groups, compounds containing two or more acyl bromide groups, compounds containing two or more isocyanate groups, compounds containing two or more oxirane groups, compounds containing two or more isothiocyanate groups, compounds containing two or more nitrile groups, compounds containing two or more azide groups, phosgene, dialkyl carbonates, dialkyl dichlorosilanes, and diaryldichlorosilanes. The repeating unit of the second monomer can for example be selected from M3, or M4 orthose formed from diacids, diesters, diacid halides or diisocyanates of M5-M13.

[0041] The invention provides polymers and copolymers of Structures 1 , 2, 3, 4, 5, 6, 7, 8 and 9 and methods of making these polymer and copolymers.

[0042] Additional aspects and embodiments of the invention will be apparent to one of ordinary skill in the art on review of the

[0043] BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 :1H-NMR spectrum of polyacetal made by polymerization of a raw material blend comprising >90% by wt of 2,5-dihydroxy-1 ,4-dioxane and the reminder <10% wt. being a mixture of 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol, 1 ,1'-oxydi(ethane-1 ,2-diol) and 1 ,2- dihydroxyethoxyacetaldehyde an example of M-PDHDO.

[0045] FIG. 2:1H-NMR spectrum of polyacetal (PDHDO) from pure 2,5-Dihydroxy-1 ,4-dioxane (DHDO).

[0046] DETAILED DESCRIPTION DEFINITIONS:

[0047] In general, the terms and phrases used in this specification have the meaning recognized in the art, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. For clarity, the following terms have the following meaning unless otherwise specified:

[0048] It will be understood by one of ordinary skill in the art that single numeric values or numeric values in a range, include slight variations or deviations from the stated value which may be used to achieve substantially the same results as the stated value. In cases, where a numeric value is one that is measured, it will be recognized that there is some level of uncertainty in the stated value due to experimental error, which can be determined by one of ordinary skill in the art. In circumstances where this definition cannot be applied to a given stated value, is exceedingly difficult to apply, or wherein an uncertainty value is not specifically recited, then the numeric value has a reasonable deviation from the value, as known to a skilled person in the art. In embodiments, the reasonable deviation for a given value is + / -10% unless otherwise indicated.

[0049] Glycolaldehyde is also known as 2-hydroxyacetaldehyde and has formula CHO-CH2-OH. dimers include all dimeric forms of glycolaldehyde Glycolaldehyde dimers include linear dimers and cyclic dimers, including six member cyclic dimers, five member cyclic dimers and four member cyclic dimers. Glycolaldehyde dimers include but are not limited to 2,5-dihydroxy-1 ,4-dioxane; (1 ,2-dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)- 1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2-diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4- diyl)dimethanol; and 2,2'-oxydiacetaldehyde and mixtures thereof. Some examples of glycolaldehyde dimers are shown in Scheme 1 .

[0050] A monovalent organic radical is a radical formally obtained by the removal of a hydrogen atom from an organic molecule. Non limiting examples of monovalent organic radical include, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, phenyl, aryl, alkyl, alkenyl, alkoxy, alkylcarbonyl, akanoyl, alkylthio, cycloalkyl, cycloalkoxy, alkyloxy, alkenyloxy, alkenyldioxy, acyl, aryl, alkylaryl, arylalkyl, aryloxy, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkylsulfinyl, aryloxyalkyl, alkoxylalkyl, heterocyclic, heteroaryl, polyetheralkyl, fluorinated alkyl, perfluoralkyl, sulfonate, alkylsulfonate, arylsulfonate, alkylsulfate, arylsulfate, nitroalkyl, alkylsilyl, and arylsilyl. In general, an organic radical can contain any number of carbon atoms. In embodiments, organic radicals contain 1-100, 1-50, 1-20, 1-10, 1-6 or 1-3 carbon atoms. In embodiments, organic radicals can contain 1-6 heteroatoms (e.g., O, N, S or P). In specific embodiments, organic radicals include alkyl, alkenyl, alkoxyl (alkyloxy), acyl, alkylamino, dialkylamino, alkylsulfinyl, haloalkyl and fluoroalkyl groups having 1-6 or 1-3 carbon atoms, In specific embodiments, organic radicals include aryl, alkylaryl, cycloalkyl, heterocyclic, and heteroaryl groups having 3-20 carbon atoms (or 3-10 or 6-10 carbon atoms and up to 4 heteroatoms.

[0051] Additional examples of monovalent organic radicals formally obtained by the removal of a hydrogen atom from an oligomeric or polymeric chain made by repeating one or more monomers selected from glycols, ethers, fluoroethers, olefins, fluoroolefins, acrylates and methacrylates, vinyl groups alkynes, esters, amino acids, lactones and lactams, urethanes, epoxies, hydroxyacids, dienes, chloroolefins, diols, diamines, polyamines, groups containing acrylates or methacrylates, groups containing esters, ethers, hydroxyls, epoxies or amines, epoxidized groups, ring-opened epoxy groups, polyglycols, polyethylene glycol, polyethers, poly(fluoroethers), polyacetals, polyenes, polyolefins, polystyrene and its copolymers, polyfluoroolefins, polyoxides, polychloroolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitrile and its copolymers, polybutadiene and its copolymers, alkyds, polyols, polyalcohols, polyurethanes, epoxies, cellulose and its derivatives, starch and its derivatives, polypeptides, oligonucleotides, nucleotides, oligosaccharides, polysaccharides, and combinations and copolymers thereof. One or more carbons of an organic radical are optionally substituted.

[0052] A bivalent organic radical is a radical formally obtained by the removal of two hydrogen atoms from an organic molecule, oligomer or polymer. Non limiting examples of divalent organic radicals include -(CH2)n-(where in embodiments n ranges from 1-20), alkylenes, arylenes, optionally substituted alkylene, methylene, linear alkylene, cyclic alkylene groups, alkenylene, and arylene groups, optionally substituted ether or polyether groups, optionally substituted thioether or polythioether groups. In general, a bivalent organic radical can contain any number of carbon atoms. In embodiments, bivalent organic radicals contain 1- 100, 1-50, 1-20, 1-10, 1-6 or 1-3 carbon atoms. In embodiments, bivalent organic radicals can contain 1-6 heteroatoms (e.g., O, N, S or P).

[0053] Bivalent organic radicals also include species formally resulting from removing two hydrogen atoms from an oligomer or a polymer chain made by repeating one or more monomers selected from glycols, ethers, fluoroethers, olefins, fluoroolefins, acrylates and methacrylates, vinyl groups alkynes, esters, amino acids, lactones and lactams, urethanes, epoxies, hydroxyacids, dienes, chloroolefins, diols, diamines, polyamines, groups containing acrylates or methacrylates, groups containing esters, ethers, hydroxyls, epoxies or amines, epoxidized groups, ring-opened epoxy groups, polyglycols, polyethylene glycol, polyethers, poly(fluoroethers), polyacetals, polyenes, polyolefins, polystyrene and its copolymers, polyfluoroolefins, polyoxides, polychloroolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitrile and its copolymers, polybutadiene and its copolymers, alkyds, polyols, polyalcohols, polyurethanes, epoxies, cellulose and its derivatives, starch and its derivatives, polypeptides, oligonucleotides, nucleotides, oligosaccharides, polysaccharides, and combinations and copolymers thereof.

[0054] A polymer is a substance composed of very large molecules, called macromolecules, that are multiples of simpler chemical units called monomers. Polymers can be linear, branched or crosslinked

[0055] A copolymer is a polymer derived from more than one species of monomer.

[0056] A prepolymer or pre-polymer refers to a monomer or system of monomers that have been reacted to an intermediate-molecular mass state. A prepolymer is capable of further polymerization by reaction with reactive groups, e.g., with a second monomer or mixture of monomers, to a fully cured, high-molecular-mass state. Prepolymer are also called resins. If OH terminated, prepolymers are also called polyols. The useful size of a prepolymer depends on specific polymerizations to be carried out as well as the desired polymerized product. Often viscosity, solubility, miscibility and reactivity with the second monomer or mixture of monomers are important factors for selection of prepolymer size. In embodiments of this invention, prepolymers nominally include species with two or more of the same or different repeating units and extend up to species having 1 ,000 or more repeating units. In embodiments of this invention, the size of the prepolymer can vary widely. In embodiments, prepolymers used in polymerizations herein range in size from 3 to 1000 repeating units. In specific embodiments, prepolymers herein range in Mw from 300 to 8,000 D. Specific prepolymers of this invention include PDHDO and M-PDHDO (of Structure 1) and more specifically PDHDO and M-PDHDO having from 3-1000 repeating units or more specifically having Mwranging from 300 to 8,000 D.

