Renewable Monomers and Their Polymers

Abstract

Compounds having the structure (I), (II), or (V), formula (I), (II), (V), are described, wherein R 1 is -H, -CHOH, or -CH(OH)CHOH; R 2 is -H, -OH, or -CHOH; R 3 is -H, -OH, or -CHOH; n is 0 or 1; p is 0 or 1; R 10 is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety may optionally be substituted with a C1-C4-alkyl group or a halogen atom; R is either -ZF or Y, and wherein Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) where R 4 is a C1-C4 alkyl group, and R 7 is a C1-C4-alkyl group, and where Y is hydrogen or a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms, with the proviso that when R is Y and n is 0, then R 1 or R 2 at least one of is not hydrogen. Also described are methods for preparing said compounds, polymers obtained from said compounds, and methods for preparing said polymers. JPEG2022551187000063.jpg44170

Description

[Technical Field]

[0001] (background) Plastics have become ubiquitous consumables in our daily lives. Global plastic production grew to over 380 million tons per year in 2015, an average annual growth rate of 8.5%. Global lifecycle greenhouse gas emissions from the production of these plastics were 1.7 billion tons of CO2 equivalent (CO2e), or 5% of global greenhouse gas emissions, in 2015 and are estimated to increase to 6.5 billion tons of CO2e by 2050 if current trends continue (Zheng, J. & Suh, S. Strategies to reduce the global carbon footprint of plastics. Nat. Clim. Chang. 9, 374-378 (2019)). Moreover, more than one-third of this plastic is discarded after an average lifespan of less than six months, with the majority of it ending up in landfills or the natural environment (Geyer, R.; Jambeck, JR; Law, KL Production, Use, and Fate of All Plastics Ever Made. Sci. Adv. 2017, 3 (7), e1700782). Not only are plastics produced from non-renewable and polluting fossil fuels, they are also non-biodegradable and harmful to the world's ecosystems.

[0002] Research into bio-based and biodegradable polymers is desperately needed to reduce emissions and pollution from plastic production. In 2018, 2,274,000 tonnes of bioplastics were produced, representing less than 1% of global plastic production. Of this 2,274,000 tonnes, 38.7% consisted of biodegradable polymers. However, with increasing consumer demand for renewable products, the bioplastics market is expected to expand significantly over the next decade (Biopolymers facts and statistics 2017 report. Institute for Bioplastics and Biocomposites).

[0003] Although polymers from renewable resources have been developed, their mechanical properties and / or processability usually fall short of those of petroleum-based plastics. Frequently used polymers derived from renewable resources, such as polylactic acid (PLA), polybutyl succinate (PBS), and polyhydroxyalkanoates (PHAs), are not suitable substitutes for packaging materials such as polyethylene terephthalate (PET), the most abundant polyester, accounting for 8% of the global polymer market (Munoz-Guerra, S.; Lavilla, C.; Japu, C.; Martinez de Ilarduya, A. Renewable Terephthalate Polyesters from Carbohydrate-Based Bicyclic Monomers. Green Chem. 2014, 16 (4), 1716-1739). This is due to their inferior mechanical properties and processability. While Coca-Cola Co. and DuPont have commercialized partially renewable PET using renewablely derived diols, they have yet to find a renewable route to economically produce or replace the hard diacid component, terephthalic acid (TPA).

[0004] A satisfactory renewable alternative to PET has yet to be found. Currently, the most promising sustainable alternative to PET appears to be poly(ethylene furanoate) (PEF), produced from 2,5-furandicarboxylic acid. While PEF can be produced from renewable resources, its multi-step reaction sequence from glucose, coupled with undesirable degradation products and the intensive separation required prior to polymerization, limits its commercialization. Furthermore, PEF has been reported to be non-biodegradable (Sajid et al., Green Chem. 2018, 20 (24), 5427-5453).

[0005] Renewable polyesters have been prepared using dianhydrohexitols, such as commercially available isosorbide, which are rigid bicyclic diols derived from sugars. Polyesters containing these cyclic sugars also have excellent thermal and mechanical properties and are more biodegradable (Zamora, F.; Hakkou, K.; Munoz-Guerra, S.; Galbis, J. A. Hydrolytic Degradation of Carbohydrate-Based Aromatic Homo- and Co-Polyesters Analogous to PET and PEI. Polymer Degradation and Stability 2006, 91 (11), 2654-2659). However, a major drawback of these sugars is their low reactivity, which is due to the secondary nature of the alcohol groups and, in some cases, a different stereo-orientation of the hydroxyl groups relative to the fused ring. Furthermore, isosorbide is typically obtained by acid-catalyzed dehydration of D-sorbitol. Obtaining the required purity of isosorbide monomer requires laborious reaction steps including distillation, recrystallization from alcohol, recrystallization from the melt, or a combination of these methods. Furthermore, the synthesis is limited to diols, and the preparation of derivatives such as amines requires additional synthetic steps.

[0006] A similar bicyclic, sugar-derived diacid (2,3:4,5-di-O-methylene-galactarate) has also been synthesized by acetalization of galactaric acid with formaldehyde in an attempt to directly replace terephthalic acid (TPA). High-molecular-weight polymers with excellent thermal and mechanical properties and enhanced aqueous biodegradability were obtained, but production of these precursors from biomass requires a tedious multistep reaction sequence using toxic paraformaldehyde, making commercial synthesis from renewable carbon impractical at present. For example, the production of glucaric acid-based polymers, which are the most promising candidates for feasible production (because they are produced from glucose), requires the fermentation of glucose to gluconic acid, followed by the oxidation of gluconic acid to glucaric acid over a Pt / C catalyst, and finally, the reaction with toxic paraformaldehyde to obtain the final product (Lavilla, C.; Alla, A.; Martinez de Ilarduya, A.; Benito, E.; Garcia-Martin, MG; Galbis, JA; Munoz-Guerra, S. Carbohydrate-Based Polyesters Made from Bicyclic Acetalized Galactaric Acid. Biomacromolecules 2011, 12 (7), 2642-2652; Lavilla, C.; Alla, A.; Martinez de Ilarduya, A.; Benito, E.; Garcia-Martin, MG; Galbis, JA; Munoz-Guerra, S. Biodegradable Aromatic Copolyesters Made from Bicyclic Acetalized Galactaric Acid. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50 (16), 3393-3406).

[0007] Acetals of carbohydrates, such as acetals of glucose, have been prepared. For example, U.S. Patent No. 6,294,666 describes tricyclic compounds prepared by acetalization of glucose. However, U.S. Patent No. 6,294,666 does not describe polymerizable monomers. Also, WO 96 / 32434 A1 describes tricyclic compounds prepared by acetalization of glucose as saccharide residues of polyethylene oxides used in pharmaceutical applications. Also, WO 96 / 32434 A1 does not describe polymerizable monomers. Summary of the Invention [Problem to be solved by the invention]

[0008] Proceeding from the prior art elucidated above, it is an object of the present invention to provide monomers that can be polymerized or copolymerized to produce, in particular, fully renewable, preferably biodegradable, polymers, and ideally, the polymers or copolymers prepared therefrom have good thermal and / or mechanical properties.

[0009] WO2011 / 021398 discloses pyranose and furanose derivatives having a polymerizable group that can be used in photosensitive resins, as well as methods for producing these pyranose and furanose derivatives.

[0010] Other, more specific objects will in part become apparent and in part be pointed out hereinafter. [Means for solving the problem]

[0011] (Summary of the Invention) Some or all of these advantages are achieved according to the present invention by the compound according to claim 1, the method according to claim 7, the polymer according to claim 13, the method according to claim 16 and the use according to claim 22.

[0012] Further advantageous embodiments of the invention are specified in the dependent claims and will be elucidated in detail herein below.

[0013] The present invention provides compounds having the structure (I) or (II) or (V):

[0014] [ka]

[0015] [where: R 1 is -H, -CHOH, or -CH(OH)CHOH; R 2 is -H, -OH, or -CHOH; R 3 is -H, -OH, or -CHOH; R 10 is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety may optionally be substituted with a C1-C4-alkyl group or a halogen atom; n is 0 or 1; p is 0 or 1; R is either -ZF or Y, and where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) and Y is hydrogen or a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms; where R 4 is a C1-C4-alkyl group; and R 7 is a C1-C4 alkyl group, with the proviso that When R is Y and n is 0, R1 or R 2 at least one of which is not hydrogen].

[0016] Preferably, when Z is a hydrocarbon moiety having 0 carbon atoms, it is a covalent bond.

[0017] Preferably, R 10 R can be a substituted or unsubstituted hydrocarbon moiety having 1 to 20 carbon atoms. The term "substituted hydrocarbon moiety having 1 to 20 carbon atoms" refers to a hydrocarbon moiety in which one or more or all hydrogen atoms can be replaced (substituted) with a C1-C4 alkyl group or a halogen atom. Each of the three hydrogen atoms on the terminal carbon atom of the hydrocarbon moiety can be replaced with a C1-C4 alkyl group or a halogen atom. R 10 can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, 1-fluoroisopropyl, 1,1-difluoroisopropyl, 1,1,1-trifluoroisopropyl, 1,1,1,2-tetrafluoro-isopropyl, pentafluoroisopropyl, hexafluoroisopropyl, and the like.

