Polymer comprising ester-imide structural unit, and preparation method therefor

Abstract

Provided are a polymer and a preparation method therefor. The polymer comprises an ester-imide structural unit of formula (I) and / or (II), and an optional structural unit of formula (III) and / or (IV) and / or (V) and / or (VI), (aa). The polymer has the properties of both a polyester and a polyimide, has a simple, green and efficient preparation process, and has industrial application prospects.

Description

Polymers containing ester-imide structural units and methods for preparing the same

[0001] The present invention claims priority from the prior application filed on July 26, 2023, entitled “A polymer comprising ester-imide structural units and a method for preparing the same” and application number 202310926011.1. The contents of the above-mentioned prior application are incorporated herein by reference. Technical Field

[0002] The present invention relates to the technical field of polymer materials and chemical engineering, and in particular to a polymer and a preparation method thereof. The polymer comprises an ester-imide structural unit. Background Art

[0003] Faced with the increasingly serious energy crisis and environmental pollution, the development of renewable resources has become an inevitable trend. With the rapid increase in human demand for biodegradable polymer materials and high-performance materials, the development of polymers derived from renewable resources has become an indispensable choice. With the rapid development of biotechnology, not only can renewable biomass resources be used to produce chemicals with the same structure as those derived from traditional petrochemical processes, which can be directly used as alternative monomers in the synthesis of polymers, such as ethylene glycol, 1,4-butanediol, ethylene, and phenol, but also novel structural compounds can be obtained for the development of new polymers, such as vanillin, furandicarboxylic acid, 2,5-pyridinedicarboxylic acid, amino acids, and amino alcohols. These novel structures give polymer materials unique properties, providing options for potential applications.

[0004] Polyesters are a class of polymer materials containing ester bonds within their repeating units and are widely used in chemical fibers, packaging, electronics, healthcare, construction, and automotive applications. Currently, only polybutylene adipate / terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), and polyhydroxyalkanoates (PHA) are considered biodegradable polyesters, which are insufficient to meet the growing demand for biodegradable, high-performance polyesters.

[0005] Currently, industrial polyester synthesis methods typically utilize condensation polymerization of dibasic acids and diols. By adjusting the structures of the dibasic acids and diols, polyester products with varying properties can be obtained. For example, aromatic polyesters, whose structures contain aromatic rings, are relatively rigid, exhibiting excellent mechanical properties and thermal stability; aliphatic polyesters, whose structures contain flexible fatty chains, exhibit excellent processing properties; and aromatic-aliphatic polyesters, which can achieve both rigidity and flexibility by adjusting the comonomers. However, the industrial polyester synthesis process inevitably involves the use of catalysts, the regulation of the ratio of raw monomers, the occurrence of side reactions, and the limited molecular weight of the produced polymer. Therefore, catalyst-free polyester synthesis methods have been developed. For example, CN110790906A and CN112831033B disclose methods for synthesizing polyesters without catalysts using an excess molar ratio of cyclic dicarboxylic acids or their cyclic anhydrides.

[0006] Polyimide, broadly speaking, refers to a class of polymer materials containing an imide ring structure within the polymer repeating unit. Polyimide exhibits excellent mechanical properties, high and low temperature resistance, chemical stability, and dielectric properties, making it widely used in aerospace, microelectronics, liquid crystal displays, and other fields. Polyimide is considered one of the polymer materials with the best overall performance, and functionalized polyimides have attracted considerable attention. Traditional polyimides suffer from poor processing properties due to their high glass transition temperature and insolubility in common organic solvents. Their thin film products are typically obtained by preparing a polyamic acid solution and then subjecting it to imidization, dehydration, and cyclization at high temperatures. Therefore, the development of new processes and materials for the synthesis of polyimides is of great research value and significance.

[0007] Polyesterimide is a novel polymer material whose backbone structure contains both ester bonds and imide rings, combining the properties of both polyester and polyimide. The present invention's one-pot synthesis of polyesterimide is simple, environmentally friendly, and offers excellent overall performance, a process previously unreported domestically or internationally.

[0008] Summary of the Invention

[0009] The present invention provides a polymer comprising an ester-imide structural unit and a method for preparing the same. The polymer can be used in fields such as engineering plastics and biodegradable plastics, has a simple preparation process, minimal pollution, and is easy to operate. The polymer exhibits excellent overall material properties and has promising industrial applications.

[0010] In one aspect of the present invention, a polymer is provided, comprising ester-imide structural units of formula (I) and / or (II), and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI),

[0011] in:

[0012] R1 is a residue of a diol containing an amino group, preferably at least one of a trivalent alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a trivalent alkyl-aryl-alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro,

[0013] R2 is a residue of an easily cyclized dibasic acid, preferably at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro,

[0014] R3 is different from R2 and is a residue of any dibasic acid, preferably at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro,

[0015] R4 is at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an -alkylene group, a cycloalkylene group, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a polyether segment or an alkylene group interrupted by one or more N atoms.

[0016] In one embodiment of the present invention, R1 is a residue of a diol containing an amino group, preferably a trivalent alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a trivalent alkyl-aryl-alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. The trivalent alkyl-aryl-alkyl group is preferably a trivalent C1-C 10 Alkyl-C6-C10 Aryl-C1-C 10 The alkyl group is preferably a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl group, and more preferably a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl group.

[0017] In the context of the present invention, halogen may be fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The alkyl group as a substituent may be a C1-C8 alkyl group, preferably a C1-C6 alkyl group, more preferably a C1-C3 alkyl group.

[0018] In a preferred embodiment of the present invention, R1 is selected from at least one of the following structures:

[0019] In the above formula, * represents the bonding site to the O atom, and ** represents the bonding site to the N atom.

[0020] In one embodiment of the present invention, R2 is a residue of an easily cyclized dibasic acid, preferably an alkylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro. The alkylene group may be C2-C 10 Alkylene, preferably C2-C6 alkylene, more preferably C2-C5 alkylene, most preferably ethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,1,2,2-tetramethylethylene, 1-phenylethylene, 1-benzylethylene, 1,1-diphenylethylene, 1,1-dibenzylethylene, 1,2-diphenylethylene, 1,2-dibenzylethylene, propylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, 1-phenylpropylene, 2-phenylpropylene, 1,2-diphenylpropylene, 2,2-diphenylpropylene or 1,3-diphenylpropylene. The alkenylene may be C2-C6 10Alkenylene, preferably C2-C6 alkenylene, more preferably C2-C3 alkenylene, most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene. Alkylene which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and which is interrupted by one or more O atoms may be interrupted by one or more O atoms, such as 1-3 oxygen atoms, such as 2-oxa-1,3-ethylene. The cycloalkylene may be C3-C8 cycloalkylene, preferably C4-C6 cycloalkylene, most preferably cyclobutylene (such as 1,2-cyclobutylene) or cyclohexylene (such as 1,6-cyclohexylene). The cycloalkenylene may be C4-C8 cycloalkenylene, preferably C4-C6 cycloalkenylene, most preferably 3-cyclohexene-1,6-diyl. The arylene may be C6-C 10 The arylene group is preferably a phenylene group, such as a 1,6-phenylene group. The heteroarylene group may be a 5-18-membered heteroaryl group containing one or more, preferably 1-3, such as 1 or 2, heteroatoms selected from N, S and O, examples of which include furanylene (e.g., 2,3-furanyl or 3,4-furanyl), pyridinylene (e.g., 2,3-pyridinyl or 3,4-pyridinyl), thienylene, pyrrolylene, imidazolylene, pyrazolylene, pyrazinylene or pyrimidinylene, preferably furanylene or pyridinylene. The cyclylene bridge group may be norbornenylene.

[0021] In one embodiment of the present invention, R3 is different from R2 and is any dibasic acid residue, for example, it can be the residue of the easily cyclized dibasic acid described above for R2; or R3 can be the residue of a dibasic acid that is not easily cyclized, and the dibasic acid that is not easily cyclized can be, for example, terephthalic acid, 2,5-furandicarboxylic acid, oxalic acid, malonic acid, 1,6-hexanediol, 1,10-decanedioic acid, or 1,18-octadecanediol. Preferably, R3 is at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. The alkylene group may be C2-C 10Alkylene, preferably C2-C6 alkylene, more preferably C2-C5 alkylene, most preferably ethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,1,2,2-tetramethylethylene, 1-phenylethylene, 1-benzylethylene, 1,1-diphenylethylene, 1,1-dibenzylethylene, 1,2-diphenylethylene, 1,2-dibenzylethylene, propylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, 1-phenylpropylene, 2-phenylpropylene, 1,2-diphenylpropylene, 2,2-diphenylpropylene or 1,3-diphenylpropylene. The alkenylene may be C2-C6 10 Alkenylene, preferably C2-C6 alkenylene, more preferably C2-C3 alkenylene, most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene. Alkylene which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and which is interrupted by one or more O atoms may be interrupted by one or more O atoms, such as 1-3 oxygen atoms, such as 2-oxa-1,3-ethylene. The cycloalkylene may be C3-C8 cycloalkylene, preferably C4-C6 cycloalkylene, most preferably cyclobutylene (such as 1,2-cyclobutylene) or cyclohexylene (such as 1,6-cyclohexylene). The cycloalkenylene may be C4-C8 cycloalkenylene, preferably C4-C6 cycloalkenylene, most preferably 3-cyclohexene-1,6-diyl. The arylene may be C6-C 10 The arylene group is preferably a phenylene group, such as a 1,6-phenylene group. The heteroarylene group may be a 5-18-membered heteroaryl group containing one or more, preferably 1-3, such as 1 or 2, heteroatoms selected from N, S and O, examples of which include furanylene (e.g., 2,3-furanyl or 3,4-furanyl), pyridinylene (e.g., 2,3-pyridinyl or 3,4-pyridinyl), thienylene, pyrrolylene, imidazolylene, pyrazolylene, pyrazinylene or pyrimidinylene, preferably furanylene or pyridinylene. The cyclylene bridge group may be norbornenylene.

