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 a ubiquitous consumable in our daily lives. Global plastic production increased to over 380 million tons per year in 2015, representing an average annual growth rate of 8.5%. The global lifecycle greenhouse gas emissions from the production of these plastics amounted to 1.7 billion tons of CO2 equivalent (CO2e) in 2015, or 5% of global greenhouse gas emissions, 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)). Furthermore, more than one-third of this plastic is discarded after an average lifespan of less than six months, and the majority of it eventually ends 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). Plastics are not only manufactured from non-renewable and polluting fossil fuels, but they are also non-biodegradable and harmful to the world's ecosystems.

[0002] Research into bio-based and biodegradable polymers is urgently needed to reduce emissions and pollution from plastic production. In 2018, 2,274,000 tons of bioplastics were produced, representing less than 1% of global plastic production. Of this 2,274,000 tons, 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] While polymers from renewable resources are being developed, their mechanical properties and / or processability typically do not reach those of petroleum-based plastics. Commonly used polymers derived from renewable resources, such as polylactic acid (PLA), polybutyl polysuccinate (PBS), and polyhydroxyalkanoates (PHA), are not suitable substitutes for packaging materials like 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. Coca-Cola Co. and DuPont have commercialized partially renewable PET using renewablely obtained diols, but they have yet to find a renewable route to economically produce or replace terephthalic acid (TPA), a hard diacid component.

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

[0005] Renewable polyesters are prepared using commercially available dianhydrohexitols such as isosorbide, which are rigid bicyclic diols derived from sugars. Polyesters containing these cyclic sugars also possess excellent thermal and mechanical properties and improved biodegradability (Zamora, F.; Hakkou, K.; Munoz-Guerra, S.; Galbis, JA 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, the main drawback of these sugars is their low reactivity, which is due to the secondary nature of the alcohol group and, in some cases, the different stereoorientation of the hydroxyl group relative to the fused ring. Furthermore, isosorbide is usually obtained by acid-catalyzed dehydration of D-sorbitol. Obtaining the required purity of isosorbide monomers requires cumbersome reaction steps, including distillation, recrystallization from alcohol, recrystallization from melt, or a combination of these methods. Furthermore, the synthesis is limited to diols, and the production of derivatives such as amines requires further synthetic steps.

[0006] Similarly, bicyclic, sugar-derived diacitors (2,3:4,5-di-O-methylene-galactarates) have been synthesized by acetalizing galactaric acid with formaldehyde, as an attempt to directly replace terephthalic acid (TPA). While high molecular weight polymers with excellent thermal and mechanical properties and enhanced hydrodegradability have been obtained, the production of these precursors from biomass requires a cumbersome multi-step 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 candidate for feasible production (because they are produced from glucose), requires fermenting glucose to gluconic acid, then oxidizing the gluconic acid to glucaric acid on a Pt / C catalyst, and finally reacting it 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] Carbohydrate acetals, such as glucose acetals, have been prepared. For example, U.S. Patent No. 6,294,666 describes a tricyclic compound prepared by the acetalization of glucose. However, U.S. Patent No. 6,294,666 does not describe polymerizable monomers. Also, in WO96 / 32434A1, a tricyclic compound prepared by the acetalization of glucose is described as a saccharide residue of polyethylene oxide used in pharmaceutical applications. Again, WO96 / 32434A1 does not describe polymerizable monomers. [Overview of the project] [Problems that the invention aims to solve]

[0008] Building upon the prior art described above, the object of the present invention is to provide monomers that can be polymerized or copolymerized, and in particular, can produce polymers that are fully regenerative and preferably biodegradable. Ideally, the polymers or copolymers prepared from such monomers have good thermal and / or mechanical properties.

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

[0010] Other, more specific objectives will be partially revealed and partially described later in this specification. [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 described in claim 1, the method described in claim 7, the polymer described in claim 13, the method described in claim 16, and the use described in claim 22.

[0012] Further advantageous embodiments of the present invention are specified in the dependent claims and are described in detail below herein.

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

[0014] [ka]

[0015] [Here, R 1 is -H, -CH2OH, or -CH(OH)CH2OH; R 2 is -H, -OH, or -CH2OH; R 3 is -H, -OH, or -CH2OH; R 10 This is a hydrocarbon moiety having hydrogen or 1 to 20 carbon atoms, where each hydrogen atom in the hydrocarbon moiety may optionally be substituted with a C1-C4 alkyl group or halogen atom; n is either 0 or 1; p is either 0 or 1; R is either -ZF or Y, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1 to C4 alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH)2, or -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CH2OH)2, and Y is a hydrogen atom or a linear, branched, or cyclic organic residue having 1 to 20 carbon atoms. Here, R 4 is a C1-C4 alkyl group; and R 7 It is a C1-C4 alkyl group, however If R is Y and n is 0, then 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 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" represents a hydrocarbon moiety in which one or more or all of the hydrogen atoms can be replaced (substituted) by a C1-C4-alkyl group or a halogen atom. Each of the three hydrogen atoms of the terminal carbon atom of the hydrocarbon moiety can be substituted by 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, etc.

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

[0019] In the case of a chemical moiety such as a substituted alkyl moiety or an aromatic or aliphatic moiety, one of the hydrogen atoms in the moiety is replaced by a substituent. For example, a -C6H4- moiety substituted with a methyl group corresponds to a -C6H3(CH3)- moiety.

[0020] Surprisingly, it has been found that polymerizable monomers can be prepared from renewable resources such as biomass using a simple synthesis protocol. By using established acetalization chemistry, the compounds reported herein can be obtained. Depending on the additional functional groups bonded to the aldehyde, monomers with different functional groups can be obtained. Alternatively, acetalization can be carried out using aldehydes having functional groups that can be readily converted to other functional groups, including vinyl, alcohol, amine, and azide groups, but are not particularly limited. Thus, polyesters, polyamides, or other types of polymers can be prepared from the compounds reported herein. While not wishing to be bound by any particular theory, the condensed rings of structures (I), (II), and (V) are considered to provide polymers with good thermal and / or mechanical properties prepared from the compounds described herein. These properties are seen in PET and PEF produced from terephthalic acid and franzicarboxylic acid. Thus, the present invention provides the first monomers from renewable resources using biodegradable carbohydrates that can be produced directly from biomass in a simple process.