[0018] The -C2H3 group represents a vinyl group, the -C2H group represents an ethynyl group, and the -N3 group represents an azide group.

[0019] In the case of a chemical moiety, such as an alkyl moiety or an aromatic or aliphatic moiety, which is substituted, one of the hydrogen atoms in the moiety is replaced with a substituent. For example, a -CH- moiety substituted with a methyl group corresponds to a -CH(CH)- moiety.

[0020] Surprisingly, it has been discovered that polymerizable monomers can be prepared from renewable resources, such as biomass, using simple synthetic protocols. The compounds reported herein can be obtained by using established acetalization chemistry. Depending on the additional functional groups attached to the aldehyde, monomers with different functional groups can be obtained. Alternatively, acetalization can be performed using aldehydes bearing functional groups that can be easily converted to other functional groups, including, but not limited to, vinyl, alcohol, amine, and azide groups. Thus, polyesters, polyamides, or other types of polymers can be prepared from the compounds reported herein. Without wishing to be bound by any particular theory, it is believed that the fused rings of structures (I), (II), and (V) provide polymers prepared from the compounds described herein with good thermal and / or mechanical properties. These properties are found in PET and PEF produced from terephthalic acid and furandicarboxylic acid. Thus, the present invention provides the first monomers from renewable resources using biodegradable carbohydrates that can be produced directly from biomass using a simple process.

[0021] The present invention also provides a compound having structure (I), (II), or (V):

[0022] [ka]

[0023] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein], or a composition comprising at least two different compounds of the invention, the method comprising the steps of: a. providing a carbohydrate or lignocellulose-containing composition; b. adding an aldehyde, optionally comprising at least one functional group selected from the group consisting of carboxylic acid, carboxylic acid amide, ether, alkyne, alkene, aldehyde, chloride, hydroxyl, and azide, carboxylic acid ester, aldehyde, vinyl, and amine, to the carbohydrate- or lignocellulose-containing composition to obtain a mixture; c. heating the mixture under acidic conditions; and d. Structure (I), (II), or (V):

[0024] [ka]

[0025] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein], or a composition comprising at least two different compounds of the invention.

[0026] Preferably, the at least one functional group is selected from the group consisting of carboxylic acid, carboxylic acid amide, ether, aldehyde, chloride, and hydroxyl.

[0027] The present invention also provides a polymer comprising as a repeat unit:

[0028] [ka]

[0029] [where R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein; and R 5 Ha-ZZ-F 1 - or Y 1 and R 6 Ha-F 2-Z- or Y 1 where Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)- or a covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 - or covalent bond; where R 8 is H or a C1-C4 alkyl group; and o is an integer from 2 to 10, particularly from 2 to 4; and Y 1 is a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms, However, R 5 and R 6 Y 1 and when n is 0, R 1 or R 2 at least one of which is different from hydrogen].

[0030] The present invention also provides a method for preparing a polymer of the present invention, wherein at least one compound of the present invention optionally has the formula R 9 -LR 9A and reacting the compound with a compound having the formula where: L is (CH2) o (VII), CO(VIII), and diphenyl sulfone (IX):

[0031] [ka]

[0032] [R 9 and R 9A -OR 11 , -OH, -NR 8 , COOH, COOR4 and halogen atoms; where R 11 is selected from the group consisting of aryl and alkyl, or a residue R 9 R 11 and residue R 9A R 11 together form a ring system; wherein the halogen atoms are selected from the group consisting of fluorine, chlorine, bromine, and iodine; and where R 4 , R 8 , and o is as defined herein].

[0033] Finally, the present invention also provides the use of the polymers of the present invention for the production of sheets, fibers or molded articles, in particular as a replacement for poly(ethylene terephthalate). [Brief explanation of the drawings]

[0034] [Figure 1] Figure 1 shows 2D HSQC NMR spectra of dimethylglyoxylate xylose (DMGX) isomers in DMSO-d6. [Figure 2] 13C NMR spectra of DMGX isomers in DMSO-d6. [Figure 3] 1 shows a gas chromatography (GC) chromatogram of purified DMGX isomers. [Figure 4] Mass spectra (MS) and fragmentation of DMGX isomers from GC-MS are shown. [Figure 5] 2D HSQC NMR spectrum of poly(ethylene dimethyl glyoxylate xylose) (PEDMGX). [Figure 6] 1 shows a reflector positive MALDI spectrum of PEDMGX. [Figure 7] Figure 1 shows the GPC chromatograms of three PEDMGX samples synthesized at different temperatures and durations. [Figure 8]1 shows the differential scanning calorimetry (DSC) curve of PEDMGX heated from 30°C to 250°C and cooled back to 30°C. [Figure 9] 1 shows a thermogravimetric analysis (TGA) curve of PEGDMX. DETAILED DESCRIPTION OF THE INVENTION

[0035] Preferred Embodiments

[0036] Compounds of the Invention Structures (I), (II), and (V) are preferably obtained from carbohydrates, such as aldoses or ketoses, by reaction with aldehydes, and those skilled in the art will recognize the impact this has on the conformation of the compounds and polymers reported herein.

[0037] residue R 1 , R 2 , R 3 , and R 10 will vary depending on the type of carbohydrate from which structure (I), (II), or (V) is derived. If structure (I), (II), or (V) is derived from an aldose, R 1 can be -H, -CHOH, or -CH(OH)CHOH, and R 2 can be -H, R 3 can be -H, -OH, or -CHOH. When structure (I), (II), or (V) is derived from a ketose, R 1 can be -H or -CHOH, R 2 can be -OH or -CHOH, R 3 may be the case of -H.

[0038] Thus, the compounds of the present invention may preferably have one of the following structures:

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] wherein Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) where R 4 is a C1-C4 alkyl group, and R 7 is a C1-C4 alkyl group.

[0043] More preferably, the compounds of the present invention have the following structure:

[0044] [ka]

[0045] [where: Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) where R 4 is a C1-C4 alkyl group, and R 7 is a C1-C4 alkyl group.

[0046] Z is preferably -(CH2) m- (where m is an integer from 0 to 10, in particular from 0 to 4); -CH- (where the aromatic ring is optionally substituted with 1 to 4 C-C alkyl groups or 1 to 4 halogen atoms); or -CH 10 - (wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups). F is preferably -COOH, -COOR 4 , -C2H3, -C2H, or -N3, where R 4 is a C1-C4 alkyl group.

[0047] Preferably, R 2 is -H. More preferably, R 2 is H and R 1 is H or CHOH, and R 3 is -H.

[0048] In structures (I) and (II), n is preferably 0. This is especially true when structure (I) or (II) is derived from an aldose.

[0049] Preferably, the compound has structure (I): Compounds having structure (I) are hard monomers that impart good thermal and / or mechanical properties to the polymer.

[0050] The compound has the structure (I), and R 2 is H and R 1 is H or CH2OH, especially R 1 When is H, very good results were obtained.

[0051] In structures (I), (II), and (V), R may contain a hydrocarbon moiety and a functional group. Advantageously, the hydrocarbon moiety is an alkylene moiety having 0 to 10, preferably 0 to 4, carbon atoms. The hydrocarbon moiety may also be an aromatic ring system having 5 to 10, preferably 6, carbon atoms. The hydrocarbon moiety may also be a cycloaliphatic ring system having 5 to 10, preferably 6, carbon atoms. Functional groups that may be contained in R include -COOH, -CH(COOH), -COOR. 4, -CHO, -CH(CHO)2, -C2H3, -NH2, -C2H, -N3, -NHR 7 , -OH, and -CH(CH2OH)2, preferably -COOH, -COOR 4 , -NH2, -NHR 7 and -OH, more preferably -COOH and -COOR 4 where R 4 is a C1-C4 alkyl group, and R 7 is a C1-C4-alkyl group. R may also consist of one of the aforementioned functional groups.

[0052] As described, in structures (I), (II), and (V), R is -ZF, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) where R 4 is a C1-C4 alkyl group; and R 7 is a C1-C4 alkyl group.

[0053] According to one embodiment of the present invention, in structures (I), (II), and (V), R is preferably -(CH2) m COOH; -CHCOOH, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; -(CH2) m CH(COOH)2; -(CH2) m COOR 4 ;-C6H4COOR 4wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOR 4 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; (CH2) m CH(COOR4)2; -(CH2) m CHO; -C6H4CHO, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 CHO, wherein the aliphatic ring is optionally substituted with 1 to 4 C-C alkyl groups; -(CH) m CH(CHO)2; -(CH2) m C2H3; -C6H4C2H3, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 C2H3 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(C2H3)2; -(CH2) m C2H; -C6H4C2H, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 C2H [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m N3; -C6H4N3, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 N3 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m NH2; -C6H4NH2, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10NH2 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(NH2)2; -(CH2) m NHR 7 ;-C6H4NHR 7 wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 NHR 7 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(NHR 7 )2; -(CH2) m OH; -C6H4OH, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 OH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or -(CH2) m CH(CHOH) where R 4 is a C1-C4 alkyl group; R 7 is a C1-C4 alkyl group; and m is an integer of 0 to 10, particularly 0 to 4.