[0057] Oligomer is used to describe species having a few monomer units linked together. For clarity herein, the term oligomer refers to species containing 10 or fewer monomer units. Oligomers can contain repeating units that are all the same or two or more different repeating units. In certain cases, oligomers and prepolymer are synonymous. For example, an oligomer can be used as a starting material in a polymerization reaction. For use herein, the term prepolymer is used for an intermediate compound used for further polymerization (including species of the size of oligomers) and the term oligomer refers to a final product.

[0058] An alpha hydroxyaldehdye (a-hvdoxyaldehdye) is chemical compound that comprises an aldehyde group and a hydroxyl group substituent on the adjacent (alpha) carbon to the aldehyde group. Examples of this group include glycolaldehyde, lactaldehyde, and mandelic aldehyde. Alpha hydroxyaldehdyes may exist in one or more dimer forms.

[0059] An a I p h a hy d roxyketo n e- (a- h yd roxvketo n e) is chemical compound that comprises an aldehyde ketone group and a hydroxyl group substituent on the adjacent (alpha) carbon to the ketone group. Examples of this group include hydroxy acetone and di hydroxyacetone.

[0060] The term monosaachride is used herein to refer generally to a sugar monomer in any form. Examples of monosaccharides include glucose, fructose and galactose.

[0061] The term disaccharide is used to refer to a sugar dimer formed when two monosaccharides are joined by a glycosidic linkage and includes any forms thereof.. Sucrose, lactose, and maltose are examples of disaccharides.

[0062] The term oligosaccharide is used herein to refer to a sugar oligomer having 3-10 sugar monomers in any form joined by glycosidic linkages,

[0063] The term polysaccharide is used herein generally to refer to a polymer of sugar monomers of any form joined by glycosidic linkages and having more than 10 sugar monomers.

[0064] PDHDO refers to a polymer including a prepolymer of Structure 1 wherein n is non-zero and all of m, I, k, j, i, g and h are zero.

[0065] M-PDHDO (mixed PDHDO) refers to a copolymer including a prepolymer of Structure 1 wherein at least two of n, m, I, k, j, i, g and h are non-zero. In embodiments, n, m and I are non-zero.

[0066] DHDO refers to 2, 5-dihydoxy-1 , 4-dioxane. DHDO of different purities is used in examples herein.

[0067] This invention provides copolymers of glycolaldehyde dimers including alternating, random and block copolymers of glycolaldehyde dimers. Copolymers of this invention may be linear, branched or crosslinked. Copolymers of glycolaldehyde dimers of this invention include copolymers in which the glycolaldehyde dimer exists in either its linear forms, six member cyclic form, five member cyclic form, four member ring form or a mixture of two or more forms. Copolymers of glycolaldehyde dimer include those in which the dimer is in the form of 2,5-dihydroxy-1 , 4-dioxane; (1 ,2-dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1,3- dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2-diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4- diyl)dimethanol; and 2,2'-oxydiacetaldehyde (see Scheme 1) and mixture thereof. Copolymers of this invention include copolymers in which all the monomers are different forms of glycolaldehyde dimers, and copolymers in which one or more glycolaldehyde dimers or two or more glycolaldehyde dimers are reacted with one or more other, chemically different, comonomers.

[0068] In one aspect, the invention provides copolymers of Structure 1 : where Q, M, L, K, J, I, H and G are divalent glycolaldehdye dimer species as illustrated and g, h, i, j, k, I, m and n are integers from zero to 10 million, wherein at least two of g, h, i, j, k, I, m and n are different from zero and p is an integer ranging from 1-10 million. Each Ri, R2and R3of structure 1 is independently selected from the group consisting of hydrogen (-H), deuterium (-D), an halogen atom ( — F, — Cl, — Br, — I), a hydroxyl group ( — OH), an amino group ( — NH2), an alkylamino group ( — NHRg), a (bisalkylamino) group [ — N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an aminoalkylene group, an (alkylamino)alkylene group, a (bisalkylamino)alkylene group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an alkyl carbonate group, an acrylate group, a methacrylate group, a group comprising an oxirane ring, a glycidyl group, a thiol group ( — SH), alkylthio ( — SR9), a nitro group ( — NO2), a cyano group ( — C N), a isocyanate group ( — N=C=O), a azide group ( — N3), a cyanate group ( — O=C=N), a nitroso group ( — NO), a phosphine group [ — P(R9)2], a phosphate group [ — OP(O)(OR9)2], a phosphonate group [ — P(O)(OR9)2], a sulfate group ( — O — SO3R9), a sulfonate group ( — SO3R9), a thiocyanate group (— S=C=N), a iso thiocyanate group ( — N=C=S), a — COR9group, a — COOR9group, a — CON(R9)2group, a — CSR9group, a — CS — OR9group, a — N(R9)2group, a —CO — O— CO— R9, a — CO — NR9— CO — R9, a — N=C(R9)2, and a — CR9=NR9; where each R9is independently, a hydrogen, deuterium, an alkyl, an aryl, an alkenyl or an alkynyl group, and each of which R9is optionally substituted with one or more halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, or thiocyanate group.

[0069] In additional embodiments, each R1 , R2and R3is independently optionally oligomeric, prepolymeric or polymeric in nature and selected from the group consisting of end-capped or uncapped polyethers, poly(fluoroethers), polyglycols, polyacetals, polyolefins, polystyrene, polyfluoroolefins, polyoxides, polychlorolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyols, polyalcohols, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitriles, polybutadiene, alkyds, polyurethanes, epoxies, cellulose and its derivatives, starch and its derivatives, polypeptides, and copolymers thereof.

[0070] In embodiments, one or both of R3is independently optionally oligomeric, pre-polymeric or polymeric. In embodiments, one or both of R3is independently oligomeric, pre-polymeric or polymeric and each of R1 and R2is non-oligomeric, not pre-polymeric or non-polymeric. In embodiments, R1 , R2and R3are non-oligomeric. In embodiments, R1 , R2and R3are not pre-polymeric. In embodiments, R1 , R2and R3are non-polymeric.

[0071] In specific embodiments of the copolymer of Structure 1 , each R1 and each R2are independently selected from H, D, optionally substituted alkyl groups having 1-3 carbon atoms, and optionally substituted aryl groups, particularly optionally substituted phenyl or benzyl groups. In specific embodiments, each R3independently is hydrogen, deuterium, alkyl, acyl, acrylic, methacrylic, glycidyl, aminoalkylene, (alkylamino)alkylene, (bisalkylamino)alkylene, in particular R9CO-, where R9is optionally substituted alkyl, optionally substituted alkenyl or optionally substituted aryl (for example, optionally substituted phenyl or benzyl).

[0072] In specific embodiments of the copolymer of Structure 1 , each R1 and each R2are hydrogen and R3 is hydrogen, alkyl or acyl.

[0073] In embodiments, R1-R3 groups include hydrogen, methyl, ethyl, n-butyl, acetyl (CH3CO-), phenyl, and benzoyl groups each of which is optionally substituted in embodiments with one or more halogen, an alkyl having 1-3 carbon atoms or a alkoxy having 1-3 carbon atoms.

[0074] In specific embodiments, (n+m+l) x p ranges from 10 to 200,000. In specific embodiments, (n+m+l) x p ranges from 10 to 100,000. In specific embodiments, (n+m+l) x p ranges from 10 to 50,000. In specific embodiments, (n+m+l) x p ranges from 10 to 20,000. In specific embodiments, (n+m+l) x p ranges from 10 to 1 ,000. In specific embodiments, (n+m+l+k+j+i+h+g) x p ranges from 10 to 1500. In specific embodiments, (n+m+l+k+j+i+h+g) x p ranges from 20 to 120.

[0075] In embodiments of Structure 1 , at least two of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , three of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least four of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least five of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least six of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at least seven of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , at all of g, h, i, j, k, I, m, or n are non-zero. In embodiments of Structure 1 , 1, m, and n are non-zero. In embodiments of Structure 1 , I, m, and n are non-zero and g, h, I, j, and k are zero. In embodiments of Structure 1 , I, m, and n are non-zero and (g+h+l+j+k) / (n+m+l+k+j+i+h+g) is less than 0.1. In embodiments of Structure 1 , 1, m, and n are non-zero and (g+h+l+j+k) / (n+m+l+k+j+i+h+g) is less than 0.2. In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.5.

[0076] In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.8. In embodiments, (n+m+l) / (n+m+l+k+j+i+h+g) is greater than or equal to 0.9. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.8. In embodiments, n / (n+m+l+k+j+i+h+g) is less than or equal to 0.9.