[0021] The present invention also relates to structure (I), (II), or (V):

[0022] [ka]

[0023] [Here, R, R 1 , R 2 , R 3 , R 10 The present invention provides a method for preparing a compound having one of the following [wherein n and p are as defined herein], or a composition comprising at least two different compounds of the present invention, the method comprising the following steps: a. A step of providing a composition containing carbohydrates or lignocellulose; b. A step of adding an aldehyde, which optionally contains at least one functional group selected from the group consisting of carboxylic acids, carboxylic acid amides, ethers, alkynes, alkenes, aldehydes, chlorides, hydroxyls, and azides, carboxylic acid esters, aldehydes, vinyls, and amines, to a carbohydrate or lignocellulose-containing composition to obtain a mixture; c. A step of heating the mixture under acidic conditions; and d. Structure (I), (II), or (V):

[0024] [ka]

[0025] [Here, R, R 1 , R 2 , R 3 , R 10 A step of separating, in particular isolating, a compound of the present invention having one of [n, and p as defined herein], or a composition comprising at least two different compounds of the present invention.

[0026] Preferably, the at least one functional group is selected from the group consisting of carboxylic acids, carboxylic acid amides, ethers, aldehydes, chlorides, and hydroxyls.

[0027] The present invention also provides a polymer comprising the following as repeating units:

[0028] [ka]

[0029] [Here, 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 Here, Z is a hydrocarbon moiety having 0 to 10 carbon atoms and optionally substituted with 1 to 4 C1 to 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 covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 -, or covalent bond; Here, R 8 is H or C1-C4 alkyl group; and o is an integer between 2 and 10, especially between 2 and 4; and Y 1 These are linear, branched, or cyclic organic residues having 1 to 20 carbon atoms, However, R 5 and R 6 Y 1 And if n is 0, R 1 or R 2 At least one of them is different from hydrogen.

[0030] The present invention also provides a method for preparing the polymer of the present invention, wherein at least one compound of the present invention is optionally of formula R 9 -LR 9A It is subjected to a reaction with a compound having, Here, L is (CH2) o Selected from the group consisting of (VII), CO(VIII), and diphenylsulfone(IX):

[0031] [ka]

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

[0033] Finally, the present invention also provides the use of the polymer of the present invention, particularly as a substitute for poly(ethylene terephthalate), for the manufacture of sheets, fibers, or molded articles. [Brief explanation of the drawing]

[0034] [Figure 1] The 2D HSQC NMR spectra of the dimethylglyoxylate xylose (DMGX) isomer in DMSO-d6 are shown. [Figure 2] The 13C NMR spectra of the DMGX isomer in DMSO-d6 are shown. [Figure 3] The gas chromatography (GC) chromatograms (GC) of the purified DMGX isomers are shown. [Figure 4] The mass spectra (MS) and fragmentation of the DMGX isomer from GC-MS are shown. [Figure 5] The 2D HSQC NMR spectrum of poly(ethylenedimethylglyoxylatexylose) (PEDMGX) is shown. [Figure 6] The reflector-positive MALDI spectrum of PEDMGX is shown. [Figure 7] The GPC chromatograms of three PEDMGX samples synthesized at various temperatures and durations are shown. [Figure 8]The differential scanning calorimetry (DSC) curves of a PEDMGX sample heated from 30°C to 250°C and then cooled back to 30°C are shown. [Figure 9] The thermogravimetric analysis (TGA) curve for PEGDMX is shown. [Modes for carrying out the invention]

[0035] Preferred Embodiment

[0036] Compound of the present invention Structures (I), (II), and (V) are preferably obtained by the reaction of carbohydrates such as aldoses or ketoses with aldehydes. Those skilled in the art will be aware of the effect this has on the stereostructure of the compounds and polymers reported herein.

[0037] residue R 1 , R 2 , R 3 , and R 10 The structure (I), (II), or (V) differs depending on the type of carbohydrate from which it is obtained. If structure (I), (II), or (V) is obtained from an aldose, R 1 R can be -H, -CH2OH, or -CH(OH)CH2OH, 2 is -H, R 3 R can be -H, -OH, or -CH2OH. If structure (I), (II), or (V) is obtained from a ketose, R 1 R can be -H or -CH2OH, 2 R can be -OH or -CH2OH, 3 This could be the case for -H.

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

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [Here, 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)2, -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CH2OH)2, where R 4 R is a C1-C4 alkyl group, 7 [It is a C1-C4 alkyl group.]

[0043] More preferably, the compound of the present invention has the following structure:

[0044] [ka]

[0045] [Here, 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)2, -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -C2H, -N3, -NH2, -NHR 7 , -OH, -CH(CH2OH)2, where R 4 is a C1-C4 alkyl group, and R 7 [It is a C1-C4 alkyl group.]

[0046] Z is preferably -(CH2) m-(where m is an integer between 0 and 10, especially between 0 and 4);-C6H4-(where the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms); or-C6H 10 -(Here 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 These are C1-C4 alkyl groups.

[0047] Preferably, R 2 is -H. More preferably, R 2 H is R 1 is H or CH2OH, 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 obtained from an aldose.

[0049] Preferably, the compound has structure (I). The compound having structure (I) is a hard monomer that imparts excellent thermal and / or mechanical properties to the polymer.