[0054] More preferably, in structures (I), (II), and (V), R is -(CH2) m COOH; -CHCOOH, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; -(CH2) m CH(COOH)2; -(CH2) m COOR 4 ;-C6H4COOR 4wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOR 4 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(COOR 4 )2, where R 4 is a C1-C4 alkyl group; R 7 is a C1-C4 alkyl group; and m is an integer of 0 to 10, particularly 0 to 4.

[0055] R is -(CH2) m COOR 4 ;-C6H4COOR 4 wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; -CH 10 COOR 4 wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups; or -(CH2) m CH(COOR 4 ) 2, where m is 0 to 4, and R 4 is a C1-C4 alkyl group. Preferably, R is -COOMe.

[0056] The aforementioned hydrocarbon moiety is usually part of an easily accessible aldehyde. If these aldehydes are not available, the compounds can be obtained by functional group transformation, such as reductive amination or hydroamination. Furthermore, the aforementioned functional group of the residue R allows the preparation of polymers from compounds having structures (I) and (II) with good thermal and / or mechanical properties. In particular, the thermal and / or mechanical properties can be tailored by selecting specific hydrocarbon moieties, such as aromatic or aliphatic ring systems for more rigid polymers or alkylene moieties for more flexible polymers. The aforementioned functional groups provide access to various types of polymers, such as polyesters, polyamides, or polyethers. Polyesters have the particular advantage that they are often biodegradable.

[0057] According to an embodiment of the present invention, R is -(CH2) m COOH, -(CH2) m CH(COOH)2, -(CH2) m COOR 4 , -(CH2) m CH(COOR 4 )2, -(CH2) m CHO, -(CH2) m CH(CHO)2;-(CH2) m C2H3, -(CH2) m CH(C2H3)2, -(CH2) m CH, -(CH) m N3, -(CH2) m NH2, -(CH2) m CH(NH2)2, -(CH2) m NHR 7 , -(CH2) m OH or -(CH2) m CH(CHOH) where R 4 is a C1-C4 alkyl group, preferably a -CH3 group; R 7 is a C1-C4 alkyl group; and m is an integer of 0 to 10, preferably 0 to 4, and more preferably 0.

[0058] If the compound has the structure (I) [R is -(CH2) m COOH, -(CH2) m CH(COOH)2, -(CH2) m COOR 4 , -(CH2) m CH(COOR 4 )2, (CH2) m CHO, -(CH2) m CH(CHO)2;-(CH2) m C2H3, -(CH2) m CH(C2H3)2, -(CH2) m CH, -(CH) m N3, -(CH2) m NH2, -(CH2) m CH(NH2)2, -(CH2) m NHR 7 , -(CH2) m OH or -(CH2) m CH(CHOH) where R 4 is a C1-C4 alkyl group, preferably a -CH3 group; R 7 is a C1-C4 alkyl group; and m is 0. More preferably, R 2 is H, and R 1 is H or CHOH, and in particular R 1 is H.

[0059] In a preferred embodiment of the present invention, good results have been obtained when Y is hydrogen or a linear or branched organic residue having 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, most preferably 1 to 3 carbon atoms, such as a hydrocarbon moiety, e.g., methylene, ethylene, propylene, etc.

[0060] Thus, preferably, the compounds of the invention have one of the following structures:

[0061] [ka]

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073] [ka]

[0074] More preferably, the compounds of the invention have one of the following structures:

[0075] [ka]

[0076] Even more preferably, the compounds of the present invention have one of the following structures:

[0077] [ka]

[0078] [ka]

[0079] In the structure shown above, the ring system preferably has the following stereochemistry:

[0080] [ka]

[0081] Methods for preparing compounds The present invention also provides a method for preparing the compounds of the present invention having structure (I), (II), or (V). The method of the present invention includes providing a carbohydrate and adding an aldehyde to the carbohydrate. When a mixture of carbohydrates is used, a mixture of compounds having structure (I), (II), or (V), particularly a mixture of compounds of the present invention having structure (I), (II), or (V), can be obtained.

[0082] Accordingly, the present invention provides a compound having structure (I), (II), or (V):

[0083] [ka]

[0084] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein], or a composition comprising at least two different compounds of the invention, the method comprising the steps of: a. providing a carbohydrate or lignocellulose-containing composition; b. adding an aldehyde, optionally comprising at least one functional group selected from the group consisting of carboxylic acid, carboxylic acid amide, ether, alkyne, alkene, aldehyde, chloride, hydroxyl, azide, carboxylic acid ester, aldehyde, vinyl, and amine, to the carbohydrate- or lignocellulose-containing composition to obtain a mixture; c. heating the mixture under acidic conditions; and d. Structure (I), (II), or (V):

[0085] [ka]

[0086] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein], or a composition comprising at least two different compounds of the invention.

[0087] In a preferred embodiment of the present invention, good results have been obtained when the aldehyde in step b) is selected from the group consisting of acetaldehyde, propionaldehyde, isobutyraldehyde, glyoxylic acid, dialdehyde, cyclopropanecarboxaldehyde, isobutyraldehyde, pivaldehyde, tolualdehyde, and benzaldehyde.

[0088] In the method for preparing the compounds of the present invention, different carbohydrates can be used as carbohydrates. The carbohydrates can be aldoses or ketoses. The carbohydrates can be pentoses, hexoses, or heptoses. Preferably, the carbohydrates are aldopentoses, aldohexoses, aldoheptoses, ketohexoses, ketoheptoses, or mixtures thereof. More preferably, the carbohydrates are aldopentoses, aldohexoses, aldoheptoses, or mixtures thereof, particularly aldopentoses, aldohexoses, or mixtures thereof.

[0089] Advantageously, the carbohydrate is selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, glucoheptose, mannoheptose, psicose, fructose, sorbose, tagatose, sedoheptulose, mannoheptulose, taloheptulose, alloheptulose, and mixtures thereof. Preferably, the carbohydrate is selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, glucoheptose, mannoheptose, or mixtures thereof, more preferably from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, or mixtures thereof. Most preferably, the carbohydrate is xylose, glucose, or a mixture thereof.

[0090] In the process for preparing the compounds of the present invention, a lignocellulose-containing composition can be used.

[0091] Lignocellulose is considered to be the most abundantly available raw material (biomass) on Earth. Lignocellulosic biomass can be classified as virgin biomass, waste biomass, and energy crops. Virgin lignocellulosic biomass includes all terrestrial plants found in nature, such as trees, shrubs, and grasses. Waste lignocellulosic biomass is produced as a low-value by-product of various industrial sectors, such as agriculture (corn stover, sugarcane bagasse, straw, etc.) and forestry (sawmill and paper mill waste).

[0092] Lignocellulose includes hemicellulose, cellulose, and lignin. Both hemicellulose and cellulose can be considered carbohydrate polymers. Carbohydrate polymers contain five- and six-carbon sugar monomers, which are linked to lignin.

[0093] Lignin can be considered an aromatic polymer, which contains methoxylated phenylpropane subunits, such as guaiacyl and syringyl subunits.

[0094] Xylan is a polysaccharide belonging to the hemicellulose family, and its main monomer unit is D-xylose. Cellulose can be considered a polysaccharide, and its main monomer unit is D-glucose linked via β-1-4 bonds.

[0095] Preferably, the lignocellulose-containing composition is biomass, particularly lignocellulosic biomass, preferably virgin lignocellulosic biomass, such as wood. The lignocellulosic biomass is preferably derived from trees such as birch, beech, poplar, cedar, Douglas fir, cypress, fir, juniper, kauri, larch, pine, hemlock, redwood, spruce, and yew. Most preferred woods for the lignocellulose-containing composition are hardwoods such as oak, poplar, maple, eucalyptus, birch, and / or beech.

[0096] Lignocellulose-containing compositions can also be derived from energy crops. Energy crops are crops that produce a high yield of lignocellulosic biomass. Furthermore, energy crops grow rapidly, so the lignocellulosic biomass is already available within a short period of time, for example, after a few months. Examples of energy crops include giant reed, big bluestem, Chinese tallow tree, cabbage, duckweed, parsley, black jasmine, switchgrass, and elephant grass.

[0097] According to one embodiment, the lignocellulose-containing composition is derived from corn cobs.

[0098] The lignocellulose-containing composition is preferably solid at a temperature of 23°C. Preferably, the lignocellulose-containing composition is air-dried at a temperature of 60°C or less. For example, the lignocellulose-containing composition is air-dried for storage to remove excess water. The air-dried lignocellulose-containing composition preferably contains less than 50% by weight of water, more preferably less than 30% by weight, and especially 0-10% by weight.

[0099] The lignocellulose-containing composition may have a lignin content of 1 to 50 wt. %, preferably 10 to 30 wt. %, based on the total weight of the lignocellulose-containing composition, preferably measured as Klason lignin.

[0100] The Klason lignin test is used to measure Klason lignin. In this test, wood particles (0.25–0.50 g) are placed in a 50 mL beaker and 7.5 mL of a 72 wt.% sulfuric acid solution is added. The mixture is left at room temperature for 2 hours, stirring every 10 minutes with a glass rod. The slurry is then transferred to a round-bottom flask and 290 mL of water is added to bring the sulfuric acid concentration to 3 wt.%. The glass bottle is sealed with a screw cap and sterilized in an autoclave at 120 °C for 1 hour. The resulting solution is filtered, and the precipitate is washed with water, dried at 105 °C, and weighed to determine the Klason lignin content.