[0077] In further embodiments, Structure 1 has (l+k+j+i+h+g) / (n+m+l+k+j+i+h+g)<0.1 , m / (n+m+l+k+j+i+h+g)<0.4 and n / (n+m+l+k+j+i+h+g)>0.5. In further embodiments, Structure 1 has (l+j+h+g) / (n+m+l+k+j+i+h+g)<0.4, (i+m+k)+ / (n+m+l+k+j+i+h+g)<0.1 , and n / (n+m+l+k+j+i+h+g)>0.5. Other embodiments of this invention include copolymers of Structure 2: where:

[0078] Ri, R2and R3are as defined in the various embodiments of Structure 1 ; n, m and I are as defined in the various embodiments of Structure 1 ; and p is an integer ranging from 1 to 10 million.

[0079] In embodiments, at least two of n, m or I are non-zero.

[0080] In embodiments, copolymers of Structure 2 have l / (n+m+i)<0.1 , m / (n+m+l)<0.4 and n / (n+m+l)>0.5. In embodiments, copolymers of Structure 2 have l / (n+m+i)<0.01 , m / (n+m+l)<0.1 and n / (n+m+l)>0.9. In embodiments, copolymers of Structure 2 have l / (n+m+i)<0.01 , m / (n+m+l)<0.1 and n / (n+m+l)>0.95. In embodiments, copolymers of Structure 2 have l / (n+m+i)<0.01 , m / (n+m+l)<0.1 and n / (n+m+l)>0.99. In embodiments, each Ri and R2are independently selected from hydrogen, methyl, ethyl, n-butyl, acetyl (CH3CO- ), phenyl, and benzoyl groups. In embodiments, each R3is independently selected from hydrogen, acyl, acetyl, phenyl, and benzoyl groups. In specific embodiments, each Ri and R2is independently selected from hydrogen, methyl, ethyl, propyl, n-butyl and each R3is independently selected from hydrogen and acetyl.

[0081] In another aspect the invention provides copolymers having Structures 3 or Structure 4 which are prepared by polymerization of 2,5-dihydroxy-1 ,4-dioxane or a prepolymer of 2,5- dihydroxy-1 ,4-dioxane with a second monomer:

[0082]

[0083] Structure 4 where: n and m independently are integers ranging from 1 to 1 million; p is an integer ranging from 2 to 100 million; each of Ri , R2and R3is independently as defined for various embodiments of Structure 1 ;

[0084] -R- is bivalent and selected from a single bond, a -O-, -NH-, -NR10-, -S-, -SO-, -SO2-, -PR10-, -O-PO(ORIQ)-O-, a linear or branched bivalent organic radical including but not limited to -

[0085] CH2-, -(CH2)X-, a linear or branched bivalent alkyl radical, a bivalent aromatic radical, a bivalent heteroaromatic aromatic radical, a bivalent oligomeric radical, or a bivalent polymeric radical; x is an integer ranging from 1 to 100 and Rio is a monovalent organic radical. In embodiments, CH2groups in Structures 3 and 4 are optionally substituted, where optional substitution includes substitution with one or more alkylalkoxy, OH group, or halogen. In embodiments, optionally substitution is with one or more alkyl or alkoxy having 1-3 carbon atoms. In embodiments of Structures 3 and 4, m is 1 and n is 1-10 million or n is 1-1000, or n is 1- 100 or n is 10 to 100. In embodiments of Structures 3 and 4, m is 1-1000 and n is 1-10 million or n is 1-1000, or n is 1-100 or n is 10 to 100. In embodiments, p is 2 to 100,00 or 2- 50,000, or 2-10,000 or 2 to 1000, or 10 to 100.

[0086] In embodiments of Structures 3 and 4, each of Ri and R2is independently hydrogen, or alkyl having 1-3 carbon atoms. In embodiments, of Structures 3 and 4, each R3is independently hydrogen or acyl and in particular is acetyl. In embodiments, each R3is hydrogen, phenyl or benzoyl.

[0087] In embodiments of Structure 3, -R- is (CH2)x with x =1 ,2,4,6,8,10,12; or a bivalent radical of benzene, naphthalene, furan, pyridine, pyrrole, cyclohexane, tertrahydrofuran, indole, thiofuran, benzofuran or cyclopentane each of which is optionally substituted .

[0088] In embodiments of Structure 4, the second monomer is a di- tri- or poly-isocyanate. Diisocyanates include among others methylenebis(phenyl isocyanate) (MDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate (HMDI)(hydrogenated MDI), and isophorone diisocyanate (IPDI) , Tetramethylxylidene diisocyanate (TMXDI ), their isomers, dimers, trimers, biuret and isocianutare derivatives.

[0089] In embodiments of Structures 3 and 4, the second monomer is selected from those of structures of M5-M13.

[0090] In embodiments, the polymerization of succinic acid or its dimethyl esters and 2,5-dihydroxy- 1 ,4-dioxane leads to a polyester-co-polyacetal with n=1 and m=1.

[0091] In embodiments, the polymerization of succinyl chloride and 2,5-dihydroxy-1 ,4-dioxane also leads to a polyester-co-polyacetal with n=1 and m=1.

[0092] In embodiments, the reaction of a diisocyanate and 2,5-dihydroxy-1 ,4-dioxane lead to a polyurethane with n=1 and m=1

[0093] Non limiting examples of the comonomer (second monomer) that can be used to make the polymer compositions in Structures 3 and 4 include those shown in Table 1 below and their acid halides, acid chloride, anhydrides, methyl esters, ethyl esters and alkyl ester derivatives:

[0094] Table 1 : Exemplary Second Monomers

[0095] The second monomers listed in Table 1 and their acid halides, acid chloride, anhydrides, methyl esters, ethyl esters and alkyl ester derivatives can be optionally substituted. For example, one or more hydrogens in these species can be substituted with one or more groups as defined in Structure 1 for R1-R3. In embodiments optional substitution includes substitution with one or more halogen, one or more alkyl, one or more alkoxy, one or more phenyl or benzyl, one or more phenoxy or benzyloxy. Alkyl and alkoxy substitutents include those having 1-3 carbon atoms.

[0096] Other embodiments of this invention include copolymers of Structure 5 and Structure 6 below. and their acid halides, acid chloride, anhydrides, methyl esters, ethyl esters and alkyl ester derivatives: where:

[0097] Q, M, L, K, J, I, H. and G are as defined in various embodiments of Structure 1 ; n, m, 1, k, j, I, h, and g are as defined in various embodiments of Structure 1; each R3is as defined in the various embodiments of Structure 1 ; p and q are independently integers ranging from 1 to 10 million;

[0098] -R- is a bivalent radical as generally defined in certain Structures herein; and r is an integer ranging from 1 to 10 million.

[0099] In embodiments, at least one of n, m or I is non-zero. In embodiments, n, m and I are nonzero and each of k, j, I, h and g is zero. In embodiments, p is 1 and r ranges from 1-10 million. In embodiments, p and q are 1 and r ranges from 1-10 million. In embodiments, p and q are1 and r ranges from 10-10 million. In embodiments, p is 1 and r ranges from 10 to 1000. In embodiments, p is 1 and r ranges from 10 to 100.

[0100] In embodiments, p is 1-10, q is 1 and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100. In embodiments, p is 1-300, q is 1-3 and r ranges from 1- 10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100. In embodiments, p is 1-10,00, q is 1-3 and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100.

[0101] In embodiments, each of Ri and R2of Q, M, L, K, J, I, H and G is hydrogen and R3is hydrogen, acyl, or alkyl. In embodiments, each of Ri and R2of Q, M, L, K, J, I, H and G is hydrogen or methyl or phenyl and R3is hydrogen, acyl, or alkyl.

[0102] In embodiments, -R- is as defined in all embodiments of Structures 3 and 4.

[0103] In embodiments, -R- is a bivalent organic radical.

[0104] In certain embodiments, copolymers of this invention have Structures3, 4, 5, or 6 wherein n>m+l

[0105] In embodiments of Structures 3, 4, 5 and 6, n / (n+m+l) ranges between 0.1 and 0.9999.

[0106] In embodiments of Structures 3, 4, 5 and 6, n / (n+m+l) ranges between 0.5 and 0.999.

[0107] In embodiments of Structures 3, 4, 5 and 6, n / (n+m=l) ranges between 0.95 and 0.999. In embodiments, the invention also provides polymer compositions comprising, consisting essentially of or consisting of one or more copolymers of Structure 3, 4, 5 or 6.

[0108] Copolymers of this invention also include those of Structures 7 and 8 as well as polymer compositions comprising, consisting essentially of or consisting of one or more copolymer of structures 7 or 8:

[0109] Structure 8 where each Ri, R2 and R3 are independently defined as in Structure 1 in all its listed embodiments; and n and m are integers independently ranging from 1 to 10 million.