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

[0051] In structures (I), (II), and (V), R may comprise 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 cyclic aliphatic ring system having 5 to 10, preferably 6, carbon atoms. Possible functional groups in R include -COOH, -CH(COOH)2, and -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 can be selected from the group consisting of, where R 4 is a C1-C4 alkyl group, and R<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​[Here, the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms];-C6H 10 COOR 4 [Here, the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]; (CH2) m CH(COOR4)2; -(CH2) m CHO;-C6H4CHO[where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 CHO[where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups];-(CH2) m CH(CHO)2; -(CH2) m C2H3;-C6H4C2H3[where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 C2H3 [where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups];-(CH2) m CH(C2H3)2; -(CH2) m C2H;-C6H4C2H[where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 C2H [where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]; -(CH2) m N3;-C6H4N3[where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 N3 [where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]; -(CH2) m NH2;-C6H4NH2[where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10NH2 [where 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 [Here, the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms];-C6H 10 NHR 7 [Here, the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups];-(CH2) m CH(NHR 7 )2; -(CH2) m OH;-C6H4OH [where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 OH [where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]; or -(CH2) m It is CH(CH2OH)2, Here, R 4 It is a C1-C4 alkyl group; R 7 is a C1-C4 alkyl group; and m is an integer between 0 and 10, especially between 0 and 4.

[0054] More preferably, in structures (I), (II), and (V), R is -(CH2) m COOH;-C6H4COOH [where the aromatic ring is optionally substituted with 1-4 C1-C4 alkyl groups or 1-4 halogen atoms];-C6H 10 COOH [where 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[Here, the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms];-C6H 10 COOR 4 [Here, the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups];-(CH2) m CH(COOR 4 )2, Here, R 4 It is a C1-C4 alkyl group; R 7 is a C1-C4 alkyl group; and m is an integer between 0 and 10, especially between 0 and 4.

[0055] R is -(CH2) m COOR 4 ;-C6H4COOR 4 [Here, the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups];-C6H 10 COOR 4 [Here, the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]; or -(CH2) m CH(COOR 4 )When it is 2, very good results are obtained, where m is 0 to 4 and R 4 R is a C1-C4 alkyl group. Preferably, R is -COOMe.

[0056] The aforementioned hydrocarbon moieties are typically readily accessible aldehydes. If these aldehydes are unavailable, the compounds can be obtained by functional group transformation, such as reductive amination or hydroamination. Furthermore, the functional groups of the aforementioned residue R enable the preparation of polymers from compounds having structures (I) and (II) with good thermal and / or mechanical properties. In particular, thermal and / or mechanical properties can be tuned by selecting specific hydrocarbon moieties, such as aromatic or aliphatic rings for more rigid polymers, or alkylene moieties for more flexible polymers. The aforementioned functional groups provide access to various types of polymers, including polyesters, polyamides, or polyethers. Polyesters have the particular advantage of being very often biodegradable.

[0057] According to embodiments 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 C2H, -(CH2) m N3, -(CH2) m NH2, -(CH2) m CH(NH2)2, -(CH2) m NHR 7 ,-(CH2) m OH, or -(CH2) m It is CH(CH2OH)2, and here R 4 R is a C1-C4 alkyl group, preferably a -CH3 group; 7 m is a C1-C4 alkyl group; and m is an integer from 0 to 10, preferably from 0 to 4, more preferably 0.

[0058] The compound has 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 C2H, -(CH2) m N3, -(CH2) m NH2, -(CH2) m CH(NH2)2, -(CH2) m NHR 7 ,-(CH2) m OH, or -(CH2) m It is CH(CH2OH)2, and here R 4 R is a C1-C4 alkyl group, preferably a -CH3 group; 7 The optimal result was obtained when [ is a C1-C4 alkyl group; and m is 0]. More preferably, R 2 H is H, and R 1 is H or CH2OH, and especially R 1 H is H.

[0059] In preferred embodiments of the present invention, good results were 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, and most preferably 1 to 3 carbon atoms, such as a hydrocarbon moiety like methylene, ethylene, or propylene.

[0060] Therefore, preferably the compound of the present invention has 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 compound of the present invention has one of the following structures:

[0075] [ka]

[0076] More preferably, the compound of the present invention has one of the following structures:

[0077] [ka]

[0078] [ka]

[0079] In the structure shown above, the ring system preferably has the following three-dimensional structure:

[0080] [ka]

[0081] Method 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 comprises 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), in particular a mixture of the compounds of the present invention having structure (I), (II), or (V), can be obtained.

[0082] Therefore, the present invention relates to structure (I), (II), or (V):

[0083] [ka]

[0084] [Here, R, R 1 , R 2 , R 3 , R 10 The present invention provides a method for preparing a compound having one of the following [wherein n and p are as defined herein], or a composition comprising at least two different compounds of the present invention, the method comprising the following steps: a. A step of providing a composition containing carbohydrates or lignocellulose; b. A step of adding an aldehyde, which optionally contains at least one functional group selected from the group consisting of carboxylic acids, carboxylic acid amides, ethers, alkynes, alkenes, aldehydes, chlorides, hydroxyls, azides, carboxylic acid esters, aldehydes, vinyls, and amines, to a carbohydrate or lignocellulose-containing composition to obtain a mixture; c. A step of heating the mixture under acidic conditions; and d. Structure (I), (II), or (V):

[0085] [ka]

[0086] [Here, R, R 1 , R 2 , R 3 , R 10 A step of separating, in particular isolating, a compound of the present invention having one of [n, and p as defined herein], or a composition comprising at least two different compounds of the present invention.

[0087] In a preferred embodiment of the present invention, good results were obtained when the aldehyde in step b) was 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 the carbohydrate. The carbohydrate may be an aldose or a ketose. The carbohydrate may be a pentose, a hexose, or a heptose. Preferably, the carbohydrate is an aldopentose, an aldhexose, an aldohepose, a ketohexose, a ketohepose, or a mixture thereof. More preferably, the carbohydrate is an aldopentose, an aldhexose, an aldohepose, or a mixture thereof, particularly an aldopentose, an aldhexose, or a mixture thereof.