[0101] The content of Klason lignin can be calculated using the following formula: Klason lignin content [%] = KL / LCC × 100, where KL is the amount of Klason lignin [g] and LCC is the amount of lignocellulose-containing composition [g].

[0102] In the process for preparing the compounds of the present invention, different aldehydes can be used. Preferably, the aldehyde has the formula R-CHO, where R is as defined herein. More preferably, the aldehyde has the formula CHO-(CH2). m COOH; CHO-C6H4COOH (wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups); CHO-C6H 10 COOH (wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups); or CHO-(CH2) m It has CH(COOH)2.

[0103] The lignocellulose-containing composition can be mixed with a solvent, for example, dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydrofuran, or an ether solvent such as gamma valerolactone, glyme, or diglyme.

[0104] To produce the monomer, the mixture containing the substrate (sugar or lignocellulose) and the aldehyde can be heated at various temperatures in step c. Advantageously, the mixture is heated at 50-120°C, preferably 60-110°C, more preferably 60-100°C, and most preferably 60-85°C. At temperatures below 50°C, the reaction has been found to proceed very slowly. At all temperatures, the reaction can be accelerated by the presence of an acid catalyst. At temperatures above 120°C, undesirable by-products have been found to be formed.

[0105] The mixture can also be heated under various pressures depending on the raw materials. In the case of carbohydrates, heating is advantageously carried out at a pressure of less than 150 mbar. In particular, the reaction can be carried out at a pressure of 70 to 130 mbar, preferably 80 to 120 mbar, more preferably 90 to 110 mbar. It has been found that the reaction proceeds more quickly under reduced pressure.

[0106] For carbohydrates, very good results are obtained when the mixture is heated to 50-120°C, preferably 60-110°C, more preferably 60-100°C, and most preferably 60-85°C, and at a pressure of 70-130 mbar, preferably 80-120 mbar, and more preferably 90-110 mbar. Under these conditions, water produced during the reaction can be removed from the reaction, which helps to obtain high yields of the desired product and also helps to accelerate the reaction.

[0107] According to one embodiment, in the case of biomass, steps a. to c. are advantageously carried out in a solvent that is preferably a polar aprotic solvent, even more preferably an ethereal solvent, most preferably dioxane, γ-valerolactone, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, or tetrahydrofuran. According to this embodiment, steps a. to c. are preferably carried out for 0.5 to 72 hours, more preferably 1 to 24 hours, and most preferably 2 to 4 hours. According to this embodiment, steps a. to c. are advantageously carried out at a temperature of 50 to 120°C, preferably 60 to 110°C, more preferably 60 to 100°C, and most preferably 60 to 85°C. The cellulose is then preferably removed from the reaction mixture by filtration. The solvent is then preferably removed from the reaction mixture by evaporation under reduced pressure, such as 1 mbar to 150 mbar. The lignin is then preferably removed by precipitation in the solvent, followed by filtration of the precipitation mixture to obtain a filtrate. The resulting filtrate is then preferably concentrated and acid is added, followed by heating and vacuum as described for carbohydrates above.

[0108] The acidic condition of the mixture can be achieved by various means. Advantageously, an acid is added to the mixture. Various acids can be used for this purpose. Examples of suitable acids are sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, and toluenesulfonic acid. The acid is preferably used at a concentration of 0.1 to 1 M, more preferably 0.2 to 0.6 M. Preferably, sulfuric acid is added to the mixture. Acidic aldehydes such as, but not limited to, glyoxylic acid can self-catalyze the reaction.

[0109] The process for preparing the compounds of the invention may comprise additional steps. Advantageously, the process of the invention comprises the step of adding an alcohol, especially when the aldehyde comprises a carboxylic acid group, more particularly when the aldehyde has the formula CHO-(CH2) mCOOH; CHO-C6H4COOH [wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; CHO-C6H 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups; or CHO-(CH2) m When the mixture has CH(COOH)2, where m is an integer of 0 to 10, preferably 0 to 4, an alcohol can be added. The alcohol is preferably added after the mixture is heated under acidic conditions. Preferably, the alcohol is a C1 to C4 alkyl alcohol, more preferably methanol.

[0110] Advantageously, the aldehyde has the formula CHO-(CH2) m COOH; CHO-C6H4COOH [wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; CHO-C6H 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups; or CHO-(CH2) m CH(COOH)2, where m is an integer from 0 to 10, preferably from 0 to 4, and the method comprises the additional step of adding a C1-C4-alkyl alcohol, preferably methanol, after step c. and before step d.

[0111] The alcohol, such as a C1-C4-alkyl alcohol, preferably methanol, may be added in a ratio of from 1:1 by volume of alcohol to mass of reaction mixture to a ratio of from 20:1 by volume of alcohol to mass of reaction mixture, preferably from 5:1 by volume of alcohol to mass of reaction mixture to a ratio of from 15:1 by volume of alcohol to mass of reaction mixture, more preferably 10:1 by volume of alcohol to mass of reaction mixture.

[0112] The mixture containing the C1-C4-alkyl alcohol, preferably methanol, can then be heated, preferably to the boiling point of the mixture, for 1 to 10 hours, preferably 2 to 5 hours, and more preferably 2 to 4 hours.

[0113] Step d. may comprise a neutralization step. Neutralization is preferably carried out using a weak base. Examples of suitable weak bases are bicarbonates such as sodium bicarbonate or potassium bicarbonate, preferably as an aqueous solution.

[0114] Separation, particularly isolation, of a compound of the present invention or a composition comprising at least two different compounds of the present invention may involve several steps. Separation may involve dissolving one or more compounds of the present invention in an organic solvent. Separation may also preferably involve one or more filtration and / or drying steps before dissolving one or more compounds of the present invention in an organic solvent. Examples of suitable organic solvents are diethyl ether, tetrahydrofuran, ethyl acetate, glyme, diglyme, dichloromethane, chloroform, and tetrachloromethane, particularly diethyl ether, tetrahydrofuran, ethyl acetate, and dichloromethane, more particularly ethyl acetate or dichloromethane. Separation may also include one or more washing steps using an aqueous solution, such as aqueous sodium bicarbonate and / or aqueous sodium chloride. Separation may also include a purification step, such as distillation. Distillation is preferably carried out as a final purification step. Alternatively, crystallization can be carried out as a final purification step before polymerization. For example, in the case of dimethylglyoxylate xylose, cyclopentyl methyl ether, toluene, or alcohol can be used for crystallization. Chiral separation of isomers is possible by performing temperature-controlled crystallization.

[0115] Polymers of the Invention The compounds of the present invention can be used in the preparation of polymers, for example, as monomers for the preparation of polyesters or polyamides.

[0116] Thus, the present invention also provides a polymer comprising as a repeat unit:

[0117] [ka]

[0118] [where: R 1 , R 2 , R 3 , R 10 , n, and p are as defined herein; and R 5 Ha-ZF 1 - and R 6 Ha-F 2 -Z-, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and where F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)- or a covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 - or a covalent bond; where R 8 is H or a C1-C4-alkyl group; and o is an integer from 2 to 10, in particular from 2 to 4.

[0119] residue R 1 , R 2 , and R 3 will vary depending on the type of carbohydrate from which the monomer used to prepare the polymer of the invention is derived. If the monomer is derived from an aldose, R 1 can be -H, -CHOH, or -CH(OH)CHOH, and R 2 can be -H, and R 3 can be -H, -OH, or -CHOH. If the monomer is derived from a ketose, R 1 can be -H or -CHOH, R 2 can be -OH or -CHOH, and R 3 can be -H.

[0120] Thus, the polymers of the present invention preferably contain, as repeat units, at least one of the following structures:

[0121] [ka]

[0122] [ka]

[0123] wherein Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)- or a covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 - or a covalent bond; where R 8 is H or a C1-C4 alkyl group; R 10 is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety can be optionally substituted with a C1-C4-alkyl group or a halogen atom; and o is an integer from 2 to 10, especially from 2 to 4].

[0124] More preferably, the polymers of the present invention comprise, as repeat units, at least one of the following structures:

[0125] [ka]

[0126] [ka]

[0127] wherein Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)- or a covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 - or a covalent bond; where R 8 is H or a C1-C4 alkyl group; R 10 is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety can be optionally substituted with a C1-C4-alkyl group or a halogen atom; and o is an integer from 2 to 10, especially from 2 to 4].

[0128] Z can also be an alkylene moiety having 0 to 10, preferably 0 to 4, carbon atoms. Furthermore, Z can also be an aromatic ring system having 5 to 10, preferably 6, carbon atoms. Furthermore, Z can also be a cycloaliphatic ring system having 5 to 10, preferably 6, carbon atoms.

[0129] Z is preferably -(CH2) m - [wherein m is an integer from 0 to 10, in particular from 0 to 4]; -CH- [wherein the aromatic ring is optionally substituted with 1 to 4 C-C alkyl groups or 1 to 4 halogen atoms]; or -CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups. F is preferably -COOH, -COOR 4 , -C2H3, where R 4 is a C1-C4 alkyl group.