[0110] In embodiments, m is 1 and n ranges from 1-10 million. In embodiments, m is 1 and n ranges from 10-10 million. In embodiments, m is 1 and n ranges from 10 to 1000. In embodiments, m is 1 and n ranges from 10 to 100.

[0111] In embodiments, m is 1-10 and n ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100.

[0112] In embodiments, each of R1 and R2is hydrogen and R3is hydrogen, acyl, or alkyl. Copolymers of this invention also include those of structure 9 as well as polymer compositions comprising, consisting essentially of or consisting of one or more cpolymer of structure 9:

[0113] Structure 9 where:

[0114] Q, M, L, K, J, I, H, and G are as defined in Structure 1 ; n, m, I, k, j, I, h, and g are as defined in various embodiments of Structure 1 ; each R3is as defined in the various embodiments of Structure 1 ; p is an integer ranging from 1 to 10 million; and r is an integer ranging from 1- 10 million. in embodiments, at least one of n, m or I is non-zero. In embodiments, n, m and I are nonzero and each of k, j, I, h and g is zero. In embodiments, p is 1 and r ranges from 1-10 million. In embodiments, p is 1 and r ranges from 10-10 million. In embodiments, p is 1 and r ranges from 10 to 1000. In embodiments, p is 1 and r ranges from 10 to 100. In embodiments, p is 1-300, and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100. In embodiments, p is 1-10,000, and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100.

[0115] In embodiments, p is 1-10 and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100.

[0116] In embodiments, each of Ri and R2 of Q, M, L, K, J, I, H and G is hydrogen and R3 is hydrogen, acyl, or alkyl.

[0117] In embodiments, each of R1 and R2 of Q, M, L, K, J, I, H and G is hydrogen or methyl or phenyl and R3 is hydrogen, acyl, or alkyl.

[0118] In embodiments, the reaction between a PDHDO or M-PDHDO prepolymers with a second monomer is used to create a copolymer that has different properties from the starting PDHDO or M-PDHDO prepolymer including, but not limited to, tensile strength, elasticity, or barrier to oxygen and water. In other embodiments the reaction between a PDHDO or M- PDHDO prepolymers with a small amount of a second monomer is used to increase the molecular weight of the starting PDHDO or M-PDHDO prepolymer by chain extension. Polyester copolymers of Structure 3 and Structure 5 are prepared by the condensation polymerization of dibasic acids, diesters, diacid halides, or anhydrides with either DHDO, a mixture of glycolaldehyde dimers, PDHDO or M-PDHDO, and mixture thereof. The reaction is carried out either in the solid state or in solution and optionally a catalyst is used. Catalysts includes basic compounds such as carbonates, primary secondary and tertiary amines, as well as aluminum alkoxides, or metal compounds and oxides including but not limited to zinc, tin, antimony, and titanium compounds. Various methods are used to remove the byproduct of the reaction, which may include water, hydrochloric acid, methanol, ethanol or acidic acid. Said method includes running the reaction under reduced pressure, the use of dehydrating reagents, or by using reactors that allows the condensation of water away from the reaction mixture such as a Dean-Stark trap. The reaction is run at a temperature ranging from 0 °C to 280 °C, but preferably between 30 °C and 120 °C. In embodiments other additive may be added during the polymerization including surfactants, stabilizers, antioxidants, nucleating agents, fillers, pigments and dyes.

[0119] Polyurethane copolymers of Structure 4 and Structure 6 and related materials including coatings adhesives, foams and sealants are prepared by the reaction of di- tri- and polyisocyanates with either DHDO, a mixture of glycolaldehyde dimers, PDHDO or M-PDHDO, and mixture thereof. Polyurethanes copolymers of Structures 4 and 6 maybe linear, branched or crosslinked. The polymerization reaction is carried out either by mixing the reagents in their neat liquid or viscous state or in solution and optionally a catalyst is used. Catalysts include metal compounds and amines. Often a metal compound such as an organotin compound is combined with a tertiary amine. Other useful catalysts include guanidines, amidines, / V-heterocyclic carbenes, and organic “strong or super-strong’’ Bronsted acids. In embodiments dibutyltin dilaurate and dibutyltin diacetate catalysts are used. In embodiments the catalyst is selected from the group of 1 ,4- diazabicyclo[2.2.2]octane (DABCO); 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), A / -methyl- 1 ,5,7-triazabicyclododecene (MTBD), and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1 ,3-bis(ditertiobutyl)imidazol-2-ylidene. The reaction is run at a temperature ranging from 0 °C to 280 °C, but preferably between 20 °C and 80 °C. In embodiments the polymerization process is at or near room temperature. In embodiments the polymerization process is run in a reactor to produce a plastic product (resin) that is further transformed into the finished good (elastomer, fiber, plastic item) by an extrusion, molding, spinning, or casting method. In other embodiments the polymerization process is run in situ and the product is in the form of a coated good, a cured adhesive, or a blown foam. In embodiments, water or a blowing aged are added during the polymerization to cause the product to foam. In embodiments other additive may be added during the polymerization including surfactants, stabilizers, antioxidants, nucleating agents, fillers, pigments, and dyes.

[0120] Polycarbonate copolymers of Structure 7, Structure 8 and Structure 9 are prepared by the condensation polymerization of di alkyl carbonates, alkylene carbonate or phosgene, diphosgene, triphosgene, carbonyl diimidazole, disuccinimidyl carbonate, carbon monoxide with either DHDO, a mixture of glycolaldehyde dimers, PDHDO or M-PDHDO, and mixture thereof. The reaction is carried out either in the solid state or in solution and optionally a catalyst is used. Catalysts include basic compounds such as primary secondary and tertiary amines, as well as metals supported on carbon such as palladium, iron, bismuth and copper. In embodiments an organometallic complex of zinc, cobalt, vanadium, manganese is used. In embodiment the ligand is / V, / V-bis(salicylidene)ethylenediamine. Various methods are used to remove the byproduct of the reaction, which may include hydrochloric acid, methanol, ethanol, ethylene glycol pr propylene glycol. Said method includes running the reaction under reduced pressure, the use of dehydrating reagents, or by using reactors that allows the condensation of water methanol or other biproducts away from the reaction mixture such as a Dean-Stark trap. The reaction is run at a temperature ranging from 60 °C to 280 °C. In embodiments other additive may be added during the polymerization including surfactants, stabilizers, antioxidants, nucleating agents, fillers, pigments and dyes.

[0121] In embodiments, the invention provides a polymer comprising two or more glycolaldehyde dimers selected from the group of 2,5-dihydroxy-1 ,4-dioxane; (1 ,2- dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2- diol); 1 ,2-dihydroxyethoxyacetaldehyde; (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'- oxydiacetaldehyde. In embodiments, the invention provides a polymer comprising two or more glycolaldehyde dimers selected from the group of 2,5-dihydroxy-1 ,4-dioxane; (1 ,2- dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2- diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'- oxydiacetaldehyde.

[0122] In embodiments, the invention provides a method of making the recited polymes by polymerization of a mixture comprising two or more glycolaldehyde dimers in the presence of a Lewis acid catalysts

[0123] In embodiments, the invention provides products of this recited method. The products may be polymeric or prepolymeric.

[0124] In embodiments, the invention provides a polymer comprising one or more glycolaldehyde dimer selected from the group of 2, 5-dihydroxy-1 ,4-dioxane; (1 ,2- dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2- diol); 1 ,2-dihydroxyethoxyacetaldehyde; (1 ,3-dioxetane-2,4-diyl)dimethanol; 2,2'- oxydiacetaldehyde and a second monomer. In embodiments, the invention provides a polymer comprising one or more glycolaldehyde dimer selected from the group 2,5- dihydroxy-1 ,4-dioxane; (1 ,2-dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan- 4-ol; 1 ,1'-oxydi(ethane-1 ,2-diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4- diyl)dimethanol; and 2,2'-oxydiacetaldehyde.

[0125] In embodiments, the second monomer is selected from the group of glycolaldehyde, hydroxyaldehydes, carbohydrates, polysaccharides, diols, polyols, compounds containing two or more carboxylic acid groups, hydroxyacids, aminoacids, compounds containing two or more carboxylic acid ester groups, compounds containing two or more acyl chloride groups, compounds containing two or more acyl bromide groups, compounds containing two or more isocyanate groups, compounds containing two or more oxirane groups, compounds containing two or more isothiocyanate groups, compounds containing two or more nitrile groups, compounds containing two or more azide groups, phosgene, dialkyl carbonates, dialkyl dichlorosilanes, and diaryldichlorosilanes.