[0089] Advantageously, the carbohydrate is selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, growth, 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, growth, idose, galactose, glucoheptose, mannoheptose, or mixtures thereof, and more preferably, it is selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, growth, idose, galactose, or mixtures thereof. Most preferably, the carbohydrate is xylose, glucose, or a mixture thereof.

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

[0091] Lignocellulose is considered to be the most abundant raw material (biomass) available on Earth. Lignocellulosic biomass can be classified into unused biomass, waste biomass, and energy crops. Unused lignocellulosic biomass includes all naturally occurring terrestrial plants, such as trees, shrubs, and grasses. Waste lignocellulosic biomass is produced as a low-value by-product in various industrial sectors, such as agriculture (corn stalks and leaves, sugarcane bagasse, straw, etc.) and forestry (waste from sawmills and paper mills).

[0092] Lignocellulose contains hemicellulose, cellulose, and lignin. Both hemicellulose and cellulose can be considered carbohydrate polymers. Carbohydrate polymers contain five and six carbon sugar monomers, respectively, bonded to lignin.

[0093] Lignin can be considered an aromatic polymer. The aromatic polymer includes methoxylated phenylpropane subunits such as guaiacyl and syringyl subunits.

[0094] Xylan is a polysaccharide belonging to the hemicellulose class, 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 unused 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 pine, larch, pine, hemlock, redwood, spruce, and yew. The most preferred wood for the lignocellulose-containing composition is hardwood 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 yield high amounts of lignocellulosic biomass. Furthermore, because energy crops grow rapidly, the lignocellulosic biomass is already available in a short period of time, such as two or three months later. Examples of energy crops include giant reed, big bluestem, Chinese tallow tree, pheasant leaf, duckweed, purging nuts, black nut, switchgrass, and elephant grass.

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

[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 lower. 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, more preferably less than 30% by weight, and particularly 0 to 10% by weight of water.

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

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

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

[0102] In the method 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 (where the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups);CHO-C6H 10 COOH (where the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups); or CHO-(CH2) m It contains CH(COOH)2.

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

[0104] To produce monomers, a mixture containing a substrate (sugar or lignocellulose) and an 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. It has been found that the reaction proceeds very slowly at temperatures below 50°C. At all temperatures, the reaction can be accelerated by the presence of an acid catalyst. It has been found that undesirable byproducts are produced at temperatures above 120°C.

[0105] The heating of the mixture can also be carried out under various pressures depending on the raw materials. In the case of carbohydrates, heating is favorably carried out at pressures below 150 mbar. In particular, the reaction can be carried out at pressures of 70–130 mbar, preferably 80–120 mbar, and more preferably 90–110 mbar. It has been found that the reaction proceeds more rapidly under reduced pressure.

[0106] For carbohydrates, very good results are obtained when the mixture is heated at 50-120°C, preferably 60-110°C, more preferably 60-100°C, most preferably 60-85°C, and at a pressure of 70-130 mbar, preferably 80-120 mbar, more preferably 90-110 mbar. Under these conditions, water produced during the reaction can be removed from the reaction, which helps to obtain a high yield 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 preferably carried out in an aprotic polar solvent, more preferably an ether, and most preferably in a solvent which is 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. Next, the cellulose is preferably removed by filtration from the reaction mixture. Next, the solvent is preferably removed from the reaction mixture by evaporation under reduced pressure such as from 1 mbar to 150 mbar. Next, the lignin is preferably removed by precipitation in the solvent followed by filtration of the precipitation mixture, and a filtrate is obtained. Next, the obtained filtrate is preferably concentrated, an acid is added, and then it is heated and the pressure is reduced as described above for the carbohydrates.

[0108] The acidic conditions of the mixture are achieved by various means. Advantageously, an acid is added to the mixture. For this purpose, various acids can be used. 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. Without being particularly limited, acidic aldehydes such as glyoxylic acid can autocatalyze the reaction.

[0109] The method for preparing the compound of the present invention may include additional steps. Advantageously, the method of the present invention includes a step of adding an alcohol. Particularly when the aldehyde contains a carboxylic acid group, more specifically, when the aldehyde has the formula CHO-(CH2) mCOOH; CHO-C6H4COOH [where the aromatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; CHO-C6H 10 COOH [where the aliphatic ring is optionally substituted with 1 to 4 C1-C4-alkyl groups]; or CHO-(CH2) m When having CHO-(CH2)

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

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

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

[0113] Step d may include a neutralization step. Neutralization is preferably carried out using a weak base. Suitable examples of weak bases are bicarbonates such as sodium bicarbonate or potassium bicarbonate, preferably in aqueous solution.

[0114] The separation, particularly isolation, of the compounds of the present invention or compositions comprising at least two different compounds of the present invention may comprise several steps. The separation may comprise dissolving one or more compounds of the present invention in an organic solvent. The separation may also comprise one or more filtration and / or drying steps, preferably before dissolving one or more compounds of the present invention in an organic solvent. Suitable organic solvents include diethyl ether, tetrahydrofuran, ethyl acetate, glyme, diglyme, dichloromethane, chloroform, and tetrachloromethane, particularly diethyl ether, tetrahydrofuran, ethyl acetate, and dichloromethane, more specifically ethyl acetate or dichloromethane. The separation may also comprise one or more washing steps using aqueous solutions, such as aqueous sodium bicarbonate and / or aqueous sodium chloride. The separation may also comprise 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 resolution of isomers is possible by performing temperature-controlled crystallization.

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

[0116] Accordingly, the present invention also provides the following polymers comprising repeating units:

[0117] [ka]

[0118] [Here, 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 to C4 alkyl groups or 1 to 4 halogen atoms, and here F 1 -C(=O)O-, -OC(=O)-, -C(=O)NR 8 -, -R 8 NC(=O)-, or covalent bond, and F 2 -OC(=O)-, -C(=O)O-, -R 8 NC(=O)-, -C(=O)NR 8 -, or covalent bond; where R 8 [where is H or a C1-C4 alkyl group; and o is an integer between 2 and 10, particularly between 2 and 4].