[0022] R4 is an alkylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, an -alkylene-cycloalkylene-alkylene- which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, a polyether segment, or an alkylene group which is interrupted by one or more N atoms. The alkylene group may be C2-C 30 Alkylene, preferably C2-C 25 Alkylene, more preferably C2-C 20Alkylene groups include ethylene, isopropyl (e.g., 1,3-propylene), butylene (e.g., 1,4-butylene), pentylene (e.g., 1,5-pentylene), hexylene (e.g., 1,6-hexylene), heptylene (e.g., 1,7-heptylene), octylene (e.g., 1,8-octylene), decylene (e.g., 1,10-decylene), and octadecylene (e.g., 1,18-octadecylene). The cycloalkylene group may be cyclopropylene, cyclobutylene, cyclopentylene, or cyclohexylene. The polyether segment may be a polyethylene glycol segment, a polypropylene glycol segment, or a polytetramethylene glycol segment, each of which may contain 2 to 1000 repeating structural units, preferably 2 to 500 repeating structural units, more preferably 2 to 250 repeating structural units, and most preferably 2 to 100 repeating structural units. The chain of the alkylene group interrupted by one or more N atoms may be interrupted by 1-10 N atoms, more preferably 1-5 N atoms, more preferably 1-3 N atoms, and most preferably 1 N atom; wherein the N atoms are substituted by alkyl groups, such as methyl or ethyl groups. Preferably, R4 is at least one of the following structural formulas,

[0023] wherein * is a site of attachment to the rest of the molecule, x is an integer from 2 to 20, preferably an integer from 2 to 18, m is an integer from 2 to 8, preferably an integer from 2 to 6, more preferably an integer from 2 to 4, and y is an integer from 2 to 1000, preferably an integer from 2 to 500, more preferably from 2 to 250, and most preferably an integer from 2 to 100.

[0024] In the polymers of the present invention, the number of structural units of formulae (I), (II), (III), (IV), (V) and (VI) is not particularly limited and may be a number from 0 to 1000, preferably from 0 to 500, more preferably from 0 to 250, for example, 5, 10, 15, 20, 25, 30, 35, provided that the sum of the numbers of structural units of formulae (I) and (II) is at least 5, preferably at least 10, more preferably at least 15. Due to the characteristics of the polymers, this number is the average degree of polymerization and therefore may be an integer or a fraction.

[0025] In one embodiment of the present invention, in one aspect of the present invention, the polymer of the present invention comprises ester-imide structural units of formula (I) and / or (II), and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI); preferably consists of ester-imide structural units of formula (I) and / or (II), and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI). In another embodiment of the present invention, the polymer of the present invention comprises structural units of formula (I) and optionally structural units of formula (III), preferably consists of structural units of formula (I) and optionally structural units of formula (III). In another embodiment of the present invention, the polymer of the present invention comprises structural units of formula (I), optionally structural units of formula (III), optionally structural units of formula (V) and optionally structural units of formula (VI), preferably consists of structural units of formula (I), optionally structural units of formula (III), optionally structural units of formula (V) and optionally structural units of formula (VI). In another embodiment of the present invention, the polymer of the present invention comprises structural units of formula (II) and optionally structural units of formula (IV), preferably consists of structural units of formula (II) and optionally structural units of formula (IV). In another embodiment of the present invention, the polymer of the present invention comprises structural units of formula (II), optionally structural units of formula (IV), optionally structural units of formula (V) and optionally structural units of formula (VI), preferably consists of structural units of formula (II), optionally structural units of formula (IV), optionally structural units of formula (V) and optionally structural units of formula (VI).

[0026] In a preferred embodiment of the present invention, the polymer of the present invention has the structural formula shown below:

[0027] wherein m1 is 5-1000, preferably 10-500, more preferably 15-200; m2 is 0-100, preferably 0-25, more preferably 0-10; m3 is 5-1000, preferably 10-500, more preferably 15-200; m4 and m5 are each independently 0-1000, preferably 10-500, more preferably 15-200, provided that m3+m4 is at least 5, preferably is at least 10, more preferably at least 15; m6 is 0-100, preferably 0-25, more preferably 0-10, m7 is 5-1000, preferably 10-500, more preferably 15-200; m8 and m9 are each independently 0-1000, preferably 10-500, more preferably 15-200, provided that m8+m9 is at least 5, preferably at least 10, more preferably at least 15, m 10 and m 11 Each independently represents a number from 0 to 1000, preferably from 0 to 250, more preferably from 0 to 50; m12 is a number ranging from 0 to 100, preferably from 0 to 25, more preferably from 0 to 10, m 13 is 5-1000, preferably 10-500, more preferably 15-200, m 14 and m 15 Each independently represents a number of 0-1000, preferably 0-250, more preferably 0-50.

[0028] The polymer of the present invention can be a random copolymer or a block copolymer, and it can have a number average molecular weight of 3000-500000Da, preferably 8000-200000Da, more preferably 10000-100000Da, most preferably 12000-50000Da. The polymer of the present invention can have a weight average molecular weight of 6000-600000Da, preferably 9000-300000Da, more preferably 12000-120000Da, most preferably 15000-80000Da. The polymer of the present invention can have a molecular weight distribution of 1.01-8.00, preferably 1.10-5.00, more preferably 1.15-3.00, most preferably 1.20-2.00. The parameters are obtained by gel permeation chromatography (GPC) test.

[0029] In another aspect of the present invention, there is provided a method for preparing a polymer comprising ester-imide structural units of formula (I) and / or (II), and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI),

[0030] Wherein R1, R2, R3 and R4 are as defined above, and the method is selected from at least one of the following methods 1 or 2, wherein:

[0031] Method 1 includes the following steps:

[0032] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0033] In the second stage, cyclic anhydride and water are removed in the absence of a catalyst or in the presence of a catalyst to obtain a high molecular weight polymer.

[0034] Method 2 includes the following steps:

[0035] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0036] The second stage: in the absence of a catalyst or in the presence of a catalyst, a diacid (such as HOOC-R2-COOH or HOOC-R3-COOH) or / and a diol such as HO-R4-OH are added to further react;

[0037] The third stage: in the absence of a catalyst or in the presence of a catalyst, removing the cyclic anhydride and / or HO-R4-OH and / or water to obtain a high molecular weight polymer.

[0038] The method 2 is further selected from method 2-1, 2-2, 2-3 or 2-4, wherein:

[0039] Method 2-1 includes the following steps:

[0040] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0041] The second stage: in the absence of a catalyst or in the presence of a catalyst, HOOC-R2-COOH or HOOC-R3-COOH is added to further carry out esterification reaction and imide cyclization reaction to obtain a carboxyl-terminated prepolymer;

[0042] The third stage: in the absence of a catalyst or in the presence of a catalyst, the cyclic anhydride and water are removed to obtain a high molecular weight polymer;

[0043] Method 2-2 includes the following steps:

[0044] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0045] The second stage: adding catalyst and HO-R4-OH to react to obtain a hydroxyl-terminated prepolymer.

[0046] The third stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer;

[0047] Method 2-3 includes the following steps:

[0048] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0049] The second stage: adding HOOC-R2-COOH or HOOC-R3-COOH, catalyst and HO-R4-OH to react to obtain a prepolymer,

[0050] The third stage: in the presence of a catalyst, HO-R4-OH, cyclic anhydride and water are removed to obtain a high molecular weight polymer;

[0051] Methods 2-4 include the following steps:

[0052] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as raw materials to carry out esterification reaction, amidation reaction and imide cyclization reaction;

[0053] The second stage: adding HOOC-R2-COOH or HOOC-R3-COOH, further carrying out esterification reaction and imide cyclization reaction to obtain a carboxyl-terminated prepolymer, and then adding a catalyst and reacting with HO-R4-OH to obtain a hydroxyl-terminated prepolymer.

[0054] The third stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer.

[0055] The HOOC-R2-COOH is a dicarboxylic acid that readily cyclizes, i.e., a dicarboxylic acid that readily forms a cyclic anhydride in the absence of a catalyst or under catalytic conditions. Dicarboxylic acids that readily cyclize are known to those skilled in the art, for example, see CN110790906B. HOOC-R2-COOH may be selected from an alkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen or alkyl, a cycloalkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an aromatic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged cyclic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. Preferably, HOOC-R2-COOH can be selected from at least one of succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, methylmaleic acid, dimethylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, and 3,4-pyridinedicarboxylic acid. The cyclic anhydride of HOOC-R2-COOH can be preferably selected from succinic anhydride, 2-methylsuccinic anhydride, 2-phenylbutyric anhydride, 2-benzylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,3-diphenylsuccinic anhydride, 1,2-cyclosuccinic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, methylmaleic anhydride, dimethylmaleic anhydride, phthalic anhydride At least one of dihydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, 2-methylglutaric anhydride, 3-methylglutaric anhydride, 3-phenylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride and diglycolic anhydride, 2,3-furandicarboxylic anhydride, 3,4-furandicarboxylic anhydride, 2,3-pyridinedicarboxylic anhydride and 3,4-pyridinedicarboxylic anhydride.