[0126] In embodiments, the invention provides a polymer obtained by reaction of one or more glycolaldehyde dimer selected from the group of 2,5-dihydroxy-1 ,4-dioxane; (1 ,2- dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'-oxydi(ethane-1 ,2- diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'- oxydiacetaldehyde and a second monomer selected from the group of glycolaldehyde, hydroxyaldehydes, carbohydrates, polysaccharides, diols, polyols, compounds containing two or more carboxylic acid groups, hydroxyacids, aminoacids, compounds containing two or more carboxylic acid ester groups, compounds containing two or more acyl chloride groups, compounds containing two or more acyl bromide groups, compounds containing two or more isocyanate groups, compounds containing two or more oxirane groups, compounds containing two or more isothiocyanate groups, compounds containing two or more nitrile groups, compounds containing two or more azide groups, phosgene, dialkyl carbonates, dialkyl dichlorosilanes, and diaryldichlorosilanes.

[0127] Groups herein are optionally substituted most generally with one or more alky, alkenyl, alkynyl, and aryl, heteroaryl, carbocyclyl, and heterocyclyl groups can be substituted, for example, with one or more oxo group, thioxo group, halogen, nitro, cyano, cyanate, azido, thiocyano, isocyano, isothiocyano, sulfhydryl, hydroxyl, alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl, carbocyclyloxy, heterocyclyl, heterocyclyloxy, alkylthio, alkenylthio, alkynylthio, arylthio, thioheteroaryl, thioheteroaryl, thiocarbocyclyl, thioheterocyclyl, -CORs, -COH, -OCORs, -OCOH, -CO-ORs, -CO-OH, -CO-O-CO-Rs, -CON(Rs)2, -CONHRs, -CONH2, -NRs-CORs, -NHCORs, -NHRs, - N(Rs)2, -O-SO2-RS, -SO2-Rs, -SO2-NHRs, -SO2-N(Rs)2, -NRs-SO2-Rs, -NH-SO2-Rs,- NRsCO-N(Rs)2, -NH-CO-NHRs, -O-PO(ORs)2, -O-PO(ORs)(N(Rs)2), -O-PO(N(Rs)2)2, -N- PO(ORs)2, -N-PO(ORs)(N(Rs)2), -P(Rs)2 , -B(OH)2, -B(OH)(ORs), -B(ORs)2, where each Rs independently is an organic group and more specifically is an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl group or two Rs within the same substituent can together form a carbocyclic or heterocyclic ring having 3 to 10 ring atoms. Organic groups of non-hydrogen substituents are in turn optionally substituted with one or more halogens, nitro, cyano, isocyano, isothiocyano, hydroxyl, sulfhydryl, haloalkyl, hydroxyalkyl, amino, alkylamino, dialkylamino, arylalkyl, unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl alkylalkenyl, alkylalkynyl, haloaryl, hydroxylaryl, alkylaryl, unsubstituted aryl, unsubstituted carbocylic, halo-substituted carbocyclic, hydroxyl-substituted carbocyclic, alkyl-substituted carbocyclic, unsubstituted heterocyclic, unsubstituted heteroaryl, alkylsubstituted heteroaryl, or alkyl-substituted heterocyclic. In specific embodiments, Rs groups of substituents are independently selected from alkyl groups, haloalkyl groups, phenyl groups, benzyl groups and halo-substituted phenyl and benzyl groups. In specific embodiments, non-hydrogen substituents have 1-20 carbon atoms, 1-10 carbon atoms, 1-7 carbon atoms, 1-5 carbon atoms or 1-3 carbon atoms. In specific embodiments, nonhydrogen substituents have 1-10 heteroatoms, 1-6 heteroatoms, 1-4 heteroatoms, or 1 , 2, or 3 heteroatoms. Heteroatoms include O, N, S, P, B and Se and preferably are O, N or S.

[0128] In embodiments, optional substitution is substitution with one or more of the groups listed in the definitions of R1-R3 of Structure 1.

[0129] In specific embodiments, optional substitution is substitution with 1-12 (or 1-3 or 1 to 3 or 1 to 6) non-hydrogen substituents. In specific embodiments, optional substitution is substitution with 1-6 non-hydrogen substituents. In specific embodiments, optional substitution is substitution with 1-3 non-hydrogen substituents. In specific embodiments, optional substituents contain 6 or fewer carbon atoms. In specific embodiments, optional substitution is substitution by one or more halogen, hydroxyl group, cyano group, oxo group, thioxo group, unsubstituted C1-C6 alkyl group or unsubstituted aryl group. The term oxo group and thioxo group refer to substitution of a carbon atom with a =0 or a =S to form respectively — CO — (carbonyl) or — CS — (thiocarbonyl) groups.

[0130] In specific embodiments, non-hydrogen substituents for optional substitution include alkyl, alkoxy, halogen (F, Cl, Br or I and preferably Cl or F), haloalkyl, or haloalkoxy. In specific embodiments, non-hydrogen substituents for optional substitution include methyl, ethyl, methoxy, ethoxy, F, Cl, and trifluormethyl. Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl groups and specifically trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri, tetra- and pentahalo-substituted phenyl groups; mono-, di, tri-, tetra-, penta-, hexa-, and hepta-halo-substituted naphthalene groups; 3- or 4-halo-substituted phenyl groups, 3- or 4- alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted phenyl groups, 3- or 4-RsCO- substituted phenyl, 5- or 6-halo-substituted naphthalene groups. More specifically, substituted aryl groups include acetylphenyl groups, particularly 4-acetylphenyl groups; fluorophenyl groups, particularly 3-fluorophenyl and 4-fluorophenyl groups; chlorophenyl groups, particularly 3-chlorophenyl and 4-chlorophenyl groups; methylphenyl groups, particularly 4-methylphenyl groups, and methoxyphenyl groups, particularly 4- methoxyphenyl groups.

[0131] As to any of the above groups which contain one or more substituents, it is understood, that such groups do not contain any substitution or substitution patterns which are sterically impractical and / or synthetically non-feasible. In addition, the compounds of this invention include all stereochemical isomers arising from the substitution of these compounds.

[0132] Polymers and copolymers of the invention may contain chemical groups (acidic or basic groups) that can be in the form of salts. Exemplary acid addition salts include acetates (such as those formed with acetic acid or trihaloacetic acid, for example, trifluoroacetic acid), adipates, alginates, ascorbates, aspartates, benzoates, benzenesulfonates, bisulfates, borates, butyrates, citrates, camphorates, camphorsulfonates, cyclopentanepropionates, digluconates, dodecylsulfates, ethanesulfonates, fumarates, glucoheptanoates, glycerophosphates, hemisulfates, heptanoates, hexanoates, hydrochlorides (formed with hydrochloric acid), hydrobromides (formed with hydrogen bromide), hydroiodides, 2- hydroxyethanesulfonates, lactates, maleates (formed with maleic acid), methanesulfonates (formed with methanesulfonic acid), 2-naphthalenesulfonates, nicotinates, nitrates, oxalates, pectinates, persulfates, 3-phenylpropionates, phosphates, picrates, pivalates, propionates, salicylates, succinates, sulfates (such as those formed with sulfuric acid), sulfonates (such as those mentioned herein), tartrates, thiocyanates, toluenesulfonates such as tosylates, undecanoates, and the like.

[0133] Exemplary basic salts include ammonium salts, alkali metal salts such as sodium, lithium, and potassium salts, alkaline earth metal salts such as calcium and magnesium salts, salts with organic bases (for example, organic amines) such as benzathines, dicyclohexylamines, hydrabamines [formed with N,N-bis(dehydro-abietyl)ethylenediamine], N-methyl-D- glucamines, N-methyl-D-glucamides, t-butyl amines, and salts with amino acids such as arginine, lysine and the like. Basic nitrogen-containing groups may be quaternized with agents such as lower alkyl halides (e.g., methyl, ethyl, propyl, and butyl chlorides, bromides and iodides), dialkyl sulfates (e.g., dimethyl, diethyl, dibutyl, and diamyl sulfates), long chain halides (e.g., decyl, lauryl, myristyl and stearyl chlorides, bromides and iodides), aralkyl halides (e.g., benzyl and phenethyl bromides), and others.

[0134] Compounds of the present invention, and salts thereof, may exist in their tautomeric form, in which hydrogen atoms are transposed to other parts of the molecules and the chemical bonds between the atoms of the molecules are consequently rearranged. It should be understood that all tautomeric forms, insofar as they may exist, are included within the invention.