[0119] residue R 1 , R 2 , and R 3 The monomer used in the preparation of the polymer of the present invention differs depending on the type of carbohydrate obtained therefrom. If the monomer is obtained from an aldose, 1 R can be -H, -CH2OH, or -CH(OH)CH2OH, 2 is -H, and R 3 R can be -H, -OH, or -CH2OH. If the monomer is obtained from a ketose, 1 R can be -H or -CH2OH, 2 R can be -OH or -CH2OH, and 3 It can be -H.

[0120] Therefore, the polymer of the present invention preferably comprises at least one of the following structures as a repeating unit:

[0121] [Chemistry]

[0122] [Chemistry]

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

[0124] More preferably, the polymer of the present invention contains, as a repeating unit, at least one of the following structures:

[0125] [Chemistry]

[0126] [Chemistry]

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

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

[0129] Z is preferably -(CH2) m -[where m is an integer between 0 and 10, especially between 0 and 4]; -C6H4-[where the aromatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms]; or -C6H 10 -[Here, the aliphatic ring is optionally substituted with 1 to 4 C1-C4 alkyl groups]. F is preferably -COOH, -COOR 4 , -C2H3, where R 4 These are C1-C4 alkyl groups.

[0130] Preferably, R 2 is -H. More preferably, R 2 H is R1 is H or CH2OH, 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 obtained 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 and optionally substituted with 1 to 4 C1-C4 alkyl groups or 1 to 4 halogen atoms, and F is -COOH, -CH(COOH)2, -COOR 4 , -CHO, -CH(CHO)2, -C2H3, -NH2, -NHR 7 , -OH, -CH(CH2OH)2, where R 4 is a C1-C4 alkyl group; and, R 7 These are C1-C4 alkyl groups.

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

[0135] Therefore, preferably, the polymer of the present invention comprises at least one of the following structures as a repeating unit:

[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] (Here, o is an integer between 2 and 10, especially between 2 and 4).

[0154] Preferably, the polymer of the present invention comprises repeating units having structure (III), where n is 0 and R 2 is -H, and R 1 is H or CH2OH, and especially R 1 H is and m is 0.

[0155] According to one embodiment of the present invention, the polymer does not contain repeating 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 polymer of the present invention comprises the following as repeating units:

[0158] [ka]

[0159] Here, o is 2; and does not contain repeating units having structure (IV).

[0160] In the structure shown above, the ring system preferably has the following three-dimensional structure:

[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 through simple processes.

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

[0164] R 9 and R 9A In a preferred embodiment of the present invention where these factors are identical, very good results were obtained.

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

[0166] A more preferred embodiment of the present invention, R 9 -LR 9A When the compound is bis-(4-halogen phenyl)sulfone, particularly bis-(4-chlorophenyl)sulfone or bis-(4-fluorophenyl)sulfone, good results were obtained.

[0167] According to a more preferred embodiment of the present invention, R 9 -LR9A is the organic carbonate of LCO in formula (VIII), and R 9 and R 9A The same or different OR 11 When this is the case, good results are obtained, and here R 11 is selected from the group consisting of aryl and alkyl, or residue R 9 R 11 and residue R 9A R 11 These compounds together form a ring system, i.e., a cyclic carbonate. For example, organic carbonates can be dialkyl carbonates, diaryl carbonates, or cyclic carbonates. Examples of dialkyl carbonates are dimethyl carbonate, diethyl carbonate, or methylethyl carbonate. Examples of diaryl carbonates are diphenyl carbonate or dimethylphenyl carbonate. Examples of cyclic carbonates are ethylene carbonate or trimethylene carbonate.

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

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

[0170] Preferably, the reaction is carried out in the presence of a catalyst. A non-exclusive 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, particularly a radical initiator. This is especially true when the compound of the present 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 50 to 230°C, and most preferably 100 to 220°C. If the reaction is carried out in the presence of a radical initiator, the temperature is preferably adjusted considering the radical initiator, and in particular considering 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 polymer preparation method of the present invention may also include several steps. According to one embodiment of the polymer preparation method of the present invention, in the first step, the compound of the present invention and formula R 9 -LR 9A Compounds having the following properties can be reacted to produce intermediates. For example, structure:

[0174] [ka]

[0175] A compound containing is reacted with an ethanediol to form an intermediate consisting of two ethanediol units:

[0176] [ka]

[0177] A corresponding transesterification intermediate containing the specified compound can be produced.

[0178] Next, in the second step, the intermediate can be polymerized to obtain the polymer of the present invention. For example, structure:

[0179] [ka]

[0180] An intermediate having the above 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. Furthermore, 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 process can be carried out over a variety of periods. For example, the first step of the reaction may be carried out for 1 to 15 hours, preferably 1 to 10 hours, and more preferably 1 to 7 hours. The second step of the reaction may be carried out for 2 to 15 hours, preferably 3 to 10 hours, and more preferably 3 to 8 hours.

[0183] In the first and second steps, the pressure can be reduced, especially in the case of transesterification reactions, in order to achieve high yield and high molecular weight. For example, in the transesterification reaction using ethanediol as the reagent, the reaction can be carried out first at atmospheric pressure and then under 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, and 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, and most preferably 1 mbar or less. By reducing the pressure during the reaction, particularly during the first and / or second steps, higher yields and / or higher molecular weights 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 polymer of the present invention is a promising candidate to replace poly(ethylene terephthalate). Accordingly, the present invention also provides the use of the polymer of the present invention for the manufacture of sheets, fibers, or molded articles, particularly as a substitute for poly(ethylene terephthalate).