[0056] The HO-R1(NH2)-OH is an amino-containing diol. The amino-containing diol can be selected from an alkanediolamine that is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group, or a nitro group, or an alkyl-aryl-alkanediolamine that is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group, or a nitro group. Preferably, the amino-containing diol can be selected from at least one of 3-amino-1,2-propylene glycol, 2-amino-1,3-propylene glycol, 2-amino-1,3-butanediol, 2-amino-1,4-butanediol, 2-amino-1,5-pentanediol, 3-amino-1,5-pentanediol, 5-amino-1,3-benzenedimethanol, and 2-amino-1,3-phenylenedimethanol.

[0057] The HOOC-R3-COOH can be any dibasic acid different from HOOC-R2-COOH, for example, it can be the easily cyclized dibasic acid described above for HOOC-R2-COOH; or it can be a dibasic acid that is not easily cyclized, such as terephthalic acid, 2,5-furandicarboxylic acid, oxalic acid, malonic acid, 1,6-hexanediol, 1,10-decanedioic acid, and 1,18-octadecanediol. Preferably, HOOC-R3-COOH can be selected from an alkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen or alkyl, a cycloalkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an aromatic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged cyclic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. Preferably, HOOC-R3-COOH can be selected from succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanediol, 2,2,3,3-tetramethylsuccinic acid, oxalic acid, malonic acid, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, maleic acid, methylmaleic acid, dioctadecanedioic ... 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hex At least one of methylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornenic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, terephthalic acid, and 2,5-furandicarboxylic acid.

[0058] The HO-R4-OH diol may be selected from an alkylene glycol that is unsubstituted or substituted with a substituent selected from a halogen, alkyl, or nitro group, an OH-alkylene-cycloalkylene-alkylene-OH that is unsubstituted or substituted with a substituent selected from a halogen, alkyl, or nitro group, a polyether glycol, or an alkylene glycol interrupted by one or more nitrogen atoms; preferably, at least one selected from an alkylene glycol containing 2 to 18 carbon atoms, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, N-methyldiethanolamine, and N-ethyldiethanolamine. The HO-R4-OH diol may be preferably selected from at least one selected from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,18-octadecanediol, polyethylene glycol, and 1,4-cyclohexanedimethanol.

[0059] The first and second stages are carried out in the absence of a catalyst or in the presence of a catalyst, preferably in the absence of a catalyst. The third stage, if the cyclic anhydride is removed, can be carried out in the absence of a catalyst or in the presence of a catalyst; if the glycol is removed, the third stage is carried out in the presence of a catalyst. The catalyst can be selected from at least one of aluminum chloride, ferric chloride, boron trifluoride, stannous chloride, stannous octoate, stannous isooctanoate, dibutyltin dilaurate, monobutyltin oxide, antimony trioxide, zinc oxide, isopropyl titanate, and tetrabutyl titanate. If used, the catalyst can be used in an amount of 1-2000 ppm, preferably 10-1000 ppm, based on the total weight of the reactants.

[0060] The excess molar ratio in the first stage refers to the molar ratio of (HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH) to (HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH) is (1.01 to 10):1, preferably (1.5 to 4):1.

[0061] The amidation reaction, esterification reaction and imide cyclization reaction in the first and second stages may be carried out at a temperature of 60-300° C., preferably 100-250° C., and for a reaction time of 0.1-72 hours, preferably 3-24 hours.

[0062] The first stage can be carried out in air or an inert atmosphere, for example, a nitrogen or argon atmosphere. The second stage can be carried out in an inert atmosphere, for example, a nitrogen or argon atmosphere.

[0063] The prepolymer obtained in the second stage may have a number average molecular weight of 2000-10000 Da, preferably 4000-8000 Da, a weight average molecular weight of 2500-30000 Da, preferably 5000-10000 Da, and a molecular weight distribution of 1.01-5.00, preferably 1.10-4.00, more preferably 1.15-3.00, and most preferably 1.20-2.00.

[0064] In the third stage, the carboxyl- or hydroxyl-terminated prepolymer forms anhydrides or diols through "biting back" at the ends of the molecular chain and evaporates to obtain a high molecular weight polyester. The reaction temperature in the third stage can be 150-300°C, preferably 180-250°C, and the reaction time can be 6-72 hours, preferably 6-48 hours. The vacuum degree during decompression is less than 200 Pa, preferably less than 100 Pa. The third stage is carried out under reduced pressure conditions. The purpose of the reduced pressure is to separate small molecules with relatively low boiling points, such as water, cyclic anhydrides, or diols, from the product system, promote polymer chain growth, and improve polymerization efficiency.

[0065] The first and second stages of the polymer preparation method of the present invention include the reaction process shown in the following formula:

[0066] The polymer of the present invention can have a number average molecular weight of 3000-500000Da, preferably 8000-200000Da, more preferably 10000-100000Da, most preferably 12000-50000Da. The polymer of the present invention can have a weight average molecular weight of 6000-600000Da, preferably 9000-300000Da, more preferably 12000-120000Da, most preferably 15000-80000Da. The polymer of the present invention can have a molecular weight distribution of 1.01-8.00, preferably 1.10-5.00, more preferably 1.15-3.00, most preferably 1.20-2.00. The parameters are obtained by gel permeation chromatography (GPC) test.

[0067] The polymers of the present invention can be synthesized using monomers of biological origin. As a characteristic of polymers synthesized using monomers of biological origin, the polymers of the present invention have a 14 C / 12 C ratio. Alternatively, the polymers of the present invention may also be synthesized using monomers of petroleum origin.

[0068] In one embodiment of the present invention, the polymer of the present invention can also be obtained by subjecting an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH to an amide-acid structure-containing diol represented by formula (VII) to esterification and imide cyclization to obtain a carboxyl-terminated prepolymer, followed by removal of the cyclic anhydride and water, or by reacting the prepolymer with HO-R4-OH to obtain a hydroxyl-terminated prepolymer, followed by removal of HO-R4-OH and water; or by subjecting an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH to an imide structure-containing diol represented by formula (VIII) to esterification to obtain a carboxyl-terminated prepolymer, followed by removal of the cyclic anhydride and water, or by reacting the prepolymer with HO-R4-OH to obtain a hydroxyl-terminated prepolymer, followed by removal of HO-R4-OH and water:

[0069] wherein R1, R2, R3 and R4 are as defined above.

[0070] Therefore, in another aspect of the present invention, the present invention relates to a process for preparing a polymer comprising ester-imide structural units of formula (I) and / or (II) and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI),

[0071] wherein R1, R2, R3 and R4 are as defined above, the method comprising:

[0072] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an amide-acid structure represented by formula (VII) as raw materials, and performing an esterification reaction and an imide cyclization reaction to obtain a carboxyl-terminated prepolymer;

[0073] The second stage: removing the cyclic anhydride and water in the absence of a catalyst or in the presence of a catalyst to obtain a high molecular weight polymer; or

[0074] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an amide-acid structure represented by formula (VII) as raw materials, an esterification reaction and an imide cyclization reaction are carried out to obtain a carboxyl-terminated prepolymer, and then a catalyst is added to react with HO-R4-OH to obtain a hydroxyl-terminated prepolymer.

[0075] The second stage: in the presence of a catalyst, remove HO-R4-OH and water to obtain a high molecular weight polymer; or

[0076] The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an imide structure represented by formula (VIII) as raw materials to carry out an esterification reaction to obtain a carboxyl-terminated prepolymer;

[0077] The second stage: removing the cyclic anhydride and water in the absence of a catalyst or in the presence of a catalyst to obtain a high molecular weight polymer; or

[0078] The first stage: in the absence of a catalyst or in the presence of a catalyst, an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an imide structure represented by formula (VIII) are used as raw materials to carry out an esterification reaction to obtain a carboxyl-terminated prepolymer, and then a catalyst is added to react with HO-R4-OH to obtain a hydroxyl-terminated prepolymer.

[0079] The second stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer.

[0080] The specific reaction conditions are the same as those described above for the method using diolamine monomers.

[0081] The diol containing an amide-acid structure represented by formula (VII) can be synthesized by methods known in the art. Preferably, the diol containing an amide-acid structure represented by formula (VII) can be obtained by reacting an amino-containing diol of HO-R1(NH2)-OH with an acid anhydride of HOOC-R2-COOH in an organic solvent at room temperature in the presence of a catalyst, followed by acidification with an acidifying agent.

[0082] Therefore, in another aspect of the present invention, the present invention relates to a method for preparing a diol containing an amide-acid structure represented by formula (VII), which comprises: reacting the corresponding amino diol of HO-R1(NH2)-OH with the anhydride of HOOC-R2-COOH in water or an organic solvent under the action of a catalyst, and then acidifying with an acidifying agent, wherein R1 and R2 are as defined above.

[0083] The organic solvent may be selected from esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide; dioxane; ethers such as trimethyl glycerol and dimethyl sorbitol, etc. The catalyst may be selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, triethylamine, triisopropylamine, trioctylamine, tetramethylguanidine, pyridine, piperidine, 1,8-diazacyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4.3.0]non-5-ene, etc.