[0135] Additionally, inventive compounds may have trans and cis isomers and may contain one or more chiral centers, therefore exist in enantiomeric and diastereomeric forms. The invention includes all such isomers, as well as mixtures of cis and trans isomers, mixtures of diastereomers and racemic mixtures of enantiomers (optical isomers). When no specific mention is made of the configuration (cis, trans or R or S) of a compound (or of an asymmetric carbon), then any one of the isomers or a mixture of more than one isomer is intended. The processes for preparation can use racemates, enantiomers, or diastereomers as starting materials. When enantiomeric or diastereomeric products are prepared, they can be separated by conventional methods, for example, by chromatographic or fractional crystallization. The inventive compounds may be in the free or hydrate form. With respect to the various compounds of the invention, the atoms therein may have various isotopic forms, e.g., isotopes of hydrogen include deuterium and tritium. All isotopic variants of compounds of the invention are included within the invention and particularly included at deuterium and 13C isotopic variants. It will be appreciated that such isotopic variants may be useful for carrying out various chemical and biological analyses, investigations of reaction mechanisms and the like. Methods for making isotopic variants are known in the art.

[0136] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although this invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the claims. The specific embodiments provided are examples of useful embodiments of the invention and it will be apparent to one skilled in the art that the invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the description.

[0137] As used in this specification and in the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Also, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably. It is also to be noted that the terms "comprising", "including", and "having" can be used interchangeably. The expression “of any of claims XX- YY” (wherein XX and YY refer to claim numbers) is intended to provide a multiple dependent claim in the alternative form, and in some embodiments is interchangeable with the expression “as in any one of claims XX- YY.’’

[0138] All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.

[0139] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (particularly in referenced patent documents), are not intended to be included in the claim.

[0140] When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups, including any isomers and enantiomers of the group members, and classes of compounds that can be formed using the substituents are disclosed separately. When a compound is claimed, it should be understood that compounds known in the art including the compounds disclosed in the references disclosed herein are not intended to be included. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure.

[0141] Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. When a compound is described herein such that a particular isomer or enantiomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination.

[0142] One of ordinary skill in the art will appreciate that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials, and synthetic methods are intended to be included in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.

[0143] As used herein, “comprising” is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.

[0144] Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.

[0145] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention. THE EXAMPLES

[0146] Example 1: Synthesis of Polyacetals

[0147] A. A polymer of Structure (m+l+g+ h+i+ k+j) / (n+m+l+g+h+

[0148] A raw material blend of glyaldehyde dimer comprising >90% by wt of 2,5-dihydroxy-1 ,4- dioxane and the reminder <10% wt. being a mixture of 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol, 1 ,1'-oxydi(ethane-1 ,2-diol) and 1 ,2-dihydroxyethoxyacetaldehyde is obtained from a commercial source. This raw material is a sticky waxy semi-clear material.

[0149] 1 g of this raw material is dissolved in 70 mL of anhydrous acetonitrile in oven-dried glassware and 0.2 g of scandium triflate is added. The reaction is refluxed in the presence of freshly activated molecular sieves 3A at 45 °C under reduced pressure (105 Torr) overnight. The solvent is evaporated at the end of the reaction and the crude product is washed with water, and dried under vacuum.1H NMR spectrum of the product (Fig. 1) showed signal typical of six-member cycles, five-member cycles and linear repeat units. Specifically, the large peak of 4.0 ppm indicates the presence of a significant fraction of linear repeat units. This material is an example of mixed dimer PDHDO (M-PDHDO). This polymer is cast on a Teflon® (Trademark, The Chemours Company) fluoropolymer mold into a thin film from an acetone solution. The film is clear and can be easily removed from the Teflon® fluoropolymer block without cracking. The film shows good flexibility when bent over a glass rod.

[0150] B. Comparative Example: a polymer of Structure 1 with n / (n+m+l++g+h+i+k+j)>0.95 and (m+l+g+h+i+k+j) / (n+m+l+g+h+i+k+j)<0.05 and RtR2, Rs=H..

[0151] A sample of 2,5-dihydroxy-1 ,4-dioxane with with purity of > 99.5% is obtained from commercial sources. This raw material is a white crystalline powder.

[0152] 1 g of this raw material is dissolved in 70 mL of anhydrous acetonitrile in oven-dried glassware and 0.2 g of scandium triflate is added. The reaction is refluxed in the presence of freshly activated molecular sieves 3A at 40 °C and the pressure is progressively reduced over a three day period until the solvent is completely removed. The crude product is washed with water, and dried under vacuum.1H NMR spectrum of the product (Fig. 2) shows the predominant proton signals typical of six-member cycles units. Specifically, the axial CH_are at 5.00-5.60 ppm,_the equatorial CH_are at 4.5-5.0 ppm and the six-member ring CH2 are at 3.2-4.2 ppm. This polymer is an example of PDHDO which does not contain any significant level of glycolaldehyde dimers other than the six member ring repeat unit Q in Structure 1. This polymer is cast on a Teflon® fluoropolymer mold into a thin film from an acetone solution. The film is hazy upon drying and it is difficult to remove from the Teflon® fluoropolymer block without cracking. It cannot be bent over a glass rod without cracking.

[0153] C. 2,5-Dihydroxy-1 ,4-dioxane with 95% purity (4 g, 33 mmoles) is dissolved in 70 mL of anhydrous acetonitrile in oven-dried glassware and 0.244 g of lanthanum triflate is added. The reaction is refluxed in the presence of freshly activated molecular sieves 3A at 45 °C under reduced pressure (105 Torr) for 48 hrs. The solvent is evaporated at the end of the reaction and the crude product is washed with water, and dried under vacuum. The purity of reactant 2,5-dihydroxy-1 ,4-dioxane can be selected to prepare desired copolymers of Structure 1.

[0154] D. 2,5-Dihydroxy-1 ,4-dioxane with purity of > 99.5% (1 g) is dissolved in 20 mL of moist acetonitrile (10% by volume minimum water content) and stirred for several hours. 50 mL of the ionic liquid1-Butyl-3-methylimidazolium trifluoromethanesulfonate is then added and the acetonitrile and water are removed by fractional distillation. After the removal of water and acetonitrile has been completed, 0.08 g of lanthanum triflate is added to the ionic liquid solution of the monomer and the reaction is placed under high vacuum for 12 hours at 30 °C. The next day, excess hexane is added to precipitate the prepared polymer, which is rinsed and dried.1H-NMR analysis shows that the prepared polymer contains repeat units that are both linear and cyclic dimers of glycolaldehyde, an example of M-PDHDO.

[0155] E. A polymer of Structure 1 with n / (n+m+l+g+h+i+k+j)<0.95 and (m+l+g+h+i+k+j) / (n+m+l+g+h+i+k+j)>0.05, Ri R2=H and R3=COCH3.

[0156] The product of example 1A (1 eq) is end-capped by reaction with acetic anhydride (2.2 eq) in chloroform in the presence of 0.1 molar% of 4-dimethylaminepyridine. After stirring the reaction for 4 hours, the solvent is evaporated under vacuum. The crude product is dissolved in CHCI3, washed with a 5% aqueous solution of sodium bicarbonate and then washed with water, dried over MgSO4, and evaporated under reduced pressure to produce a solid.

[0157] F. A copolymer of Structure 1 with n / (n+m+l+g+h+i+k+j)<0.95 and (m+l+g+h+i+k+j) / (n+m+l+g+h+i+k+j)>0.05, Ri=H, R2=H and CH3, and R3=H.is prepared my mixing 1 g of 2,5-dihydoxy-1 ,4-dioxane with purity of > 99.5% with 0.7 g of lactaldehyde dimer in 50 mL of anhydrous acetonitrile. 0.15 g scandium triflate is added and the reaction is set to reflux at 40 °C at reduced pressure of 110 Torr and in the presence of freshly activated molecular sieves for three days. After polymerization begins, the solvent is gradually removed and the reaction is allowed to continue. After 72 hours the reaction is stopped by rinsing the solid with water and drying under vacuum. Example 2: Synthesis of Polyesters

[0158] A. A polyester copolymer of Structure 3, with n = 1 and m=1 and R = -CH2CH2- is prepared by reaction of 2,5-dihydroxy-1 ,4-dioxane with succinyl dichloride. 2,5-Dihydroxy- 1 ,4-dioxane (DOHD, 1.2 g, 100 mmoles) with purity of > 99.5% is dissolved in a dicholoromethane / acetonitrile mixture. Triethylamine (2.2 g, 220 mmoles) is added and the mixture is cooled in an ice bath. Succinic acid dichloride (1.55 g, 100 mmoles) is added dropwise. The reaction is allowed to warm up to room temperature and then brought to gentle reflux for 1 hr. A white precipitate forms, which is decanted off and then rinsed with a 5% sodium bicarbonate solution until pH>8 is obtained. The product is then filtered off and dried. A small potion is dissolved in deuterated chloroform and the structure is confirmed by1H-NMR analysis.