[0130] Preferably, R 2 is -H. More preferably, R 2 is H and R1 is H or CHOH, and R 3 is -H.

[0131] In structures (III) and (IV), n is preferably 0. This is especially true when structure (III) or (IV) is derived from an aldose.

[0132] As described, in structures (I), (II), and (V), R is -ZF, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -NH2, -NHR 7 , -OH, -CH(CHOH) where R 4 is a C1-C4 alkyl group; and R 7 is a C1-C4 alkyl group.

[0133] According to one embodiment of the present invention, in structures (III), (IV), and (VI), R 5 is preferably -(CH2) m C(=O)O-, and R 6 is -OC(=O)(CH2) m - is; or R 5 is -C6H4C(=O)O-, and R 6 is -OC(=O)C6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 is -C6H4C(=O)O-, and R 6 -OC(=O)CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m OC(=O)-, and R 6is -C(=O)O(CH2) m -is; or R 5 is -C6H4OC(=O)-, and R 6 is -C(=O)OC6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 OC(=O)-, and R 6 is -C(=O)OC6H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)(CH2) m -is; or R 5 is -C6H4C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)C6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m R 8 NC(=O)-, and R 6 is -C(=O)NR 8 (CH2) m -is; or R 5 Ha-C6H4R 8 NC(=O)-, and R 6 is -C(=O)NR8 C6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 R 8 NC(=O)-, and R 6 is -C(=O)NR 8 C6H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 8 is H or a C1-C4 alkyl group; and m is an integer of 0 to 10, particularly 0 to 4.

[0134] More preferably, in structures (III), (IV), and (VI), R 5 is preferably -(CH2) m C(=O)O-, and R 6 is -OC(=O)(CH2) m -Can be; or R 5 is -C6H4C(=O)O-, and R 6 is -OC(=O)C6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 C(=O)O-, and R 6 -OC(=O)CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m OC(=O)-, and R 6 is -C(=O)O(CH2) m -, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 is -C6H4OC(=O)-, and R 6is -C(=O)OC6H4-, in which the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 OC(=O)-, and R 6 is -C(=O)OC6H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; m is an integer of 0 to 10, particularly 0 to 4.

[0135] Thus, preferably the polymers of the present invention comprise, as repeat units, at least one of the following structures:

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148]

change

[0149]

change

[0150]

change

[0151]

change

[0152]

change

[0153] (where o is an integer from 2 to 10, particularly from 2 to 4).

[0154] Preferably, the polymers of the present invention comprise repeat units having structure (III), where n is 0 and R 2 is -H and R 1 is H or CHOH, and in particular R 1 is H and m is 0.

[0155] According to one embodiment of the present invention, the polymer does not contain repeat units having structure (IV).

[0156] In structures (III), (IV), and (VI), R 5 is -C(=O)O- and R 6 When is -OC(=O)- and o is 2, very good results were obtained.

[0157] Most preferably, the polymers of the present invention comprise as repeat units:

[0158] [ka]

[0159] wherein o is 2; and does not include repeat units having structure (IV).

[0160] In the structure shown above, the ring system preferably has the following stereochemistry:

[0161] [ka]

[0162] Polymers containing the aforementioned repeating units, particularly those derived from xylose, have been found to exhibit good thermal and / or mechanical properties. Furthermore, these polymers can be easily prepared from inexpensive and abundant resources using simple processes.

[0163] Method for preparing the polymer The present invention also provides a method for preparing a polymer of the present invention, wherein at least one compound of the present invention optionally has the formula R 9 -LR 9A where R 9 and R 9A -OR 11 , -OH, -NHR 8 , -COOH, -COOR 4 and halogen atoms; where R 11 is selected from the group consisting of aryl and alkyl, or a residue R 9 R 11 and residue R 9A R 11 together form a ring system; wherein the halogen atoms are selected from the group consisting of fluorine, chlorine, bromine, and iodine; where R 4 , R 8 , and o are as defined herein. This means that R 9 and R 9A may be the same or different.

[0164] R 9 and R 9A Very good results have been obtained in the preferred embodiment of the present invention where

[0165] According to another preferred embodiment of the present invention, L is (CH2) o When this is the case, good results were obtained.

[0166] In a further preferred embodiment of the present invention, R 9 -LR 9A Good results have been obtained when is a bis-(4-halogenphenyl)sulfone, especially bis-(4-chlorophenyl)sulfone or bis-(4-fluorophenyl)sulfone.

[0167] According to a further preferred embodiment of the present invention, R 9 -LR9A is a group in which L is CO of formula (VIII) and R 9 and R 9A are the same or different OR 11 When the organic carbonate is Good results have been obtained when R 11 is selected from the group consisting of aryl and alkyl, or a residue R 9 R 11 and residue R 9A R 11 together form a ring system, i.e., cyclic Carbonate For example, organic Carbonate is a dialkyl carbonate, diaryl carbonate, or cyclic Carbonate Examples of dialkyl carbonates are dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate. Examples of diaryl carbonates are diphenyl carbonate or dimethylphenyl carbonate. Cyclic Carbonate Examples are ethylene carbonate or trimethylene carbonate.

[0168] Preferably, the reaction is a polymerization reaction.

[0169] 1. A method for treating a subject with at least one compound of the present invention and formula R 9 -LR 9A The compounds of formula R may be provided in different ratios, for example, 1:10 to 10:1. Preferably, at least one compound of the invention and a compound of formula R 9 -LR 9A are provided in a ratio of 1:1 to 1:10, more preferably 1:1 to 1:8, most preferably 1:1 to 1:5.

[0170] Preferably, the reaction is carried out in the presence of a catalyst. A non-exhaustive list of polycondensation catalysts that can be used includes antimony trioxide, titanium isopropoxide, titanium butoxide, dibutyltin oxide, and zinc acetate.

[0171] The reaction can also be carried out in the presence of an initiator, especially a radical initiator, which is especially true when the compound of the invention contains a vinyl group.

[0172] The reaction can be carried out at different temperatures. Preferably, the reaction is carried out at a temperature of 30 to 250°C, more preferably at a temperature of 50 to 230°C, and most preferably at a temperature of 100 to 220°C. If the reaction is carried out in the presence of a radical initiator, the temperature is preferably adjusted taking into account the radical initiator, in particular the half-life of the initiator. Examples of suitable radical initiators are peroxides, such as benzoyl peroxide, or azo initiators, such as azoisobutyronitrile.

[0173] The reaction in the preparation method of the polymer of the present invention may also include several steps. According to one embodiment of the preparation method of the polymer of the present invention, in the first step, the compound of the present invention and a compound of formula R 9 -LR 9A can be reacted to produce an intermediate, for example, a compound having the structure:

[0174] [ka]

[0175] with ethanediol to produce two ethanediol units as intermediates:

[0176] [ka]

[0177] The corresponding transesterification intermediates can be produced, including

[0178] In a second step, the intermediate can then be polymerized to obtain a polymer of the invention, for example, a polymer having the structure:

[0179] [ka]

[0180] can be polymerized in a second step.

[0181] The first and second steps can be carried out at different temperatures, for example, the first step can be carried out at a temperature of 100°C to 200°C, preferably 120°C to 160°C, and most preferably 130°C to 150°C, and the second step can be carried out at a temperature of 150°C to 250°C, preferably 170°C to 230°C, and most preferably 180°C to 220°C.

[0182] The reaction steps can be carried out over various time periods. For example, the first reaction step can be carried out for 1 to 15 hours, preferably 1 to 10 hours, and more preferably 1 to 7 hours. The second reaction step can be carried out for 2 to 15 hours, preferably 3 to 10 hours, and more preferably 3 to 8 hours.

[0183] In order to achieve high yields and high molecular weights in the first and second steps, the pressure can be reduced, especially in the case of transesterification. For example, in the transesterification reaction using ethanediol as the reagent, the reaction can be first carried out at normal pressure and then reduced pressure. However, this can also be applied to the preparation of amides, polyesters, or polyamides.

[0184] Preferably, during the first step, the pressure is reduced to 100 mbar or less, more preferably 50 mbar or less, most preferably 10 mbar or less. Advantageously, during the second step, the pressure is reduced to 100 mbar or less, more preferably 50 mbar or less, more preferably 10 mbar or less, most preferably 1 mbar or less. By reducing the pressure during the reaction, especially during the first and / or second steps, a higher yield and / or a higher molecular weight of the polymer can be achieved.

[0185] The method of the present invention may also include a purification step. The polymer can be purified by precipitation, extraction, and / or column chromatography. Preferably, the polymer is purified by precipitation.

[0186] The polymers of the present invention are promising candidates to replace poly(ethylene terephthalate). The present invention therefore also provides the use of the polymers of the present invention for the manufacture of sheets, fibers, or molded articles, in particular as a replacement for poly(ethylene terephthalate).