[0084] The acidifying agent can be selected from, for example, hydrochloric acid, phosphoric acid, boric acid, nitric acid, sulfuric acid, acetic acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and the like.

[0085] The reaction can be carried out at a temperature of -20-100° C. Preferably, the reaction temperature is 0-50° C. The molar ratio of the amino-containing diol to the acid anhydride can be 1:5 to 5:1, preferably 1:2 to 2:1, and more preferably 1:1.

[0086] The diol containing an imide structure represented by formula (VIII) can be synthesized by methods known in the art. Preferably, the diol containing an imide structure represented by formula (VIII) can be obtained by reacting an amino-containing diol of HO-R1(NH2)-OH with an acid anhydride of HOOC-R2-COOH in an organic solvent in the presence of a catalyst.

[0087] Therefore, in another aspect of the present invention, the present invention relates to a method for preparing a diol containing an imide structure shown in formula (VIII), which comprises: reacting the corresponding HO-R1(NH2)-OH amino diol with the HOOC-R2-COOH anhydride in water or an organic solvent under the action of a catalyst, wherein R1 and R2 are as defined above.

[0088] The organic solvent may be selected from esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide; dioxane; ethers such as trimethyl glycerol and dimethyl sorbitol, etc. The catalyst may be selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, triethylamine, triisopropylamine, trioctylamine, tetramethylguanidine, pyridine, piperidine, 1,8-diazacyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4.3.0]non-5-ene, etc.

[0089] The reaction may be carried out at a temperature of 0-200° C. Preferably, the reaction temperature is 80-150° C. The molar ratio of the amino-containing diol to the acid anhydride may be 1:5 to 5:1, preferably 1:2 to 2:1, and more preferably 1:1.

[0090] When HOOC-R2-COOH is succinic acid, the diol containing an imide structure represented by formula (VIII) is a structure represented by the following formula:

[0091] It can be achieved through Obtained by hydrogenation of double bonds.

[0092] The hydrogenation conditions are selected from methods known in the art. Preferably, the double bond hydrogenation reaction can be carried out using Ru / C (5 wt% Ru loading) catalyst, tetrahydrofuran solvent, 10-100 bar hydrogen pressure, and room temperature reaction conditions.

[0093] The polymer material protected by the present invention has the following characteristics:

[0094] 1. The monomer raw materials are derived from biomass resources. For example, 3-amino-1,2-propanediol and 2-amino-1,3-propanediol can be derived from glycerol, and succinic acid can be obtained by biological fermentation. They are green polymer materials.

[0095] 2. The sources of raw materials are diverse, including amino diols, diols, easily cyclized dibasic acids, and dibasic acids with a wide range of selectivity.

[0096] 3. The polymer structure is diverse and has adjustable properties, and rigid aromatic structures or flexible aliphatic structures can be introduced.

[0097] 4. The polymer synthesized by the present invention has the properties of both polyester and polyimide, and has melt processing properties and high and low temperature resistance.

[0098] 5. The polymerization process provided by the present invention is simple, green and environmentally friendly, has high polymerization efficiency, and has broad industrial application prospects.

[0099] The polymer of the present invention can be degraded and can be used as degradable plastics. In addition, it can also be used in the fields of optoelectronic materials, engineering plastics, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] FIG1 is a comparison diagram of H NMR spectra during the reaction process of Example 1.

[0101] FIG2 is a hydrogen NMR spectrum of the prepolymer of Example 1.

[0102] FIG3 is a hydrogen nuclear magnetic spectrum of the product removed under reduced pressure in Example 1.

[0103] FIG4 is an infrared spectrum of the target product prepared in Example 1.

[0104] FIG5 is a hydrogen NMR spectrum of the target product prepared in Example 1.

[0105] FIG6 is a carbon NMR spectrum of the target product prepared in Example 1.

[0106] FIG7 is a TGA test curve of the target product prepared in Example 1.

[0107] FIG8 is a DSC test curve of the target product prepared in Example 1.

[0108] FIG9 is a comparison chart of the GPC test curves of the target products prepared in Examples 2, 3, 4, 5, 9 and 11.

[0109] Figure 10 is the H NMR spectrum of the target product prepared in Example 12.

[0110] FIG11 is a comparison diagram of the GPC test curves of the target products prepared in Examples 1, 15 and 16.

[0111] Figure 12 is the H-NMR spectrum of the target product prepared in Example 17.

[0112] Figure 13 is the H-NMR spectrum of the target product prepared in Example 18.

[0113] Figure 14 is the H-NMR spectrum of the target product prepared in Example 19.

[0114] Figure 15 is the H-NMR spectrum of the target product prepared in Example 20.

[0115] Figure 16 is the H-NMR spectrum of the target product prepared in Example 21.

[0116] Figure 17 is the H-NMR spectrum of the target product prepared in Example 23.

[0117] Figure 18 is the H-NMR spectrum of the target product prepared in Example 24.

[0118] Figure 19 is the H-NMR spectrum of the target product prepared in Example 25.

[0119] Figure 20 is the H-NMR spectrum of the target product prepared in Example 28.

[0120] Figure 21 is the H-NMR spectrum of the target product prepared in Example 29.

[0121] Figure 22 is the NMR carbon spectrum of the target product prepared in Example 29.

[0122] Figure 23 is the H-NMR spectrum of the target product prepared in Example 30.

[0123] Figure 24 is the NMR carbon spectrum of the target product prepared in Example 30.

[0124] Figure 25 is the H-NMR spectrum of the target product prepared in Example 31.

[0125] Figure 26 is the H-NMR spectrum of the target product prepared in Example 32.

[0126] Figure 27 is the H-NMR spectrum of the target product prepared in Example 33.

[0127] Figure 28 is the H NMR spectrum of the target product prepared in Example 34.

[0128] Figure 29 is the H NMR spectrum of the target product prepared in Example 35.

[0129] Figure 30 is the H NMR spectrum of the target product prepared in Example 36.

[0130] FIG31 is a comparison of H NMR spectra of the target products prepared in Examples 37 to 41.

[0131] Figure 32 is the H-NMR spectrum of the target product prepared in Example 42.

[0132] Figure 33 is the H NMR spectrum of the target product prepared in Example 43. DETAILED DESCRIPTION

[0133] The following specific embodiments are provided to help understand the present invention, but these embodiments do not limit the scope of the present invention.

[0134] Example 1

[0135] 3-Amino-1,2-propanediol (40 mmol) and succinic acid (88 mmol) were added to a 150 mL three-necked flask, mechanically stirred, and heated to 180°C under nitrogen to carry out esterification and imide cyclization reactions. Water vapor was observed at the outlet in the initial stage of the reaction. The reaction was carried out for 16 hours to obtain a succinic acid-terminated prepolymer. The nitrogen was turned off, and an oil pump was used to evacuate the mixture to a vacuum degree of less than 100 Pa. The temperature was gradually raised to 220°C and the reaction was completed after 16 hours. During the reaction, white solids were observed adhering to the vacuum inlet. Gel permeation chromatography (GPC) analysis showed that the number average molecular weight of the prepolymer was 7575 Da, the weight average molecular weight was 9318 Da, and the molecular weight distribution was 1.23. The number average molecular weight of the final polycondensation product was 22311 Da, the weight average molecular weight was 29161 Da, and the molecular weight distribution was 1.31.

[0136] Figure 1 shows a comparison of H NMR spectra during the reaction of this example. Samples were taken at 10 min, 30 min, 60 min, 120 min, 180 min, 240 min, and 360 min, respectively, and H NMR spectra were measured using DMSO-d6 as solvent. The chemical shift of 7.8 to 7.9 ppm represents the amide bond hydrogen proton peak in the reaction system. As the reaction time increases, the amide bond hydrogen proton peak gradually disappears during the reaction. Combined with the H NMR spectrum of the prepolymer in Figure 2, it can be seen that the following reaction process exists during the reaction:

[0137] Figure 2 is the H NMR spectrum of the prepolymer. In the spectrum, the hydrogen proton chemical shift peak of the carboxyl group can be clearly observed, while the hydrogen proton chemical shift peak of the amide group and the hydrogen proton chemical shift peak of 3-amino-1,2-propanediol are not observed, indicating that 3-amino-1,2-propanediol is completely reacted to obtain a succinic acid-terminated prepolymer.

[0138] Figure 3 is the H-NMR spectrum of the white solid attachment, indicating that the substance is succinic anhydride, indicating that succinic anhydride is included in the components removed during the polycondensation stage.

[0139] FIG4 is an infrared spectrum of the target product prepared in this example.

[0140] FIG5 and FIG6 are respectively the H-NMR spectrum and C-NMR spectrum of the target product prepared in this example.

[0141] FIG7 and FIG8 are TGA and DSC test curves of the target product prepared in this example, respectively.

[0142] Examples 2 to 7

[0143] The synthesis steps are the same as those in Example 1, except that the feed ratio of 3-amino-1,2-propanediol and succinic acid is replaced with 1:2 (Example 2), 1:2.1 (Example 3), 1:2.3 (Example 4), 1:2.4 (Example 5), 1:2.5 (Example 6) and 1:3 (Example 7) in sequence.

[0144] The target product obtained in Example 2 has a number average molecular weight of 13767 Da, a weight average molecular weight of 17453 Da, and a molecular weight distribution of 1.27.