[0159] B. A polyester copolymer of Structure 3 with n = 1 and m=1 and R= -CH2CH2- is prepared by reaction of 2,5-dihydroxy-1 ,4-dioxane with dimethyl succinate. 2,5-Dihydroxy- 1 ,4-dioxane (12 g, 1 eq.) with purity of > 99.5%, is dissolved in propionitrile (50 mL) and 25mL of boron trifluoride acetonitrile complex solution (Sigma Aldrich) is added. Dimethyl succinate (1 eq.) is added and the mixture is set to gentle reflux overnight. The methanol byproduct is condensed in a Dean Stark trap. The mixture is allowed to cool and the solvent is removed using a rotary evaporator. After solvent evaporation, a white precipitate formed. The solid product is then filtered off, rinsed and dried.

[0160] C. A polyester copolymer of Structure 5 with p=1 , q =1 and R=-CH2CH2- is prepared by reaction of a mixture of various glycolaldehyde dimers with succinyl dichloride. A mixture (1 .2 g, 100 mmoles) containing 95 wt% of 2, 5-dihydroxy-1 ,4-dioxane and the reminder 5 wt% being a mixture of glycolaldehyde; (1 ,2-dihydroxyethoxy)acetaldehyde; 2- (hydroxymethyl)-l ,3-dioxolan-4-ol; 1,1'-oxydi(ethane-1 ,2-diol); 1 ,2- dihydroxyethoxyacetaldehyde; (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'- oxydiacetaldehyde) is dissolved in a dicholoromethane / acetonitrile mixture. Triethylamine (2.2 g, 220 mmoles) is added and the mixture is cooled in an ice bath. Succinic acid dichloride (1 .55 g, 100 mmoles) is added dropwise. The reaction is allowed to warm up to room temperature and then brought to gentle reflux for 1 hr. A white precipitated forms, which is rinsed with a 5 wt% sodium bicarbonate solution until pH>8 is obtained. The polymer product is then filtered off and dried.

[0161] D. A polyester copolymer of Structure 3 with n=1 and m>1 and R = -CH2CH2- is prepared by reaction of the polymer product PDHDO of Example 1B with succinic acid dichloride. The PDHDO prepolymer is prepared as described in Example 1 B. 1 .20 gr of PDHDO is dissolved in chloroform, 0.13 gr of triethylamine is added and the mixture is cooled in an ice bath. Succinic acid dichloride (0.01 g) is added dropwise. The reaction is allowed to warm up to room temperature and then brought to gentle reflux for 1 hr. The crude reaction is cooled to room temperature, washed with sodium bicarbonate until pH = 8. The organic phase is separated and the solvent evaporated at the rotary evaporator. A powdery material is obtained. This material is too brittle to be cast into thin films.

[0162] E. A polyester copolymer of Structure 5 with q=1 and p>1 , Ri and R2 =H, and R = - CH2CH2- is prepared by reaction of the polymer product containing two or more glycolaldhyde dimers as monomers (Mixed-PDHDO) of Example 1 A with succinic acid dichloride. The polyacetal prepolymer (Mixed-PDHDO) is prepared as described in Example 1A. 1.20 gr of this prepolymer is dissolved in chloroform, 0.13 gr of triethylamine is added and the mixture is cooled in an ice bath. Succinic acid dichloride (0.01 g) is added dropwise. The reaction is allowed to warm up to room temperature and then brought to gentle reflux for 1 hr. The crude reaction is cooled to room temperature, washed with sodium bicarbonate until pH = 8. The organic phase is separated and the solvent evaporated at the rotary evaporator. An amorphous semi clear material is obtained. This material is cast into thin films from a chloroform solution.

[0163] F. A polyester copolymer of Structure 3 with n = 1 and m=1 R = phenylene is prepared by reaction of 2,5-dihydroxy-1 ,4-dioxane with dimethyl terephthalate. 2,5-Dihydroxy-1 ,4- dioxane (12 g, 1 eq.) with purity of > 99.5%is dissolved in propionitrile (50 mL) and 25 mL of boron trifluoride acetonitrile complex solution (Sigma Aldrich) is added. Dimethyl terephthalate (1 eq.) is added and the mixture is set to gentle reflux overnight. The methanol byproduct is condensed in a Dean Stark trap. The reaction mixture is allowed to cool and the solvent removed using a rotary evaporator. After solvent evaporation, a white precipitate formed. The solid product is then filtered off, rinsed and dried.

[0164] G. A polyester copolymer of Structure 3 with n = 1 and m=1 R = 2,5-furanylene is prepared by reaction of 2,5-dihydroxy-1 ,4-dioxane with 2,5-furandicarbonyl dichloride . 2,5- Dihydroxy-1 ,4-dioxane (DOHD, 1 .2 g, 100 mmoles) with purity of > 99.5%is dissolved in a dicholoromethane / acetonitrile mixture. Triethylamine (2.2 g, 220 mmoles) is added and the mixture is cooled in an ice bath. 2,5-furandicarbonyl dichloride (100 mmoles) is added dropwise. The reaction is allowed to warm up to room temperature and then brought to gentle reflux for 1 hr. A white precipitate forms, which is decanted off and then rinsed with a 5% sodium bicarbonate solution until pH>8 is obtained. The product is then filtered off and dried. A small potion is dissolved in deuterated chloroform and the structure is confirmed by1H-NMR analysis. Example 3: Synthesis of polyurethanes

[0165] A. A polyurethane copolymer of Structure 4 with n=1and m=1 and R = -(CH2)6- is prepared by reaction of DHDO with hexamethylene diisocyanate. 0.1 mol of DHDO with nominal purity of 100% is dissolved in minimal amount of acetonitrile and 0.5% by mole of dibutyltin dilaurate and 0.5% of 1 ,8-diazabicyclo[5.4.0]undecen-7-ene were added. 0.1 mol of hexamethylene diisocyanate is added under vigorous stirring to form a fibrous material after solvent evaporation.

[0166] B. A polyurethane copolymer of Structure 6 with q=1 and p>1 and R = -(CH2)6- is prepared by reaction of the product of example 1A (M-PDHDO) with hexamethylene diisocyanate 1 .20 gr of the polymer prepared in example 1A is dissolved in acetone, 0.13 gr of hexamethylene diisocyanate is added dropwise followed by a catalytic amount of dibutyl tin dilaurate and triethylamine, and the reaction is allowed to stir for a few hours at 60C. The crude reaction is cooled to room temperature, washed and the solvent evaporated at the rotary evaporator. An amorphous semi clear material is obtained. This material is cast into thin films from a chloroform solution.

[0167] C. A polyurethane copolymer of Structure 4 with n=1and m>1 and R = -(CH2)e- is prepared by reaction of the product of example 1 B (PDHDO) with hexamethylene diisocyanate 1 .20 gr of the polymer prepared in example 1 B is dissolved in acetone, 0.13 gr of hexamethylene diisocyanate is added dropwise followed by a catalytic amount of dibutyl tin dilaurate and triethylamine, and the reaction is allowed to stir for a few hours at 60C. The crude reaction is cooled to room temperature, washed and the solvent evaporated at the rotary evaporator. An amorphous semi clear material was obtained. This material was cast into thin films from a chloroform solution.

[0168] D. A polyurethane foam was prepared following the general recipe described in J. Chem. Educ. 2010, 87, 2, 212-215. A polyol mixture is prepared by mixing with a high shear mixer 5 g of PDHDO prepolymer prepared using example 1 B, with 15 g of a 3000MW glycerin and propylene oxide based polyether polyol triol (Carpol GP-3000). Once the mixture is homogeneous 0.6 g of deionized water, 0.2 g of dibutyltin dilaurate (DBTL), and 0.4 g of silicone surfactant (Dow Corning, 193 Surfactant) are added. The components are mixed vigorously for 1 min with a mechanical stirrer in a 500 ml_ beaker. Then 11 .5 g of diphenylmethane 4,4-diisocyanate (MDI) was added to the same beaker and rigorously stirred for 15 s. The resulting mixture is left to rest and react for a few minutes, which allows the formation of the foam. E. A polyurethane foam is prepared following the general recipe described in J. Chem. Educ. 2010, 87, 2, 212-215. A polyol mixture is prepared by mixing with a high shear mixer 15 g of a polyacetal prepolymer M-PDHDO prepared using example 1A, with 5 g of a 1000 MW glycerin and propylene oxide based polyether polyol triol (Carpol GP-1000). Once the mixture is homogeneous 0.6 g of deionized water, 0.2 g of dibutyltin dilaurate (DBTL), and 0.4 g of silicone surfactant (Dow Corning, 193 Surfactant) are added. The components are mixed vigorously for 1 min with a mechanical stirrer in a 500 mL beaker. Then 13.5 g of diphenylmethane 4,4-diisocyanate (MDI) was added to the same beaker and rigorously stirred for 15 s. The resulting mixture is left to rest and react for a few minutes, which allows the formation of the foam.