[0187] The following examples are set forth but are not meant to be limiting. [Example]

[0188] method MALDI-TOF: Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) spectra of the synthesized polymers were acquired using a Bruker AutoFlex Speed ​​instrument (Bremen, Germany). Samples were prepared by dissolving the polymer in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) at a concentration of 1 mg / mL. A solution of 10 mg of 2,5-dihydroxybenzoic acid and 10 μL of trifluoroacetic acid (TFA) in 1 mL of THF was prepared. Subsequently, 0.5 μL of the polymer / HFIP solution was deposited onto a steel analysis plate, followed by 0.5 μL of the DHB / TFA solution. To achieve optimal signal, the laser power for the various polymer samples was set at 60–90%.

[0189] Gel permeation chromatography: The number-average and weight-average molecular weights (Mn and Mw) of the synthesized polymers were determined via gel permeation chromatography (GPC). An Agilent 1100 GPC / SEC column equipped with one PFG linear M column (PSS) was connected to an Agilent 1100 VWD / UV detector operating at 294 nm, a DAWN HELEOS II multi-angle laser light scattering (MALS) detector (Wyatt Technology Europe), and an Optilab TrEX RI detector (Wyatt). Samples were eluted at 1 mL / min at room temperature with HFIP containing 0.03 M K-TFAc. To ensure instrument accuracy, each polymer sample was analyzed in duplicate. To accurately determine molecular weights, polymethyl methacrylate (PMMA) standards were purchased from PSS Polymer Standards Service, Germany, and used to generate a calibration curve that was applied to the data.

[0190] GC-MS analysis: Gas chromatography-mass spectrometry spectra were obtained using an Agilent 7890B series GC equipped with an HP5-MS capillary column and an Agilent 5977A series mass spectrometry detector. The GC-MS method was performed as follows: injection temperature 250°C, column temperature program started at 50°C for 1 min, then increased to 300°C with a gradient of 15°C / min, held at 300°C for 7 min, and detection temperature was 290°C.

[0191] NMR Analysis: All NMR spectra were obtained using a Bruker Avance III 400 MHz spectrometer.

[0192] synthesis

[0193] General reaction scheme:

[0194] [ka]

[0195] To prepare the monomer, glyoxylic acid, which is commercially available and easily produced from renewable ethylene glycol, was reacted with D-xylose (step a in the above scheme). Next, the glyoxylic acid-protected xylose was esterified with methanol to increase the rate of polycondensation and facilitate the separation of the protected sugar (step b in the above scheme). Finally, the diester-protected xylose, dimethylglyoxylate xylose (DMGX), was polymerized with ethylene glycol to produce the fully renewable polyester poly(ethylene dimethylglyoxylate xylose) (PEDMGX) (step c in the above scheme).

[0196] Synthesis of dimethylglyoxylate xylose from xylose D-xylose (200 g, 1.33 mol, 1.00 equiv.) was combined with glyoxylic acid monohydrate (500 g, 5.43 mol, 4.08 equiv.) in a 2 L round-bottom flask and heated to 95 °C on a rotary evaporator. After dissolving the xylose in molten glyoxylic acid, 98% w / w sulfuric acid (28.57 g, 270.8 mmol, 0.2 equiv.) was added dropwise. The pressure in the rotary evaporator was then slowly reduced to 20 mbar to continuously remove water produced as a by-product of the reaction. The di-glyoxylic acid-protected xylose was then dissolved in molten glyoxylic acid. GC-FIDThe reaction was stopped after the yield, as determined by GC-FID, exceeded 93% (approximately 3 hours). Methanol (1 L) was then added to the reaction mixture, and the resulting solution was heated to reflux using an 80 °C oil bath until the yield of the diglyoxylic acid-protected dimethyl ester of xylose exceeded 95% (approximately 1 hour), as determined by GC-FID. The reaction was then cooled to room temperature and neutralized with sodium hydroxide. The resulting salt was removed by filtration, and the filtrate was concentrated under vacuum on a rotary evaporator at 45 °C and 100 mbar. The residue was then dissolved in DCM (0.6 L) and transferred to a (2 L) separatory funnel. The organic phase was then washed three times with deionized water (1 L) to remove dark glycolysis products and unreacted carboxylate salts. The organic phase was then extracted once with brine (1 L) and then transferred to a 1 L round-bottom flask and concentrated under vacuum. The resulting residue was distilled using a distillation bridge at 0.02 mbar pressure and an oil bath temperature of 80 to 180 °C. The distillate containing methyl glyoxylate and residual solvent obtained during the gradient between 80 and 180 °C was discarded. A second flask was attached, and the second fraction containing the product was collected. This viscous yellow oil was dissolved in DCM (0.5 L) and treated with activated carbon (30 g). After stirring at 700 RPM using a PTFE-coated stir bar for 4 h, the solution was filtered through a 0.2 μm nylon membrane filter to remove the activated carbon and concentrated under vacuum to give dimethyl glyoxylate xylose as a viscous colorless oil (205 g, 53%). This oil is a mixture of four stereoisomers. Alternatively, crystallization can be used instead of activated carbon treatment to remove the yellow impurity. Crystallization was successfully performed with methanol, cyclopentyl methyl ether, and toluene. Additionally, by using temperature-controlled crystallization, the most abundant isomer could be selectively crystallized, leaving the other three isomers in the mother liquor.

[0197] Figures 1-4 show analytical data for DMGX. Figure 1 shows 2D HSQC NMR, demonstrating the successful synthesis of DMGX isomers. Different isomers of DMGX give different sets of peaks in the NMR spectrum. The letters in parentheses next to the peaks indicate the conformations of carbons 6 and 9, respectively. Figure 2 shows the 2D HSQC NMR of only the DMGX isomers.13 The C NMR spectra are shown. The letters in parentheses next to the peaks indicate the configurations at carbons 6 and 9, respectively. Figure 3 clearly shows the different retention times in gas chromatography for the purified DMGX isomers. Figure 4 shows the corresponding GC-MS mass peaks for the DMGX isomers and fragmentation products.

[0198] Exemplary Synthesis of Poly(ethylene dimethyl glyoxylate xylose) One molar equivalent of dimethylglyoxylated xylose was placed in a two-neck round-bottom flask with an excess of freshly distilled ethanediol (2.2 equivalents) and 0.4 wt% antimony trioxide. The reaction vessel was fitted with a distillation tube, purged with nitrogen three times, and then heated. The vessel was heated to 140 °C in a sand bath with continuous stirring under a steady nitrogen flow for 2 hours, and methanol was removed by distillation. The bath was then heated to 200 °C for 2 hours under a continuous nitrogen flow. A vacuum was then applied at 0.1 mbar pressure, and the reaction was continued for an additional 3 hours to distill off ethylene glycol and allow transesterification to proceed. The reaction was cooled to room temperature and subsequently dissolved in a minimum amount of 1,1,1,3,3,3-hexafluoro-2-propanol and precipitated by dropwise addition to stirring methanol. The polymer was filtered from the solution, washed with methanol, and then dried under vacuum. Various transesterification catalysts, reaction times, and temperatures can be used to produce the same polymer with varying molecular weights.

[0199] Figures 5–9 show analytical data for PEDMGX. Figure 5 shows the 2D HSQC NMR spectrum demonstrating the successful synthesis of PEDMGX. The letters in parentheses next to the peaks indicate the conformations of carbons 6 and 9, respectively. Figure 6 shows the reflector-positive MALDI spectrum of PEDMGX. The distance between prominent peaks corresponds to the molecular weight of the repeating unit. Figure 7 shows GPC chromatograms of three different PEDMGX samples synthesized at various temperatures and times (not all are described here). To ensure instrument accuracy, each polymer sample was analyzed twice. Polymethyl methacrylate (PMMA) molecular weight standards from PSS Polymer Standards Service (Germany) were used as external standards for molecular weight measurements. Molecular weights in the 10–50 kDa range were achieved, which is well within the commercial range for PET (20–60 kDa). Figure 8 shows the DSC curve for PEDMGX heated from 30°C to 250°C and cooled back to 30°C. The DSC indicates a glass transition of 125°C, which is 45-55°C higher than PET and 30°C higher than PEF. This allows the polyester to be used in very high-temperature applications without losing its properties, including those requiring contact with boiling water. Figure 9 shows the TGA curve for PEGDMX. The TGA indicates a decomposition temperature of approximately 348°C, which is lower than the 400°C decomposition temperature of PET, but still much higher than the processing and end-use temperatures of the polymer.