[0145] The target product obtained in Example 3 has a number average molecular weight of 18138 Da, a weight average molecular weight of 25008 Da, and a molecular weight distribution of 1.38.

[0146] The target product obtained in Example 4 had a number average molecular weight of 21799 Da, a weight average molecular weight of 28718 Da, and a molecular weight distribution of 1.32.

[0147] The target product obtained in Example 5 has a number average molecular weight of 21829 Da, a weight average molecular weight of 32102 Da, and a molecular weight distribution of 1.47.

[0148] The target product obtained in Example 6 had a number average molecular weight of 22103 Da, a weight average molecular weight of 32831 Da, and a molecular weight distribution of 1.49.

[0149] The target product obtained in Example 7 has a number average molecular weight of 21089 Da, a weight average molecular weight of 34006 Da, and a molecular weight distribution of 1.61.

[0150] Examples 8 to 11

[0151] The synthesis steps are the same as those in Example 1, except that the reaction temperature in the prepolymerization stage is replaced with 140°C (Example 8), 160°C (Example 9), 200°C (Example 10) and 220°C (Example 11) in sequence.

[0152] The target product obtained in Example 8 had a number average molecular weight of 15410 Da, a weight average molecular weight of 19379 Da, and a molecular weight distribution of 1.26.

[0153] The target product obtained in Example 9 had a number average molecular weight of 18162 Da, a weight average molecular weight of 24020 Da, and a molecular weight distribution of 1.32.

[0154] The target product obtained in Example 10 had a number average molecular weight of 19079 Da, a weight average molecular weight of 25610 Da, and a molecular weight distribution of 1.34.

[0155] The target product obtained in Example 11 had a number average molecular weight of 17512 Da, a weight average molecular weight of 22106 Da, and a molecular weight distribution of 1.26.

[0156] FIG9 is a comparison chart of the GPC test curves of the target products prepared in Examples 2, 3, 4, 5, 9 and 11.

[0157] Example 12

[0158] The synthesis steps were the same as in Example 1, except that the reaction time in the prepolymerization stage was changed to 3 hours. The target product obtained had a number average molecular weight of 12,670 Da, a weight average molecular weight of 17,358 Da, and a molecular weight distribution of 1.37. The H-NMR spectrum results in Figure 10 indicate the presence of an amide bond in the product structure.

[0159] Example 13

[0160] The synthesis steps were the same as those in Example 1, except that the reaction time in the prepolymerization stage was changed to 24 hours. The target product obtained had a number average molecular weight of 22038 Da, a weight average molecular weight of 30096 Da, and a molecular weight distribution of 1.36.

[0161] Example 14

[0162] The synthesis steps were the same as in Example 1, except that the reaction time of the polycondensation stage was changed to 48 hours. The target product obtained had a number average molecular weight of 23048 Da, a weight average molecular weight of 30189 Da, and a molecular weight distribution of 1.31.

[0163] Examples 15-16

[0164] The synthesis steps were the same as those in Example 1, except that 10 mg of antimony trioxide (Example 15) and 2 mg of tetrabutyl titanate (Example 16) were added during the polycondensation stage.

[0165] The target product obtained in Example 15 has a number average molecular weight of 31684 Da, a weight average molecular weight of 43152 Da, and a molecular weight distribution of 1.36.

[0166] The target product obtained in Example 16 had a number average molecular weight of 32271 Da, a weight average molecular weight of 50697 Da, and a molecular weight distribution of 1.57.

[0167] FIG11 is a comparison diagram of the GPC test curves of the target products prepared in Examples 1, 15 and 16.

[0168] Examples 17 to 22

[0169] The synthesis steps are the same as those in Example 1, except that 3-amino-1,2-propanediol is replaced by 2-amino-1,3-propanediol (Example 17), 2-amino-2-methyl-1,3-propanediol (Example 18), 2-amino-1,3-butanediol (Example 19), 2-amino-1,4-butanediol (Example 20), 2-amino-1,5-pentanediol (Example 21), and 5-amino-1,3-benzenedimethanol (Example 22).

[0170] The target product obtained in Example 17 has a number average molecular weight of 31938 Da, a weight average molecular weight of 58389 Da, and a molecular weight distribution of 1.83. FIG12 is a hydrogen NMR spectrum of the target product prepared in Example 17.

[0171] The target product obtained in Example 18 has a number average molecular weight of 29705 Da, a weight average molecular weight of 50381 Da, and a molecular weight distribution of 1.70. FIG13 is a hydrogen NMR spectrum of the target product prepared in Example 18.

[0172] The target product obtained in Example 19 has a number average molecular weight of 28630 Da, a weight average molecular weight of 50271 Da, and a molecular weight distribution of 1.76. FIG14 is a hydrogen NMR spectrum of the target product prepared in Example 19.

[0173] The target product obtained in Example 20 has a number average molecular weight of 41269 Da, a weight average molecular weight of 68370 Da, and a molecular weight distribution of 1.66. FIG15 is a hydrogen NMR spectrum of the target product prepared in Example 20.

[0174] The target product obtained in Example 21 has a number average molecular weight of 38670 Da, a weight average molecular weight of 61392 Da, and a molecular weight distribution of 1.59. FIG16 is a hydrogen NMR spectrum of the target product prepared in Example 21.

[0175] The target product obtained in Example 22 has a number average molecular weight of 23271 Da, a weight average molecular weight of 44380 Da, and a molecular weight distribution of 1.91.

[0176] Examples 23 to 26

[0177] The synthesis steps are the same as those in Example 1, except that 3-amino-1,2-propanediol is replaced by 2-amino-1,3-propanediol, and succinic acid is replaced by 2-methylsuccinic acid (Example 23), 2-phenylsuccinic acid (Example 24), 2,2-dimethylsuccinic acid (Example 25), and phthalic acid (Example 26) in sequence.

[0178] The target product obtained in Example 23 has a number average molecular weight of 39266 Da, a weight average molecular weight of 67536 Da, and a molecular weight distribution of 1.72. FIG17 is a hydrogen NMR spectrum of the target product prepared in Example 23.

[0179] The target product obtained in Example 24 has a number average molecular weight of 39683 Da, a weight average molecular weight of 60709 Da, and a molecular weight distribution of 1.53. FIG18 is a hydrogen NMR spectrum of the target product prepared in Example 24.

[0180] The target product obtained in Example 25 has a number average molecular weight of 41603 Da, a weight average molecular weight of 62369 Da, and a molecular weight distribution of 1.50. FIG19 is a hydrogen NMR spectrum of the target product prepared in Example 25.

[0181] The target product obtained in Example 26 has a number average molecular weight of 40359 Da, a weight average molecular weight of 61950 Da, and a molecular weight distribution of 1.53.

[0182] Examples 27-28

[0183] The synthesis steps are the same as those in Example 1, except that 3-amino-1,2-propanediol is replaced by 2-amino-1,3-propanediol, and succinic acid is replaced by succinic anhydride (Example 27) and phthalic anhydride (Example 28) in sequence.

[0184] The target product obtained in Example 27 has a number average molecular weight of 38352 Da, a weight average molecular weight of 63966 Da, and a molecular weight distribution of 1.67.

[0185] The target product obtained in Example 28 has a number average molecular weight of 25401 Da, a weight average molecular weight of 32407 Da, and a molecular weight distribution of 1.28.

[0186] Figure 20 is the H-NMR spectrum of the target product prepared in Example 28.

[0187] Example 29

[0188] 3-Amino-1,2-propanediol (50 mmol), 1,4-butanediol (50 mmol), and succinic acid (160 mmol) were added to a 150 mL three-necked flask, mechanically stirred, and heated to 180°C under nitrogen to carry out esterification and imide cyclization reactions. In the initial stage of the reaction, water vapor can be observed at the outlet. The reaction was carried out for 16 hours to obtain a succinic acid-terminated prepolymer. Turn off the nitrogen, use an oil pump to evacuate the air to a vacuum degree of less than 100 Pa, gradually raise the temperature to 240°C, and react for 24 hours. During the reaction, a white solid can be observed adhering to the vacuum inlet. The number average molecular weight of the final polycondensation product obtained by gel permeation chromatography (GPC) test is 36670 Da, the weight average molecular weight is 55560 Da, and the molecular weight distribution is 1.52.

[0189] Figures 21 and 22 are respectively the H-NMR spectrum and C-NMR spectrum of the target product prepared in this example.

[0190] Example 30

[0191] The synthesis steps were the same as those in Example 29, except that 1,4-butanediol was replaced with an equal molar amount of 1,4-cyclohexanedimethanol. The target product obtained had a number average molecular weight of 36419 Da, a weight average molecular weight of 48560 Da, and a molecular weight distribution of 1.33.

[0192] FIG23 is a hydrogen NMR spectrum of the target product prepared in this example.

[0193] FIG24 is a carbon-NMR spectrum of the target product prepared in this example.

[0194] Example 31

[0195] 2-Amino-1,3-propanediol (40 mmol) and succinic acid (65 mmol) were added to a 150 mL three-necked flask, mechanically stirred, and reacted at 100°C for 1 hour. Terephthalic acid (20 mmol) was added, the temperature was raised to 160°C, and the reaction was carried out under nitrogen for 10 hours. The temperature was raised to 200°C and the reaction was continued under nitrogen for 16 hours to obtain a prepolymer with a carboxyl end group. The nitrogen was turned off, and an oil pump was used to evacuate the mixture to a vacuum degree of less than 100 Pa. The temperature was raised by 10°C every 4 hours from 200°C to 260°C. The number average molecular weight of the polymer obtained by gel permeation chromatography (GPC) was 27080 Da, the weight average molecular weight was 46306 Da, and the molecular weight distribution was 1.71.