[0187] Examples are described below, but they are not intended to be limiting. [Examples]

[0188] method MALDI-TOF: Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) spectra of 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 in 1 ml of THF and 10 μL of trifluoroacetic acid (TFA) was prepared. Subsequently, 0.5 μL of the polymer / HFIP solution was deposited on a steel analysis plate, followed by 0.5 μL of the DHB / TFA solution. To achieve optimal signal, the laser power for various polymer samples was set to 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 was fitted with a single PFG linear M column (PSS) and coupled to an Agilent 1100 VWD / UV detector operating at 294 nm, a DAWN HELEOS II multi-angle laser scattering (MALS) detector (Wyatt Technology Europe), and an Optilab TrEX RI detector (Wyatt). Samples were eluted at room temperature at 1 mL / min using HFIP containing 0.03 MK-TFAc. Each polymer sample was analyzed twice to ensure instrument accuracy. To accurately measure molecular weight, polymethyl methacrylate (PMMA) standards were purchased from PSS Polymer Standards Service in Germany and used to create a calibration curve applicable to the data.

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

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

[0192] synthesis

[0193] General reaction scheme:

[0194] [ka]

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

[0196] Synthesis of dimethylglyoxylate xylose from xylose D-xylose (200 g, 1.33 mol, 1.00 equivalent) was combined with glyoxylic acid monohydrate (500 g, 5.43 mol, 4.08 equivalents) in a 2 L round-bottom flask and heated at 95°C in a rotary evaporator. After dissolving the xylose in the molten glyoxylic acid, 98 wt / wt% sulfuric acid (28.57 g, 270.8 mmol, 0.2 equivalents) was added dropwise. Next, the pressure in the rotary evaporator was slowly reduced to 20 mbar to continuously remove the water produced as a byproduct of the reaction. The reaction was stopped after the yield of xylose protected with diglyoxylic acid exceeded 93% (approximately 3 hours). Next, methanol (1 L) was added to the reaction mixture, and the resulting solution was heated under reflux using an oil bath at 80°C until the yield of dimethyl ester of xylose protected with diglycylic acid, as determined by GC-FID, exceeded 95% (approximately 1 hour). The reaction mixture 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 at 45°C in a rotary evaporator at 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-colored sugar decomposition products and unreacted carboxylates. 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 a pressure of 0.02 mbar and an oil bath temperature of 80–180°C. The distillate containing methyl glyoxylate and residual solvent obtained during a gradient between 80°C and 180°C was discarded. A second flask was fitted, 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 for 4 hours using a PTFE-coated stirring rod, the solution was filtered through a 0.2 μm nylon membrane filter to remove the activated carbon, and concentrated under vacuum to obtain 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 impurities. Crystallization was successfully carried out with methanol, cyclopentyl methyl ether, and toluene.Furthermore, by using temperature-controlled crystallization, we were able to selectively crystallize the most abundant isomer while leaving the other three isomers in the mother liquor.

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

[0198] Exemplary synthesis of poly(ethylenedimethylglyoxylatexylose) One molar equivalent of dimethylglyoxylate xylose was placed in a two-necked round-bottom flask, to which an excess of freshly distilled ethanediol (2.2 equivalents) and 0.4 wt% antimony trioxide were added. The reaction vessel was attached to a distillation tube, purged three times with nitrogen, and then heated. The vessel was heated to 140°C in a sand bath with continuous stirring for 2 hours under a stable nitrogen flow, and methanol was removed by distillation. Next, the bath was heated to 200°C for 2 hours under a continuous nitrogen flow. Then, a vacuum of 0.1 mbar was applied, and the reaction was continued for a further 3 hours to remove ethylene glycol by distillation and allow transesterification to proceed. The reactants were cooled to room temperature and then dissolved in a minimum amount of 1,1,1,3,3,3-hexafluoro-2-propanol, which was added dropwise to methanol with stirring to precipitate. The polymer was filtered from the solution, washed with methanol, and dried under vacuum. By using various transesterification catalysts, reaction times, and temperatures, the same polymer with various molecular weights can be produced.

[0199] Figures 5-9 show the analytical data for PEDMGX. Figure 5 shows the 2D HSQC NMR spectrum indicating the successful synthesis of PEDMGX. The letters in parentheses next to the peaks indicate the stereostructures of carbon 6 and 9, respectively. Figure 6 shows the reflector-positive MALDI spectrum of PEDMGX. The distances between prominent peaks correspond to the molecular weight of the repeating units. Figure 7 shows the GPC chromatograms of three different PEDMGX samples synthesized at various temperatures and times (not all are explained here). Each polymer sample was analyzed twice to ensure instrument accuracy. For the measurements, polymethyl methacrylate (PMMA) molecular weight standards from PSS Polymer Standards Service (Germany) were used as external standards for molecular weight measurement. Molecular weights in the range of 10-50 kDa were achieved, which is well within the commercial range of PET (20-60 kDa). Figure 8 shows the DSC curve of PEDMGX after heating to 30°C–250°C and then cooling back to 30°C. The DSC shows a glass transition at 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, especially those requiring contact with boiling water. Figure 9 shows the TGA curve of PEGDMX. The TGA shows 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 temperature and final use temperature of the polymer.