[0200] General procedure for the preparation of DMGX-based polyesters The following polymers were synthesized using the following method: poly(ethylene dimethylglyoxylate xylose), poly(propylene dimethylglyoxylate xylose), poly(butylene dimethylglyoxylate xylose), poly(pentylene dimethylglyoxylate xylose), and poly(hexylene dimethylglyoxylate xylose) were prepared by polymerizing DMGX with ethanediol, propanediol, butanediol, pentanediol, and hexanediol, respectively. Dimethylglyoxylated xylose (10 g, 34.4 mmol, 1.0 equiv.) was combined with the diol (86 mmol, 2.5 equiv.), reesterification catalyst: zinc acetate (2 mg, 0.011 mmol, 0.00032 equiv.), antioxidant: pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (13 mg, 0.011 mmol, 0.00032 equiv.), and triphenyl phosphite (13 mg, 0.042 mmol, 0.0012 equiv.) in a 250 mL, two-neck round-bottom flask. The reaction vessel was then equipped with a distillation bridge, a vacuum adapter, a valve for nitrogen flow, and a 250 mL collection flask and connected to a Schlenk line. The reaction vessel was backfilled with nitrogen three times. The reaction mixture was then heated to 140 °C in an oil bath with stirring under a steady stream of nitrogen. During the course of the reaction, the methanol by-product was distilled from the reaction mixture and collected in a collection flask. 1 Once complete re-esterification was observed (approximately 1-4 hours), as monitored by H-NMR, the transesterification catalyst antimony trioxide (2 mg, 0.0069 mmol, 0.0002 equiv.) was added to the reaction mixture as a suspension in diol (0.5 mL) under positive nitrogen pressure. The reaction mixture was then heated to 190 °C, and the reaction vessel was slowly evacuated to a pressure of 0.02 mbar over 30 minutes to distill off the diol reaction by-product and allow the polycondensation reaction to proceed. 1The reaction was monitored by H-NMR and terminated when the desired molecular weight was observed by end-group analysis (high molecular weight, approximately 8–14 h). Polymers derived from a mixture of the four DMGX isomers were typically orange in color. Polymers synthesized from the most abundant DMGX isomer were generally clear and colorless. The reaction mixture was cooled to room temperature and dissolved in a minimum amount of 1,1,1,3,3,3-hexafluoroisopropanol (250 mL). The resulting solution was added dropwise to a stirred solution of isopropanol (1 L) for butanediol, pentanediol, and hexanediol polymers, or methanol (1 L) for shorter-chain diols, to precipitate the polymer. The polymer was collected by filtration, washed with isopropanol followed by diethyl ether, and dried overnight under vacuum at 60 °C and 0.02 mbar to yield the product as a bright white powder. For polymerizations with ethanediol and propanediol, where high molecular weights were more difficult to achieve, a more active transesterification catalyst, dibutyltin oxide (45 mg, 0.184 mmol, 0.0053 equiv.), was used instead of zinc acetate and antimony trioxide.

[0201] Synthesis of dimethylglyoxylate xylose from lignocellulosic biomass Biomass (extract-free, dried, 90.0 g) was collected in a tared 1 L reagent bottle. Next, glyoxylic acid monohydrate (60.753 g, 660 mmol, 3.3 equiv.), 1,4-dioxane (250 mL), hydrochloric acid (37 wt.%, 16.7 mL, 200 mmol, 1.0 equiv.), and two large PTFE-coated stir bars were added to the bottle. The flask was sealed with a GL45 cap and placed in a shaking incubator at 300 RPM for 24 hours. Upon completion, the reaction was cooled to room temperature (approximately 23–30 °C). A filtration apparatus was assembled consisting of a 2 L filter flask, a neoprene adapter, and a Büchner funnel equipped with a piece of qualitative filter paper. The reaction was filtered through the Büchner funnel by washing with dioxane (250 mL) to remove cellulose-rich solids. The filtrate was then transferred to a 2 L round-bottom flask (29 / 32°C) and concentrated on a rotary evaporator at a bath temperature of 45 °C and an ultimate pressure of 10 mbar. An oval PTFE-coated stir bar was then added to the concentrated lignin solution, followed by the addition of 1 L of deionized water to precipitate the lignin. The mixture was stirred at 500 RPM for 30 minutes to break up large agglomerates. The stir bar was then removed. A filtration apparatus was assembled consisting of a 2 L filter flask, a neoprene adapter, and a membrane filtration apparatus equipped with a 0.8 μm nylon membrane filter. The precipitated lignin solution was then filtered through the nylon membrane filter by washing with 100 mL of deionized water to collect the lignin.