[0196] FIG25 is a hydrogen NMR spectrum of the target product prepared in this example.

[0197] Examples 32 to 34

[0198] The synthesis steps are the same as those in Example 30, except that terephthalic acid is replaced by 20 mmol of oxalic acid (Example 32), 20 mmol of 1,6-hexanediol (Example 33), and 20 mmol of 1,10-decanedioic acid (Example 34).

[0199] The target product obtained in Example 32 has a number average molecular weight of 25308 Da, a weight average molecular weight of 41506 Da, and a molecular weight distribution of 1.64. FIG26 is a H NMR spectrum of the target product prepared in Example 32.

[0200] The target product obtained in Example 33 has a number average molecular weight of 29481 Da, a weight average molecular weight of 47169 Da, and a molecular weight distribution of 1.60. FIG27 is a hydrogen NMR spectrum of the target product prepared in Example 33.

[0201] The target product obtained in Example 34 has a number average molecular weight of 32096 Da, a weight average molecular weight of 54242 Da, and a molecular weight distribution of 1.69. FIG28 is a hydrogen NMR spectrum of the target product prepared in Example 34.

[0202] Example 35

[0203] 2-Amino-1,3-propanediol (40 mmol), ethylene glycol (20 mmol), and succinic acid (90 mmol) were added to a 150 mL three-necked flask with mechanical stirring. The mixture was reacted at 100°C for 1 hour. Terephthalic acid (20 mmol) was added, the temperature was raised to 160°C, and the reaction was continued under nitrogen for 10 hours. The temperature was then raised to 200°C and the reaction was continued under nitrogen for 16 hours to obtain a prepolymer with carboxyl end groups. The nitrogen was turned off, and an oil pump was used to evacuate the mixture to a vacuum of less than 100 Pa. The temperature was raised by 10°C every 4 hours from 200°C to 260°C. Gel permeation chromatography (GPC) analysis showed that the number average molecular weight of the polymer was 25061 Da, the weight average molecular weight was 46864 Da, and the molecular weight distribution was 1.87.

[0204] Figure 29 is the H NMR spectrum of the target product prepared in Example 35.

[0205] Example 36

[0206] 2-Amino-1,3-propanediol (20 mmol), 1,4-butanediol (40 mmol), and succinic acid (70 mmol) were added to a 150 mL three-necked flask, mechanically stirred, and reacted at 100°C for 10 minutes. 1,6-hexanediol (20 mmol) was added, the temperature was raised to 160°C, and the reaction was continued under nitrogen for 10 hours. The temperature was raised to 200°C and the reaction was continued under nitrogen for 16 hours to obtain a prepolymer with carboxyl end groups. The nitrogen was turned off, and an oil pump was used to evacuate the mixture to a vacuum degree of less than 100 Pa. Starting from 200°C, the temperature was raised by 10°C every 4 hours to 260°C. Gel permeation chromatography (GPC) test showed that the number average molecular weight of the polymer was 31078 Da, the weight average molecular weight was 49414 Da, and the molecular weight distribution was 1.59.

[0207] Figure 30 is the H NMR spectrum of the target product prepared in Example 36.

[0208] Example 37

[0209] 3-Amino-1,2-propanediol (10 mmol) and succinic acid (110 mmol) were added to a 150 mL three-necked flask with mechanical stirring. The mixture was heated to 150°C under nitrogen atmosphere for amidation, imidization, and esterification reactions. H NMR spectroscopy was performed until the chemical shift of the active amine hydrogen was no longer observed at 8-9 ppm, indicating the imidization reaction was complete. Ethylene glycol (100 mmol) and zinc acetate (200 mg) were further added. When the water removal from the system approached the theoretical value, isopropyl titanate (1 mL) was added. The reaction was continued at 160°C for 6 hours. The nitrogen was turned off, and vacuum was applied using an oil pump to a vacuum of less than 100 Pa. The temperature was gradually increased to 220°C, and the reaction was continued for 8 hours. This yielded a block copolymer with 10 mol% imide repeating units. Gel permeation chromatography (GPC) analysis revealed that the final polycondensation product had a number average molecular weight of 31,060 Da, a weight average molecular weight of 65,280 Da, and a molecular weight distribution of 2.10.

[0210] Examples 38 to 41

[0211] The synthesis steps are the same as those in Example 37, except for the amounts of 3-amino-1,2-propanediol, succinic acid, and ethylene glycol used.

[0212] In Example 38, the amounts of 3-amino-1,2-propanediol, succinic acid, and ethylene glycol were 30 mmol, 130 mmol, and 80 mmol, respectively, to produce a block copolymer in which the imide repeating unit accounted for 30 mol%. Gel permeation chromatography (GPC) analysis revealed a number average molecular weight of 25,080 Da, a weight average molecular weight of 54,160 Da, and a molecular weight distribution of 2.16.

[0213] In Example 39, the amounts of 3-amino-1,2-propanediol, succinic acid, and ethylene glycol were 50 mmol, 150 mmol, and 56 mmol, respectively, to produce a block copolymer in which the imide repeating unit accounted for 50 mol%. Gel permeation chromatography (GPC) analysis revealed a number average molecular weight of 20,270 Da, a weight average molecular weight of 50,350 Da, and a molecular weight distribution of 2.48.

[0214] In Example 40, the amounts of 3-amino-1,2-propanediol, succinic acid, and ethylene glycol were 70 mmol, 170 mmol, and 35 mmol, respectively, to produce a block copolymer in which the imide repeating units accounted for 70 mol%. Gel permeation chromatography (GPC) analysis revealed a number average molecular weight of 21,050 Da, a weight average molecular weight of 48,300 Da, and a molecular weight distribution of 2.29.

[0215] In Example 41, the amounts of 3-amino-1,2-propanediol, succinic acid, and ethylene glycol were 90 mmol, 190 mmol, and 12 mmol, respectively, to produce a block copolymer in which the imide repeating units accounted for 90 mol%. Gel permeation chromatography (GPC) analysis revealed a number average molecular weight of 13,600 Da, a weight average molecular weight of 32,030 Da, and a molecular weight distribution of 2.36.

[0216] FIG31 is a comparison of H NMR spectra of the target products prepared in Examples 37 to 41.

[0217] Example 42

[0218] 5-Amino-1,3-benzenedimethanol (10 mmol) and succinic acid (110 mmol) were added to a 150 mL three-necked flask with mechanical stirring. Under nitrogen, the temperature was raised to 150°C for amidation, imidization, and esterification reactions. H-NMR spectroscopy was performed until no active hydrogen of the amine was observed at a chemical shift of 8-9 ppm, indicating the completion of the imidization reaction. 1,4-Butanediol (100 mmol) and zinc acetate (200 mg) were further added. Isopropyl titanate (1 mL) was added until the system had eliminated nearly the theoretical amount of water. The reaction was continued at 160°C for 6 hours. The nitrogen was then turned off, and an oil pump was used to evacuate the system to a vacuum of less than 100 Pa. The temperature was then gradually raised to 240°C and the reaction was continued for 12 hours to obtain a block copolymer in which the imide repeating unit accounted for 10 mol%. The number average molecular weight of the final polycondensation product obtained by gel permeation chromatography (GPC) test was 14022 Da, the weight average molecular weight was 35475 Da, and the molecular weight distribution was 2.53.

[0219] Figure 32 is the H-NMR spectrum of the target product prepared in Example 42.

[0220] Example 43

[0221] 2-Amino-1,3-propanediol (20 mmol) and succinic acid (90 mmol) were added to a 150 mL three-necked flask, and the mixture was mechanically stirred. The temperature was raised to 150°C under nitrogen atmosphere to carry out amidation, imidization and esterification reactions. H NMR tracking detection was performed until the chemical shift reached 8-9 ppm and no active hydrogen of the amine could be observed, indicating that the imidization reaction was complete. 2,5-Furandicarboxylic acid (10 mmol), 1,4-butanediol (100 mmol), and zinc acetate (200 mg) were further added. When the water removal from the system was close to the theoretical value, isopropyl titanate (1.5 ml) was added. The reaction was continued at 160°C for 8 hours. The nitrogen was turned off and an oil pump was used to evacuate the mixture to a vacuum of less than 100 Pa. The temperature was gradually raised to 240°C and the reaction was completed for 16 hours to obtain a block copolymer in which the repeating units of imide accounted for 20 mol%, the repeating units of furandicarboxylic acid butylene glycol accounted for 10 mol%, and the repeating units of butylene glycol succinate accounted for 70 mol%. The final polycondensation product was tested by gel permeation chromatography (GPC) to obtain a number average molecular weight of 23050 Da, a weight average molecular weight of 52190 Da, and a molecular weight distribution of 2.26.

[0222] Figure 33 is the H NMR spectrum of the target product prepared in Example 43.