[0200] General preparation procedure for DMGX-based polyester The following polymers were synthesized using the following method: poly(ethylenedimethylglyoxylatexylose), poly(propylenedimethylglyoxylatexylose), poly(butylenedimethylglyoxylatexylose), poly(pentylenedimethylglyoxylatexylose), and poly(hexylenedimethylglyoxylatexylose) were polymerized by polymerizing DMGX with ethanediol, propanediol, butanediol, pentanediol, and hexanediol, respectively. Dimethyl glyoxylate xylose (10 g, 34.4 mmol, 1.0 equivalent) was combined with diol (86 mmol, 2.5 equivalents), re-esterification catalyst: zinc acetate (2 mg, 0.011 mmol, 0.00032 equivalents), antioxidant: pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (13 mg, 0.011 mmol, 0.00032 equivalents), and triphenyl phosphite (13 mg, 0.042 mmol, 0.0012 equivalents) in a 250 mL two-neck round-bottom flask. Next, a distillation bridge, vacuum adapter, valve for nitrogen flow, and a 250 mL collection flask were attached to the reaction vessel and connected to a Schlenk line. The reaction vessel was backfilled with nitrogen three times. The reaction mixture was then heated to 140 °C under a steady flow of nitrogen while stirring in an oil bath. During the reaction, methanol byproducts were distilled from the reaction mixture and collected in a collection flask. 1 The reaction was monitored by 1H-NMR, and once complete re-esterification was observed (approximately 1-4 hours), the transesterification catalyst, antimony trioxide (2 mg, 0.0069 mmol, 0.0002 equivalents), was added to the reaction mixture as a suspension in diol (0.5 mL) under positive pressure nitrogen. Next, the reaction mixture was heated to 190°C, and the reaction vessel was slowly evacuated to a pressure of 0.02 mbar over 30 minutes. The diol reaction byproducts were distilled, and the polycondensation reaction proceeded. 1The reaction was stopped when the desired molecular weight was observed by end-group analysis after monitoring with 1H-NMR (high molecular weight, approximately 8-14 hours). Polymers derived from a mixture of the four DMGX isomers were typically orange. Polymers synthesized from the most abundant DMGX isomer were generally clear and colorless. The reactants were cooled to room temperature and dissolved in the minimum amount of 1,1,1,3,3,3-hexafluoroisopropanol (250 mL). The resulting solutions were added dropwise to a stirred solution of isopropanol (1 L) for butanediol, pentanediol, and hexanediol polymers, and methanol (1 L) for shorter-chain diols, to precipitate the polymers. The polymers were collected by filtration, washed with isopropanol followed by diethyl ether, and dried overnight under vacuum at 60°C and 0.02 mbar to obtain the product as a bright white powder. For polymerization with ethanediols and propanediols, where achieving high molecular weights was more difficult, dibutyltin oxide (45 mg, 0.184 mmol, 0.0053 equivalents), a more active transesterification catalyst, was used instead of zinc acetate and antimony trioxide.

[0201] Synthesis of dimethylglyoxylate xylose from lignocellulose biomass Biomass (extract-free, dried, 90.0 g) was collected in a 1 L reagent bottle weighed to tare weight. Next, glyoxylic acid monohydrate (60.753 g, 660 mmol, 3.3 equivalents), 1,4-dioxane (250 mL), hydrochloric acid (37 wt%, 16.7 mL, 200 mmol, 1.0 equivalent), and two large PTFE-coated stirring 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. After completion, the reaction mixture 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 Buchner funnel equipped with qualitative filter paper. The reaction mixture was filtered by washing with dioxane (250 mL) through the Buchner funnel to remove the cellulose-rich solid. Next, the filtrate was transferred to a 2L round-bottom flask (29 / 32) and concentrated using a rotary evaporator at a bath temperature of 45°C and an extreme pressure of 10 mbar. Then, an elliptical PTFE-coated stirring rod was added to the concentrated lignin solution, followed by the addition of deionized water (1L) to precipitate the lignin. The mixture was stirred at 500 RPM for 30 minutes to break up large aggregates. The stirring rod was then removed. A filtration apparatus was assembled consisting of a 2L filter flask, a neoprene adapter, and a membrane filter equipped with a 0.8 μm nylon membrane filter. The precipitated lignin solution was then filtered by washing with deionized water (100 mL) through the nylon membrane filter to collect the lignin.

[0202] The filtrate was transferred to a 2L round-bottom flask (29 / 32), and sulfuric acid (1.7 mL, 31 mmol, 0.16 equivalents, 98% by weight) was added. The reaction solution was then concentrated under vacuum for 3 hours in a rotary evaporator (90°C, 200 mbar to 50 mbar) to evaporate all water from the reaction solution. Methanol (400 mL) and an elliptical PTFE-coated stirring rod were added to the reaction mixture. The reaction mixture was then stirred at room temperature for 12 hours, and then neutralized with 10N NaOH (3.1 mL). A filtration apparatus consisting of a 1L filter flask, a neoprene adapter, and a Buchner funnel (ground glass frit, porosity grade 3) was assembled. The resulting salt and stirring rod were filtered off the neutralized reaction solution, and the filtrate was dried in a rotary evaporator at 45°C and 100 mbar. The residue was then dissolved in DCM (250 mL) and transferred to a 1L separatory funnel. The solution was diluted with 250 mL of water, sealed in a funnel, and shaken. The organic and aqueous phases were separated, and the aqueous phase was returned to the separatory funnel. This was extracted again with DCM (250 mL). The layers were separated again, the organic phase was combined, and dried with magnesium sulfate (1-2 g). A filtration apparatus was assembled consisting of a 1 L filter flask, a neoprene adapter, and a Buchner funnel (ground glass frit, porosity grade 3). Next, the organic phase was filtered to remove magnesium sulfate, and then transferred to a 1 L 29 / 32 round-bottom flask. Dichloromethane was removed using a rotary evaporator at 45°C and 500 mbar. The resulting oily substance was transferred to a 50 mL pear-shaped round-bottom flask, and a PTFE-coated stirring rod was added. Next, a distillation train, a two-necked round-bottom flask, and a gas adapter were attached to the flask and connected to a Schlenklein. The reaction solution was slowly heated to 180°C using an oil bath. Residual methyl glyoxylate was removed by distillation at 90–180°C and 0.1 mbar. Next, the collection flask was changed, and the desired product was collected as a distillate at 180°C and 0.01 mbar. The distilled product was used for polymerization.

Claims

1. A compound having the structure (I), or (II), or (V): 【Chemistry 1】 [where: R １ is -H, -CH ２ OH, or -CH(OH)CH ２ OH; R ２ is -H, -OH, or -CH ２ OH; R ３ is -H, -OH, or -CH ２ OH; R １０ is hydrogen or a hydrocarbon moiety having 1 to 20 carbon atoms, where each hydrogen atom of the hydrocarbon moiety is optionally １ ~C ４ - optionally substituted with an alkyl group or a halogen atom; n is 0 or 1; p 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 O.H. ２ where R ４ is C １ ~C ４ - is an alkyl group; R ７ is C １ ~C ４ -alkyl group, provided that In compound (V), F is neither —OH nor —C 2 H 3 .