[0202] The filtrate was transferred to a 2 L round-bottom flask (29 / 32 mm diameter) and sulfuric acid (1.7 mL, 31 mmol, 0.16 equiv., 98 wt%) was added. The reaction solution was then concentrated under vacuum on a rotary evaporator (90 °C, 200 mbar to 50 mbar) for 3 h to evaporate all water from the reaction solution. Methanol (400 mL) and an oval PTFE-coated stir bar were added to the reaction mixture. The reaction was then stirred at room temperature for 12 h and then neutralized with 10 N NaOH (3.1 mL). A filtration apparatus consisting of a 1 L filter flask, a neoprene adapter, and a Buchner funnel (ground glass frit, porosity grade 3) was assembled. The resulting salt and stir bar in the neutralized reaction solution were filtered off, and the filtrate was dried on a rotary evaporator at 45 °C and 100 mbar. The residue was then dissolved in DCM (250 mL) and transferred to a 1 L separatory funnel. The solution diluted with 250 mL of water was added to the separatory funnel, sealed, and shaken. The organic and aqueous phases were separated, and the aqueous phase was returned to the separatory funnel. This was extracted once more with DCM (250 mL). The layers were again separated, and the organic phases were combined and dried over magnesium sulfate (1–2 g). A filtration apparatus consisting of a 1 L filter flask, a neoprene adapter, and a Buchner funnel (ground glass frit, porosity grade 3) was assembled. The organic phase was then filtered to remove the magnesium sulfate and then transferred to a 29 / 32 1 L round-bottom flask. Dichloromethane was removed using a rotary evaporator at 45 °C and 500 mbar. The resulting oil was transferred to a 50 mL pear-shaped round-bottom flask and a PTFE-coated stir bar was added. The flask was then equipped with a distillation train, a two-neck round-bottom flask, and a gas adapter and connected to a Schlenk line. The reaction solution was slowly heated to 180 °C using an oil bath. Residual methyl glyoxylate was distilled off at 90-180°C and 0.1 mbar. The collection flask was then replaced and the desired product was removed as a distillate at 180°C and 0.01 mbar. The distilled product was used for polymerization. The present invention can be embodied in the following manner. <Aspect 1> A compound having the structure (I), or (II), or (V): [ka] [where: R 1 is -H, -CHOH, or -CH(OH)CHOH; R 2 is -H, -OH, or -CHOH; R 3 is -H, -OH, or -CHOH; R 10 is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety may optionally be substituted with a C1-C4-alkyl group or a halogen atom; n is 0 or 1; p is 0 or 1; R is either -ZF or Y, and where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CHOH) and Y is hydrogen or a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms; where R 4 is a C1-C4 alkyl group; R 7 is a C1-C4 alkyl group, with the proviso that When R is Y and n is 0, R 1 or R 2 at least one of which is not hydrogen]. <Aspect 2> 2. A compound according to aspect 1, wherein R is -ZF, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH), -COOR 4, -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CH2OH)2]; In particular, R is -(CH2) m COOH; -CHCOOH, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; -(CH2) m CH(COOH)2; -(CH2) m COOR 4 ;-C6H4COOR 4 wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 COOR 4 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(COOR4)2; -(CH2) m CHO; -C6H4CHO, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 CHO, wherein the aliphatic ring is optionally substituted with 1 to 4 C-C alkyl groups; -(CH) m CH(CHO)2; -(CH2) m C2H3; -C6H4C2H3, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 C2H3 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(C2H3)2; -(CH2) mC2H; -C6H4C2H, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 C2H [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m N3; -C6H4N3, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 N3 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m NH2; -C6H4NH2, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 NH2 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(NH2)2; -(CH2) m NHR 7 ;-C6H4NHR 7 wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -CH 10 NHR 7 [wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; -(CH2) m CH(NHR 7 )2; -(CH2) m OH; -C6H4OH, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; -C6H 10 OH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or -(CH2) m CH(CH2OH)2; where R 4 is a C1-C4 alkyl group; m is an integer from 0 to 10, particularly from 0 to 4; and R 7 is a C1-C4 alkyl group. <Aspect 3> n is 0 and R 2 The compound of embodiment 2, wherein <Aspect 4> The compound of embodiment 2 or embodiment 3, wherein R is —(CH) m COOR 4 ;-C6H4COOR 4 wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; -CH 10 COOR 4 wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups; or -(CH2) m CH(COOR 4 )2 [where m is 0 to 4, and R 4 is a C1-C4-alkyl group, in particular where R 4 is -CH3 and m is 0. <Aspect 5> The compound of any one of aspects 1 to 4, wherein the compound has the structure (I) and m is 0. <Aspect 6> The compound according to embodiment 1, wherein Y is a linear or branched organic residue having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and most preferably 1 to 3 carbon atoms. <Aspect 7> Structure (I), or (II), or (V): [ka] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined in any one of aspects 1 to 6], or a composition comprising at least two different compounds according to any one of aspects 1 to 6, the method comprising the steps of: a. providing a carbohydrate or lignocellulose-containing composition; b. adding an aldehyde, optionally comprising at least one functional group selected from the group consisting of carboxylic acid, carboxylic acid amide, ether, alkyne, alkene, aldehyde, chloride, hydroxyl, azide, carboxylic acid ester, aldehyde, vinyl, and amine, to the carbohydrate- or lignocellulose-containing composition to obtain a mixture; c. heating the mixture under acidic conditions; and d. Structure (I), or (II), or (V): [ka] [where R, R 1 , R 2 , R 3 , R 10 , n, and p are as defined in any one of aspects 1 to 6], or a composition comprising at least two different compounds according to any one of aspects 1 to 6. <Aspect 8> 8. The method of claim 7, wherein the aldehyde in step b) is selected from the group consisting of acetaldehyde, propionaldehyde, isobutyraldehyde, glyoxylic acid, dialdehyde, cyclopropanecarboxaldehyde, isobutyraldehyde, pivaldehyde, tolualdehyde, and benzaldehyde. <Aspect 9> 9. The method of any one of aspects 7 or 8, wherein the carbohydrate is an aldopentose, aldohexose, aldoheptose, ketohexose, ketoheptose, or a mixture thereof, preferably wherein the carbohydrate is ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, glucoheptose, mannoheptose, psicose, fructose, sorbose, talose, talc ... The carbohydrate is selected from the group consisting of gatose, sedoheptulose, mannoheptulose, taloheptulose, alloheptulose, and mixtures thereof, more preferably, the carbohydrate is xylose or glucose, or a mixture thereof; or the lignocellulose-containing composition has a lignin content of 20 to 40 wt. % based on the total weight of the lignocellulose-containing composition, and / or the aldehyde has the formula R-CHO, where R is as defined in aspect 1. <Aspect 10> The method of any one of aspects 7 to 9, wherein the aldehyde has the formula CHO-(CH) m COOH; CHO-C6H4COOH [wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; CHO-C6H 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups; or CHO-(CH2) m CH(COOH)2, and wherein the process comprises the additional step of adding a C1-C4-alkyl alcohol, preferably methanol, after step c. and before step d. <Aspect 11> 11. The method according to any one of aspects 7 to 10, wherein the mixture is heated to 50 to 120°C, preferably 60 to 110°C, more preferably 60 to 110°C, and most preferably 60 to 85°C, and / or the heating is carried out at a pressure of 70 to 130 mbar, preferably 80 to 120 mbar, and more preferably 90 to 110 mbar. <Aspect 12> 12. The method according to any one of aspects 7 to 11, wherein the lignocellulose-containing composition is biomass, in particular lignocellulosic biomass. <Aspect 13> A polymer comprising as repeat units: [ka] {where: R 1 , R 2 , R 3 , R 10 , n, and p are as defined in embodiment 1; and R 5 Ha-ZF 1 - or Y 1 and R 6 Ha-F 2 -Z- or Y 1 wherein Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogens, and F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)- or a covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 - or a covalent bond; and Y 1 is a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms; In particular, here, R 5 Ha-(CH2) m C(=O)O-, and R 6 is -OC(=O)(CH2) m -is; or R 5 is -C6H4C(=O)O-, and R 6 is -OC(=O)C6H4-, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R5 -CH 10 C(=O)O-, and R 6 -OC(=O)CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m OC(=O)-, and R 6 is -C(=O)O(CH2) m -is; or R 5 is -C6H4OC(=O)-, and R 6 is -C(=O)OC6H4-, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 OC(=O)-, and R 6 is -C(=O)OC6H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R 5 Ha-(CH2) m C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)(CH2) m -is; or R 5 is -C6H4C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)C6H4-, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 C(=O)NR 8 - and R 6 Ha-R 8 NC(=O)CH 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; or R5 Ha-(CH2) m R 8 NC(=O)-, and R 6 is -C(=O)NR 8 (CH2) m -is; or R 5 Ha-C6H4R 8 NC(=O)-, and R 6 is -C(=O)NR 8 C6H4-, wherein the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms; or R 5 -CH 10 R 8 NC(=O)-, and R 6 is -C(=O)NR 8 C6H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups; where R 8 is H or a C1-C4 alkyl group; m is an integer from 0 to 10, particularly from 0 to 4; and o is an integer from 2 to 10, especially from 2 to 4, with the proviso that: R 5 and R 6 If Y1 and n is 0, then R 1 or R 2 at least one of which is not hydrogen}. <Aspect 14> The polymer comprises repeating units having structure (III), where n and R 2 is as defined in aspect 3, and R 1 is H or CHOH, and in particular R 1 is H and m is as defined in embodiment 5. <Aspect 15> R 5 is -C(=O)O-, and R 6 15. The polymer of any one of embodiments 13 to 14, wherein is —O—C(═O)— and o is 2. <Aspect 16> At least one compound according to any one of aspects 1 to 6 optionally has the formula R 9 -LR 9A 16. A method for preparing a polymer according to any one of aspects 13 to 15, wherein the polymer is reacted with a compound having the formula L is (CH2) o (VII), CO(VIII), and diphenyl sulfone(IX) [ka] is selected from the group consisting of R 9 and R 9A -OR 11 , -OH, -NR 8 , -COOH, -COOR 4 and halogen atoms; where R 11 is selected from the group consisting of aryl and alkyl, or a residue R 9 R 11 and residue R 9A R 11 together form a ring system; wherein the halogen atoms are selected from the group consisting of fluorine, chlorine, bromine, and iodine; where R 8 is as defined in aspect 13; where R 4 is as defined in aspect 2 or 4; and o is as defined in embodiment 13 or 15]. <Aspect 17> R 9 and R 9A 17. The method for preparing a polymer according to embodiment 16, wherein <Aspect 18> L is (CH2) o 18. The method of any one of aspects 16 or 17, wherein <Aspect 19> R 9 -LR 9AA method for preparing a polymer according to any of aspects 16 or 17, wherein is bis-(4-halogenphenyl)sulfone, in particular bis-(4-chlorophenyl)sulfone, or bis-(4-fluorophenyl)sulfone. <Aspect 20> 18. A method for preparing the polymer according to claim 16 or 17, comprising: where: R 9 -LR 9A is organic Carbonate and preferably dialkyl carbonates, preferably dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate; diaryl carbonates, preferably diphenyl carbonate or dimethylphenyl carbonate; or circular Carbonate , preferably ethylene carbonate or trimethylene carbonate. <Aspect 21> Aspect 21. The method of any one of aspects 16 to 20, wherein the reaction is carried out in the presence of a catalyst and / or initiator and / or at a temperature of 30 to 250°C. <Aspect 22> 16. Use of a polymer according to any one of embodiments 13 to 15 for the production of sheets, fibers, or molded articles, in particular as a replacement for poly(ethylene terephthalate).

Claims

1. Compounds having structure (I): 【Chemical 1】 [where: R １ is -H, -CH ２ OH, or -CH(OH)CH ２ OH; R ２ is —H, —OH, or —CH ２ OH; n is 0 or 1; R is -Z-F, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally 1 to 4 C １ ~C ４ - is substituted with an alkyl group or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH) ２ , -COOR ４ , -CHO, -CH(CHO) ２ , -C ２ H ３ , -C ２ H, -N ３ , -NH ２ , -NHR ７ , -OH, -CH(CH ２ OH) ２ where R ４ is C １ ~C ４ - is an alkyl group; R ７ is C １ ~C ４ -alkyl group].

2. 2. The compound of claim 1, wherein R is - (CH ２ ) ｍ COOH; -C ６ H ４ COOH, wherein the aromatic ring optionally has 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ COOH, wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH(COOH) ２ ; - (CH ２ ) ｍ COOR ４ ;-C ６ H ４ COOR ４ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ COOR ４ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH (COOR ４ ) ２ ; - (CH ２ ) ｍ CHO;-C ６ H ４ CHO, wherein the aromatic ring optionally has 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ CHO, wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH (CHO) ２ ; - (CH ２ ) ｍ C ２ H ３ ;-C ６ H ４ C ２ H ３ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ C ２ H ３ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH(C ２ H ３ ) ２ ; - (CH ２ ) ｍ C ２ H; -C ６ H ４ C ２ H, wherein the aromatic ring optionally has 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ C ２ H, wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with an alkyl group; - (CH ２ ) ｍ N ３ ;-C ６ H ４ N ３ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ N ３ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with an alkyl group; - (CH ２ ) ｍ NH ２ ;-C ６ H ４ NH ２ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ NH ２ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH(NH ２ ) ２ ; - (CH ２ ) ｍ NHR ７ ;-C ６ H ４ NHR ７ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ NHR ７ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with alkyl groups]; -(CH ２ ) ｍ CH (NHR ７ ) ２ ; - (CH ２ ) ｍ OH; -C ６ H ４ OH, wherein the aromatic ring optionally has 1 to 4 C １ ~C ４ -substituted by an alkyl group or 1 to 4 halogen atoms; ６ H １０ OH, wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with an alkyl group; or - (CH ２ ) ｍ CH (CH ２ OH) ２ and Here, R ４ is C １ ~C ４ - is an alkyl group; m is an integer from 0 to 10; and R ７ is C １ ~C ４ - an alkyl group.

3. n is 0, and R ２ The compound of claim 2, wherein is —H.

4. The compound according to claim 2 or 3, wherein R is -(CH ２ ) ｍ COOR ４ ;-C ６ H ４ COOR ４ wherein the aromatic ring optionally comprises 1 to 4 C １ ~C ４ -substituted with an alkyl group; ６ H １０ COOR ４ wherein the aliphatic ring optionally contains 1 to 4 C １ ~C ４ -substituted with an alkyl group; or -(CH ２ ) ｍ CH (COOR ４ ) ２ where m is 0 to 4, and R ４ is C １ ~C ４ - Compounds which are alkyl groups.

5. The compound according to any one of claims 2 to 4, wherein m is 0.

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