[0223] Example 44

[0224] 2-Amino-1,3-propanediol (20 mmol), 1,4-butanediol (2 mmol) and succinic acid (42 mmol) were added to a 150 mL three-necked flask and mechanically stirred. The temperature was raised to 150°C under nitrogen atmosphere to carry out amidation, imidization and esterification reactions. H NMR tracking detection was performed until the chemical shift reached 8-9 ppm and no active hydrogen of the amine could be observed, indicating that the imidization reaction was complete. Further, succinic acid (48 mmol), 2,5-furandicarboxylic acid (10 mmol), 1,4-butanediol (100 mmol), and zinc acetate (200 mg) were added. When the water removal from the system was close to the theoretical value, isopropyl titanate (1.5 ml) was added. The reaction was continued at 160°C for 8 hours. The nitrogen was turned off and an oil pump was used to evacuate the mixture to a vacuum degree of less than 100 Pa. The temperature was gradually raised to 240°C and the reaction was completed for 16 hours to obtain a block copolymer in which the repeating units of imide accounted for 20 mol%, the repeating units of furandicarboxylic acid butylene glycol accounted for 10 mol%, and the repeating units of succinate butylene glycol accounted for 70 mol%. The final polycondensation product was tested by gel permeation chromatography (GPC) to obtain a number average molecular weight of 26180 Da, a weight average molecular weight of 55360 Da, and a molecular weight distribution of 2.11.

[0225] Example 45

[0226] 2-Amino-1,3-propanediol (20 mmol) and succinic acid (25 mmol) were added to a 150 mL three-necked flask with mechanical stirring. The mixture was heated to 150°C under nitrogen to allow partial amidation, imidization, and esterification to proceed. The reaction was allowed to proceed for 1 hour, followed by the addition of 2,5-furandicarboxylic acid (10 mmol) and succinic acid (65 mmol). The reaction was continued. The absence of active amine hydrogens by H NMR spectroscopy at a chemical shift of 8-9 ppm indicated the complete imidization reaction. 1,4-Butanediol (100 mmol) and zinc acetate (200 mg) were further added. When the water removal from the system was close to the theoretical value, isopropyl titanate (1.5 ml) was added. The reaction was continued at 160°C for 8 hours. The nitrogen was turned off and an oil pump was used to evacuate the mixture to a vacuum of less than 100 Pa. The temperature was gradually increased to 240°C and the reaction was completed for 16 hours to obtain a block copolymer in which the repeating units of imide accounted for 20 mol%, the repeating units of furandicarboxylic acid butylene glycol accounted for 10 mol%, and the repeating units of butylene glycol succinate accounted for 70 mol%. The final polycondensation product was tested by gel permeation chromatography (GPC) and had a number average molecular weight of 18,350 Da, a weight average molecular weight of 47,280 Da, and a molecular weight distribution of 2.58.

Claims

1. A polymer comprising ester-imide structural units of formula (I) and / or (II) and optionally structural units of formula (III) and / or (IV) and / or (V) and / or (VI), in: R1 is a residue of a diol containing an amino group, preferably at least one of a trivalent alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a trivalent alkyl-aryl-alkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, R2 is a residue of an easily cyclizable dibasic acid, preferably at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, R3 is different from R2 and is the residue of any dibasic acid, for example, it is the residue of the easily cyclizable dibasic acid described above for R2; or R2 is the residue of a dibasic acid that is not easily cyclizable, and the dibasic acid that is not easily cyclizable may be, for example, terephthalic acid or sebacic acid; preferably, R3 is an alkylene group that is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, and an alkylene group that is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, at least one of an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, R4 is an alkylene group which is unsubstituted or substituted by a substituent selected from halogen, alkyl or nitro, Or at least one of -alkylene-cycloalkylene-alkylene-substituted by a substituent selected from halogen, alkyl or nitro, a polyether segment or an alkylene segment interrupted by one or more N atoms.

2. The polymer of claim 1, wherein the trivalent alkyl-aryl-alkyl group in the definition of R1 is a trivalent C1-C 10 Alkyl-C6-C 10 Aryl-C1-C 10 Alkyl, preferably a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl, more preferably a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl, Preferably, R1 is selected from at least one of the following structures: In the above formula, * represents the connection site with the O atom, ** represents the connection site with the N atom; and / or The alkylene group in the definition of R2 is C2-C 10 The alkylene group is preferably a C2-C6 alkylene group, more preferably a C2-C5 alkylene group, and most preferably an ethylene group, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,1,2,2-tetramethylethylene, 1-phenylethylene, 1-benzylethylene, 1,1-diphenylethylene, 1,1-dibenzylethylene, 1,2-diphenylethylene, 1,2-dibenzylethylene, propylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, 1-phenylpropylene, 2-phenylpropylene, 1,2-diphenylpropylene, 2,2-diphenylpropylene or 1,3-diphenylpropylene; the alkenylene group in the definition of R2 is C2-C6 10 Alkenylene, preferably C2-C6 alkenylene, more preferably C2-C3 alkenylene, most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene; the alkylene group in the definition of R2, which is unsubstituted or substituted by a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, is interrupted by 1-3 oxygen atoms, for example 2-oxa-1,3-ethylene; The cycloalkylene group in the definition of R2 is C3-C8 cycloalkylene group, preferably C4-C6 cycloalkylene group, and most preferably cyclobutylene or cyclohexylene group; the cycloalkenylene group in the definition of R2 can be C4-C8 cycloalkenylene group, preferably C4-C6 cycloalkenylene group, and most preferably 3-cyclohexene-1,6-diyl; the arylene group in the definition of R2 is C6-C 10 Arylene, preferably phenylene, such as 1,6-phenylene; the bridging ring group in the definition of R2 is norbornene; and / or The alkylene group in the definition of R3 is C2-C 10 The alkylene group is preferably a C2-C6 alkylene group, more preferably a C2-C5 alkylene group, and most preferably an ethylene group, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,1,2,2-tetramethylethylene, 1-phenylethylene, 1-benzylethylene, 1,1-diphenylethylene, 1,1-dibenzylethylene, 1,2-diphenylethylene, 1,2-dibenzylethylene, propylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, 1-phenylpropylene, 2-phenylpropylene, 1,2-diphenylpropylene, 2,2-diphenylpropylene or 1,3-diphenylpropylene; the alkenylene group in the definition of R2 is C2-C6 10 The alkenylene group is preferably a C2-C6 alkenylene group, more preferably a C2-C3 alkenylene group, and most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene group; the alkylene group in the definition of R2, which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, is interrupted by 1-3 oxygen atoms, such as 2-oxa-1,3-ethylene; the cycloalkylene group in the definition of R2 is a C3-C8 cycloalkylene group, preferably a C4-C6 cycloalkylene group, and most preferably a cyclobutylene or cyclohexylene group; the cycloalkenylene group in the definition of R2 may be a C4-C8 cycloalkenylene group, preferably a C4-C6 cycloalkenylene group, and most preferably a 3-cyclohexene-1,6-diyl group; the arylene group in the definition of R2 is a C6-C 10 Arylene, preferably phenylene, such as 1,6-phenylene; the bridging ring group in the definition of R2 is norbornene; and / or The alkylene group in the definition of R4 is C2-C 30 Alkylene, preferably C2-C 25 Alkylene, more preferably C2-C 20 The alkylene group is an alkylene group, such as ethylene, isopropyl, butylene, pentylene, hexylene, heptylene, octylene, decylene, and octadecylene; the cycloalkylene group in the definition of R3 is cyclopropylene, cyclobutylene, cyclopentylene, or cyclohexylene; the polyether segment in the definition of R3 is a polyethylene glycol segment, a polypropylene glycol segment, or a polytetrahydrofurandiol segment, each of which contains 2 to 1000 repeating structural units, preferably 2 to 500 repeating structural units, more preferably 2 to 250 repeating structural units, and most preferably 2 to 100 repeating structural units; the alkylene group in the definition of R3, which is separated by one or more N atoms, is separated by 1 to 10 N atoms, more preferably 1 to 5 N atoms, more preferably 1 to 3 N atoms, and most preferably 1 N atom; preferably, R3 is at least one of the following structural formulas, wherein * is a connection site with other parts of the molecule, x is an integer of 2-20, preferably an integer of 2-18, m is an integer of 2-8, preferably an integer of 2-6, more preferably an integer of 2-4, y is an integer of 2-1000, preferably an integer of 2-500, more preferably an integer of 2-250, and most preferably an integer of 2-100.

3. The polymer according to claim 1 or 2, having a 14 C / 12 C ratio; or the polymer is synthesized using monomers derived from petroleum.

4. A method for preparing a polymer comprising an ester-imide structural unit of formula (I) and / or (II) and optionally a structural unit of formula (III) and / or (IV) and / or (V) and / or (VI), Wherein R1, R2, R3 and R4 are as defined in claim 1 or 2, the method comprising: The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as a raw material to carry out esterification reaction, amidation reaction and imide cyclization reaction; In the second stage, in the absence of a catalyst or in the presence of a catalyst, the cyclic anhydride and water are removed to obtain a high molecular weight polymer; or, The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or A mixture of HO-R1(NH2)-OH and HO-R4-OH is used as a raw material to carry out esterification, amidation and imide cyclization reactions; The second stage: in the absence of a catalyst or in the presence of a catalyst, a diacid (such as HOOC-R2-COOH or HOOC-R3-COOH) or / and a diol such as HO-R4-OH are added to further react; The third stage: in the absence of a catalyst or in the presence of a catalyst, removing the cyclic anhydride and / or HO-R4-OH and / or water to obtain a high molecular weight polymer.