[0169] F. A polyurethane coating is prepared by mixing hexamethylene diisocyanate trimer (HDI trimer, Desmur-N) with the polyacetal pre-polymer prepared in Example 1A (M- PDHDO). The polyacetal prepolymer is first degassed under vacuum and then mixed with the catalyst dibutyl tin dilaurate with a mechanical stirrer at 35 °C. The HDI trimer is then added and the mixture stirred until homogeneous. The mixture is then sprayed on a steel plate and allowed to cure at 50°C for 12 h to give a though coating of homogeneous thickness.

[0170] Example 4. Synthesis of polycarbonates

[0171] A. A polymer of Structure 7. 0.1 mole of 2,5-dihydroxy-1 ,4-dioxane purity of > 99.5% is dissolved in a pyridine / THF mixture and 0.05% wt of 4-dimethylaminopyridine is added. 0.1 Mole of dimethyl carbonate is added and the mixture is brought to reflux under reduced pressure. Methanol is condensed in a Dean-Stark trap. After 4 hours, the crude reaction is cooled to room temperature, washed, and the solvent evaporated at the rotary evaporator. An amorphous powdery material is obtained.

[0172] B. A polymer of Structure 9. 1.2 g of the polymer prepared in example 1A (M-PDHDO) is dissolved in dimethyl carbonate and 0.05% wt of 4-dimethylaminopyridine is added. The mixture is brought to reflux under reduced pressure. Methanol is condensed in a Dean-Stark trap. After 6 hours, the crude reaction is cooled to room temperature, washed, and the solvent evaporated at the rotary evaporator. An amorphous semi clear material was obtained. This material was cast into thin films from a chloroform solution.

Claims

We claim:1 . A polymer that comprises two or more structurally different glycolaldehyde dimers as monomer units wherein the dimers are selected from the group consisting of 2,5-dihydroxy-1.4-dioxane; (1 ,2-dihydroxyethoxy)acetaldehyde; 2-(hydroxymethyl)-1 ,3-dioxolan-4-ol; 1 ,1'- oxydi(ethane-1 ,2-diol); 2,2’-oxydi(ethane-1 ,1-diol); (1 ,3-dioxetane-2,4-diyl)dimethanol; and 2,2'-oxydiacetaldehyde.

2. The polymer of claim 1 having from 0.1% to 25% by weight of monomers other than2.5-dihydroxy-1 ,4-dioxane.

3. A polymer of claim 1 of Structure 1 :where Q, M, L, K, J, I, H and G are divalent glycolaldehdye dimer species as illustrated and g, h, i, j, k, I, m and n are integers from zero to 10 million, wherein at least two of g, h, i, j, k, I, m and n are different from zero and p is an integer ranging from 1-10 million; andeach Ri, R2and R34. is independently selected from the group consisting of hydrogen (-H), deuterium (-D), an halogen atom ( — F, — Cl, — Br, — I), a hydroxyl group ( — OH), an amino group ( — NH2), an alkylamino group ( — NHR9), a (bisalkylamino) group [ — N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an aminoalkylene group, an (alkylamino)alkylene group, a (bisalkylamino)alkylene group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an alkyl carbonate group, an acrylate group, a methacrylate group, a group comprising an oxirane ring, a glycidyl group, a thiol group (— SH), alkylthio (— SR9), a nitro group ( — NO2), a cyano group ( — CEN), a isocyanate group ( — N=C=O), a azide group ( — N3), a cyanate group ( — O=C=N), a nitroso group (—NO), a phosphine group [ — P(R9)2], a phosphate group [ — OP(O)(OR9)2], a phosphonate group [ — P(O)(OR9)2], a sulfate group ( — O — SO3R9), a sulfonate group ( — SO3R9), a thiocyanate group (— S=C=N), a iso thiocyanate group ( — N=C=S), a — CORg group, a — COORg group, a — CON(R9)2group, a — CSR9group, a — CS — ORg group, a — N(R9)2group, a —CO — O— CO— Rg, a — CO — NR9— CO — Rg, a — N=C(Rg)2, and a — CR9=NR9; where each R9is independently, a hydrogen, deuterium, an alkyl, an aryl, an alkenyl or an alkynyl group, and each of which Rg is optionally substituted with one or more halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, or thiocyanate group; and / or each Ri, R2and R3is independently optionally oligomeric, pre-polymeric or polymeric in nature and selected from the group consisting of end-capped or uncapped polyethers, poly(fluoroethers), polyglycols, polyacetals, polyolefins, polystyrene, polyfluoroolefins, polyoxides, polychlorolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyols, polyalcohols, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitriles, polybutadiene, alkyds, polyurethanes, epoxies, cellulose and its derivatives, starch and its derivatives, polypeptides, and copolymers thereof.

4. The polymer of claim 3, wherein one or both of R3is independently oligomeric, prepolymeric or polymeric.

5. The polymer of claim 3 or 4, wherein each of Ri and R2is non-oligomeric, not prepolymeric or non-polymeric.

6. The polymer of any one of claims 3-5, wherein each Ri and each R2are independently selected from H, D, optionally substituted alkyl groups having 1-3 carbon atoms, and optionally substituted aryl groups, and optionally substituted phenyl or benzyl groups.

7. The polymer of any one of claims 3-6, wherein each R3independently is hydrogen, deuterium, alkyl, acyl, acrylic, methacrylic, aminoalkylene, (alkylamino)alkylene, (bisalkylamino)alkylene, glycidyl in particular RgCO-, where R9is optionally substituted alkyl, optionally substituted alkenyl or optionally substituted aryl.

8. The polymer of any one of claims 3-7, wherein each Ri and each R2are hydrogen and each R3is indepedently hydrogen, alkyl or acyl.

9. The polymer of claim 3, wherein RI-R3groups include hydrogen, methyl, ethyl, n- butyl, acetyl (CH3CO-), phenyl, and benzoyl groups each of which is optionally substituted with one or more halogen, an alkyl having 1-3 carbon atoms or an alkoxy having 1-3 carbon atoms.

10. The polymer of any one of claims 3-9, wherein (n+m+l) x p ranges from 10 to 200,000 or optionally (n+m+l) x p ranges from 10 to 100,000.11 . The polymer of any one of claims 3-9, wherein (n+m+l+k+j+i+h+g) x p ranges from 2 to 200,000, optionally (n+m+l+k+j+i+h+g) x p ranges from 10 to 1500 or optionally (n+m+l+k+j+i+h+g) x p ranges from 20 to 120.

12. A copolymer of Structure 5, or 6:Other embodiments of this invention include copolymers of Structure 5 and Structure 6 below.or their acid halides, acid chloride, anhydrides, methyl esters, ethyl esters and alkyl ester derivatives: where:Q, M, L, K, J, I, H, and G are as defined in any one of claims 3-11; n, m, I, k, j, I, h, and g are as defined in any one of claims 3-11; each R3 is as defined in any one of claims 3-11; p and q are independently integers ranging from 1 to 10 million;-R- is a bivalent organic radical; and r is an integer ranging from 1 tolO million.

13. The copolymer of claim 12, wherein at least one of n, m or I is non-zero.

14. The copolymer of claim 12 or 13, wherein p is 1 and r ranges from 1-10 million, or p and q are 1 and r ranges from 1-10 million.

15. The copolymer of any one of claims 12-14, wherein p is 1-10, q is 1 and r ranges from 1-10 million or from 10 to 10 million or from 10 to 1000 or from 10 to 100.

16. The copolymer of any one of claims 12-15, wherein each R1 and R2of Q, M, L, K, J, I, H and G is hydrogen, methyl or phenyl and each R3is hydrogen, acyl, or alkyl.

17. A copolymer of Structure 9:Structure 9 wherein:C M, L, K, J, I, H, and G are as defined in any one of claims 3-11; n, m, I, k, j, I, h, and g are as defined in any one of claims 3-11; each R3is as defined in any one of claims 3-11; and p and r are independently integers ranging from 1 to 10 million.

18. A copolymer of any of Structures 3, 4, 7 or 8 as defined herein.

19. A method of making copolymers that comprise two or more different glycolaldehyde dimers by polymerization of a mixture comprising two or more glycolaldehyde dimers in the presence of a Lewis acid catalyst and optionally in the presence of one or more second monomer.

20. A copolymer prepared by the method of claim 19,21 . A method for preparing a copolymer which comprises preparing a prepolymer by the method of claim 19 and further polymerizing the prepolymer in the presence of one or more second monomers.

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