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

5. The compound of any one of claims 2 to 4, wherein the compound has the structure (I) and m is 0.

6. Structure (I), or (II), or (V): 【Chemistry 2】 [where R, R １ , R ２ , R ３ , R １０ , n and p are as defined in any one of claims 1 to 5], or a composition comprising at least two different compounds according to any one of claims 1 to 5, 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): 【Chemistry 3】 [where R, R １ , R ２ , R ３ , R １０ , n, and p are as defined in any one of claims 1 to 5, or a composition comprising at least two different compounds as defined in any one of claims 1 to 5.

7. 7. The method of claim 6, 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.

8. 8. The method of claim 6 or 7, wherein the carbohydrate is an aldopentose, aldohexose, aldoheptose, ketohexose, ketoheptose, 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 claim 1.

9. The method of claim 6 or 7, wherein 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.

10. The method according to any one of claims 6 to 9, wherein the aldehyde has the formula CHO-(CH ２ ) ｍ COOH;CHO-C ６ H ４ COOH, wherein the aromatic ring optionally has 1 to 4 C １ ~C ４ -alkyl group]; CHO-C ６ H １０ COOH, wherein the aliphatic ring optionally has 1 to 4 C １ ~C ４ -alkyl group]; or CHO-(CH ２ ) ｍ CH(COOH) ２ and wherein the method comprises, after step c. and before step d., １ ~C ４ - the process comprising the additional step of adding an alkyl alcohol.

11. The method according to any one of claims 6 to 10, wherein the mixture is heated at 50 to 120°C and / or the heating is carried out at a pressure of 70 to 130 mbar.

12. The method according to any one of claims 6 to 11, wherein the lignocellulose-containing composition is biomass.

13. A polymer comprising as repeat units: 【Chemistry 4】 {where: R １ , R ２ , R ３ , R １０ , n, and p are as defined in claim 1; and R ５ Ha-Z-F １ - and R ６ Ha-F ２ -Z-, where Z is a hydrocarbon moiety having 0 to 10 carbon atoms, optionally 1 to 4 carbon atoms. １ ~C ４ - substituted with an alkyl group 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; Here, R ８ is H or C １ ~C ４ - is an alkyl group; and o is an integer from 2 to 10.

14. R 5 is -(CH 2 ) m C(=O)O- and R 6 is -OC(=O)(CH 2 ) m -; or R 5 is —C 6 H 4 C(═O)O— and R 6 is —OC(═O)C 6 H 4 —, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; or R 5 is —C 6 H 10 C(═O)O— and R 6 is —OC(═O)C 6 H 10 —, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; or R 5 is --(CH 2 ) m OC(═O)-- and R 6 is --C(═O)O(CH 2 ) m --; or R 5 is —C 6 H 4 OC(═O)— and R 6 is —C(═O)OC 6 H 4 —, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; or R 5 is —C 6 H 10 OC(═O)— and R 6 is —C(═O)OC 6 H 10 —, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; or R 5 is --(CH 2 ) m C(═O)NR 8 -- and R 6 is --R 8 NC(═O)(CH 2 ) m --; or R 5 is —C 6 H 4 C(═O)NR 8 — and R 6 is —R 8 NC(═O)C 6 H 4 —, in which the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; or R 5 is —C 6 H 10 C(═O)NR 8 — and R 6 is —R 8 NC(═O)C 6 H 10 —, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; or R 5 is --(CH 2 ) m R 8 NC(═O)-- and R 6 is --C(═O)NR 8 (CH 2 ) m --; or R 5 is —C 6 H 4 R 8 NC(═O)— and R 6 is —C(═O)NR 8 C 6 H 4 —, in which the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; or R 5 is -C 6 H 10 R 8 NC(=O)- and R 6 is -C(=O)NR 8 C 6 H 10 -, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; where R 8 is H or a C 1 -C 4 -alkyl group; 14. The polymer of claim 13, wherein m is an integer from 0 to 10.

15. The polymer comprises a repeat unit having the structure (III), where n is 0 and R ２ is -H, and R １ is H or CH ２ 15. The polymer of claim 13 or 14, wherein m is OH and m is 0.

16. R ５ is -C(=O)O-, and R ６ The polymer of any one of claims 13 to 15, wherein is -OC(=O)- and o is 2.

17. A method for preparing a polymer, comprising the steps of: ９ -L-R ９Ａ and reacting with a compound having the formula L is (CH ２ ) ｏ (VII), CO (VIII), and diphenyl sulfone (IX) 【Chemistry 5】 is selected from the group consisting of R ９ and R ９Ａ is -OR １１ , —OH, —NR ８ , -COOH, -COOR ４ and halogen atoms; Here, 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; Here, R ８ is H or a C 1 -C 4 -alkyl group; Here, R ４ is a C 1 -C 4 -alkyl group; and The method wherein o is an integer from 2 to 10.

18. R ９ and R ９Ａ 18. The method for preparing the polymer of claim 17, wherein:

19. L is (CH ２ ) ｏ 19. The method of claim 17 or 18, wherein the compound is (VII).

20. R ９ -L-R ９Ａ A process for preparing a polymer according to any of claims 17 or 18, wherein is bis-(4-halogenphenyl)sulfone.

21. A process for preparing a polymer according to any of claims 17 or 18, comprising the steps of: R ９ -L-R ９Ａ is an organic carbonate.

22. The method of claim 17 or 18, wherein R 9 -LR 9A is a dialkyl carbonate, a diaryl carbonate, or a cyclic carbonate.

23. The process according to any of claims 17 to 22, wherein the reaction is carried out in the presence of a catalyst and / or an initiator and / or at a temperature of from 30 to 250°C.

24. Use of a polymer according to any one of claims 13 to 16 for the production of sheets, fibres or moulded articles.

25. Use of a polymer according to any one of claims 13 to 16 as a replacement for poly(ethylene terephthalate).

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