5. A method for preparing a polymer according to claim 4, wherein the polymer comprises an ester-imide structural unit of formula (I) and / or (II), and optionally a structural unit of formula (III) and / or (IV) and / or (V) and / or (VI), Wherein R1, R2, R3 and R4 are as defined in claim 1 or 2, and the method is selected from: The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as a raw material to carry out esterification reaction, amidation reaction and imide cyclization reaction; The second stage: in the absence of a catalyst or in the presence of a catalyst, HOOC-R2-COOH or HOOC-R3-COOH is added to further carry out esterification reaction and imide cyclization reaction to obtain a carboxyl-terminated prepolymer; The third stage: in the absence of catalyst or in the presence of catalyst, remove cyclic anhydride and water to obtain high molecular weight polymer. or, The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as a raw material to carry out esterification reaction, amidation reaction and imide cyclization reaction; The second stage: adding catalyst and HO-R4-OH to react to obtain a hydroxyl-terminated prepolymer. The third stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer; or, The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as a raw material to carry out esterification reaction, amidation reaction and imide cyclization reaction; The second stage: adding HOOC-R2-COOH or HOOC-R3-COOH, further carrying out esterification reaction and imide cyclization reaction to obtain a carboxyl-terminated prepolymer, and then adding a catalyst and HO-R4-OH to react to obtain a hydroxyl-terminated prepolymer. The third stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer. or, The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH as a raw material to carry out esterification reaction, amidation reaction and imide cyclization reaction; The second stage: adding HOOC-R2-COOH or HOOC-R3-COOH, a catalyst and HO-R4-OH to react to obtain a prepolymer, The third stage: in the presence of a catalyst, HO-R4-OH, cyclic anhydride and water are removed to obtain a high molecular weight polymer.

6. The method according to any one of claims 4-5, characterized in that: HOOC-R2-COOH is selected from the group consisting of easily cyclizable dibasic acids; preferably selected from the group consisting of unsubstituted or substituted alkanedicarboxylic acids selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, unsubstituted or substituted alkanedicarboxylic acids interrupted by one or more O atoms selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, unsubstituted or substituted alkenedicarboxylic acids selected from halogen or alkyl, unsubstituted or substituted cycloalkanedicarboxylic acids selected from halogen, alkyl or nitro, unsubstituted or substituted cycloalkenedicarboxylic acids selected from halogen, alkyl or nitro, An aromatic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged cyclic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro; more preferably selected from succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid , methylmaleic acid, dimethylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid.

7. The method according to any one of claims 4 to 6, characterized in that HO-R1(NH2)-OH is selected from an alkanediolamine which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or an alkyl-aryl-alkyldiolamine which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro; Preferably, it is at least one selected from 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-1,3-butanediol, 2-amino-1,4-butanediol, 2-amino-1,5-pentanediol, 3-amino-1,5-pentanediol, 5-amino-1,3-benzenedimethanol and (2-amino-1,3-phenylene)dimethanol.

8. The method according to any one of claims 4 to 7, characterized in that: HOOC-R3-COOH is any dibasic acid different from HOOC-R2-COOH, for example, it can be selected from the dibasic acid that is easy to cyclize as defined in claim 4, or the dibasic acid that is not easy to cyclize, such as terephthalic acid, 2,5-furandicarboxylic acid, oxalic acid, malonic acid, 1,6-hexanedicarboxylic acid, 1,10-decanedioic acid, 1,18-octadecanedicarboxylic acid; preferably, HOOC-R3-COOH is selected from a substituent that is unsubstituted or selected from halogen, alkyl, aryl, arylalkyl or alkylaryl. Substituted alkanedicarboxylic acids, alkanedicarboxylic acids which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, interrupted by one or more O atoms, alkenedicarboxylic acids which are unsubstituted or substituted with substituents selected from halogen or alkyl, cycloalkanedicarboxylic acids which are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, cycloalkenedicarboxylic acids which are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, substituted aromatic dicarboxylic acids, or bridged cyclic dicarboxylic acids which are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro; more preferably selected from succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, oxalic acid, malonic acid, 1,6-hexanedicarboxylic acid, 1,10-decanedioic acid, 1,18-octadecanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, cis-butanedicarboxylic acid At least one of maleic acid, methylmaleic acid, dimethylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornene diacid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, terephthalic acid, and 2,5-furandicarboxylic acid.

9. The method according to any one of claims 4 to 8, characterized in that: HO-R4-OH is selected from alkylene glycols which are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, OH-alkylene-cycloalkylene-alkylene-OH which are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, polyether glycols, or alkylene glycols interrupted by one or more N atoms; Preferably, at least one selected from alkylene glycols containing 2 to 18 carbon atoms, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, N-methyldiethanolamine, and N-ethyldiethanolamine; More preferably, it is at least one selected from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,18-octadecanediol, and polyethylene glycol.

10. The method according to any one of claims 4 to 9, characterized in that: The catalyst is selected from at least one of aluminum chloride, ferric chloride, boron trifluoride, stannous chloride, stannous octoate, stannous isooctanoate, dibutyltin dilaurate, monobutyltin oxide, antimony trioxide, zinc oxide, isopropyl titanate, and tetrabutyl titanate.

11. The method according to any one of claims 4 to 10, characterized in that: The molar ratio of (HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH) to (HO-R1(NH2)-OH, or a mixture of HO-R1(NH2)-OH and HO-R4-OH) in the first stage is (1.01-10):1, preferably (1.5-4):1; and / or The reaction temperature of the amidation reaction, esterification reaction and imide cyclization reaction in the first stage and the second stage is 60-300°C, preferably 100-250°C, and the reaction time can be 4-72 hours, preferably 6-24 hours; The reaction temperature in the third stage is 150-300° C., preferably 180-250° C., the reaction time can be 6-72 hours, preferably 6-48 hours, and the vacuum degree is less than 200 Pa, preferably less than 100 Pa.

12. The method according to any one of claims 4 to 11, characterized in that: The first and second stages include the following reaction processes, 13. A method for preparing a polymer comprising an ester-imide structural unit of formula (I) and / or (II) and optionally a structural unit of formula (III) and / or (IV) and / or (V) and / or (VI), Wherein R1, R2, R3 and R4 are as defined above, the method comprises: The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an amide-acid structure represented by formula (VII) as raw materials, and performing an esterification reaction and an imide cyclization reaction to obtain a carboxyl-terminated prepolymer; The second stage: removing cyclic anhydride and water in the absence of a catalyst or in the presence of a catalyst to obtain a high molecular weight polymer; or The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an amide-acid structure represented by formula (VII) as raw materials, an esterification reaction and an imide cyclization reaction are carried out to obtain a carboxyl-terminated prepolymer, and then a catalyst is added to react with HO-R4-OH to obtain a hydroxyl-terminated prepolymer. The second stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer; or The first stage: in the absence of a catalyst or in the presence of a catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an imide structure represented by formula (VIII) as raw materials, and performing an esterification reaction to obtain a carboxyl-terminated prepolymer; The second stage: removing cyclic anhydride and water in the absence of a catalyst or in the presence of a catalyst to obtain a high molecular weight polymer; or The first stage: in the absence of catalyst or in the presence of catalyst, using an excess molar ratio of HOOC-R2-COOH or its cyclic anhydride and / or HOOC-R3-COOH and a diol containing an imide structure represented by formula (VIII) are used as raw materials to carry out an esterification reaction to obtain a carboxyl-terminated prepolymer, and then a catalyst is added to react with HO-R4-OH to obtain a hydroxyl-terminated prepolymer, The second stage: in the presence of a catalyst, HO-R4-OH and water are removed to obtain a high molecular weight polymer; wherein R1, R2, R3 and R4 are as defined in claim 1 or 2.

14. A method for preparing a diol containing an amide-acid structure represented by formula (VII), comprising: exist The corresponding HO-R1(NH2)-OH amino diol is reacted with the anhydride of HOOC-R2-COOH in water or an organic solvent in the presence of a catalyst, and then acidified with an acidifying agent, wherein R1 and R2 are as defined in claim 1 or 2, 15. The method of claim 14, wherein the organic solvent is selected from esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide; dioxane; ethers such as trimethyl glycerol and dimethyl sorbitol; and / or The catalyst is selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, triethylamine, triisopropylamine, trioctylamine, tetramethylguanidine, pyridine, piperidine or 1,8-diazacyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4.3.0]non-5-ene; and / or The acidifying agent is selected from hydrochloric acid, phosphoric acid, boric acid, nitric acid, sulfuric acid, acetic acid, sodium dihydrogen phosphate or potassium dihydrogen phosphate.

16. A method for preparing a diol containing an imide structure represented by formula (VIII), comprising: exist The corresponding amino diol of HO-R1(NH2)-OH is reacted with the anhydride of HOOC-R2-COOH in water or an organic solvent in the presence of a catalyst, wherein R1 and R2 are as defined in claim 1 or 2, 17. The method of claim 16, wherein the organic solvent is selected from esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide; dioxane; ethers such as trimethyl glycerol and dimethyl sorbitol; and / or The catalyst is selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, triethylamine, triisopropylamine, trioctylamine, tetramethylguanidine, pyridine, piperidine, 1,8-diazacyclo[5,4,0]undecene-7 or 1,5-diazabicyclo[4.3.0]non-5-ene.

18. A method for synthesizing a compound represented by formula (VIIII): Including Double bond hydrogenation.

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