WO2025152975A1 - Polyester polymer containing cyclic imide structure - Google Patents
Polyester polymer containing cyclic imide structureInfo
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- WO2025152975A1 WO2025152975A1 PCT/CN2025/072532 CN2025072532W WO2025152975A1 WO 2025152975 A1 WO2025152975 A1 WO 2025152975A1 CN 2025072532 W CN2025072532 W CN 2025072532W WO 2025152975 A1 WO2025152975 A1 WO 2025152975A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
Definitions
- Polyesters based on ethylene glycol such as PES (polyethylene succinate), as aliphatic polyesters, have good biodegradability similar to PBS (polybutylene succinate), good comprehensive mechanical properties, lower price than PBS, and all its polymer monomers can be biologically derived, making it a bio-based biodegradable material with great application prospects.
- PES polyethylene succinate
- PBS polybutylene succinate
- Tm melting temperature
- PES has a lower melting temperature (Tm is about 100°C), which limits its application in some heat-resistant products; due to the shorter aliphatic carbon chain, the material itself is hard and brittle, and has poor toughness, resulting in less large-scale application.
- CN103788379B discloses a method for modifying and toughening PES, using a hyperbranched polymer to react with PES to obtain a modified PES with high tensile strength and elongation at break; specifically, a hyperbranched polymer obtained by reacting 2,2-dimethylol propionic acid with a trifunctional or higher polyol is reacted with PES in a kettle to obtain a modified PES.
- the modified functional monomer used in this method is of non-biological origin and the preparation process is relatively long.
- CN113999373A achieves the complementary performance of polylactic acid and PES through copolymerization of the two materials, but the cost of polylactic acid is relatively high, and the cost advantage of PES will be greatly reduced.
- R2 is selected from a straight-chain alkylene group having 2 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1 - C5 alkyl- C6 - C8 aryl- C1 - C5 alkyl group, optionally containing the following substituents: halogen, nitro, C1 - C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl, or C6 - C12 aryl or C6-C12 aryl - C1- C4 alkyl substituted with halogenated or C1 - C4 alkyl;
- R3 is a dibasic acid residue, more preferably a succinic acid residue.
- the polyester main structural unit in the polyester of the present invention comprises a polyester unit obtained by polymerizing a dibasic acid/anhydride/ester used for polymer synthesis with ethylene glycol; preferably selected from one or more of PES, PET, or polyethylene adipate, and further preferably PES;
- R 1 and R 2 are as defined above;
- the invention provides a polyester polymer containing a cyclic imide structure, wherein a cyclic imide side group or side chain is introduced into the polyester polymer through a diacid monomer or a diol monomer, thereby improving the hard and brittle disadvantages of the polyester, improving its comprehensive mechanical properties such as toughness, and improving the heat resistance of the polyester.
- Figure 1 1 H NMR of aspartic acid monomer in polymer synthesis example 1.
- Step 1 A primary amino diol (such as 2-amino-1,3-propanediol or 3-amino-1,2-propanediol) is subjected to an amidation reaction with a cyclic dibasic acid (such as succinic acid or glutaric acid) and/or an acid anhydride corresponding thereto to obtain a monomer composition;
- the monomer composition comprises a diol monomer containing an imide ring structure as shown in formula (V):
- R2 is selected from a straight-chain alkylene group having 2 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1 - C5 alkyl- C6 - C8 aryl- C1 - C5 alkyl group, optionally containing the following substituents: halogen, nitro, C1 - C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl, or C6 - C12 aryl or C6-C12 aryl - C1- C4 alkyl substituted with halogenated or C1 - C4 alkyl.
- the typical preparation process includes:
- diol monomers include:
- Step 2 subjecting the monomer composition and diol and dibasic acid/ester/anhydride, or subjecting the monomer composition and polyester main prepolymer to esterification/ester exchange reaction, to obtain a polyester polymer containing the first modified unit, wherein the structure of the diol monomer containing an imide ring structure and the dibasic acid polymerization is:
- R3 is a dibasic acid used for polymer synthesis or a dibasic acid residue that is easily cyclized, or a combination of the two.
- R3 is a dibasic acid residue used for polymer synthesis, preferably a succinic acid residue.
- n is an integer of 0 or greater than 0; preferably, n is any integer between 0 and 7; and/or, the aspartic acid monomer comprises one or more monomers containing an imide cyclic structure shown in (Formula VI) after the ring-opening of some cyclic imides, for example:
- the polymer of the present invention may optionally include a third modified unit that is heat-resistant, transparent or has a high barrier property.
- the third modified unit may be composed of a polymerized repeating unit composed of a dibasic acid, a diamine or an amino acid (one or more of isophthalic acid, furandicarboxylic acid, camphoric acid, adipic acid, proline, and meta-xylylenediamine) and a diol (one or more of ethylene glycol, butanediol, and 1,4-cyclohexanedimethanol).
- Asp is an aspartic acid residue
- X is defined as above, n is an integer of 0 or greater than 0, preferably, n is any integer from 0 to 7; preferably, the content of the second modified unit where n is greater than 0 is greater than 0; preferably, the aspartic acid monomer further comprises a structure after the ring-opening of a portion of the imide in (Formula VI).
- the polymers of the present invention may form alloys with each other or optionally with other polymers.
- the polyester polymer composition of the present invention may further contain a plasticizer, a crystal nucleating agent or a hydrolysis inhibitor.
- the polyester polymer composition of the present invention may contain fillers (inorganic fillers, organic fillers), flame retardants, antioxidants, hydrocarbon waxes or anionic surfactants, i.e., lubricants, ultraviolet absorbers, antistatic agents, anticorona agents, light stabilizers, pigments, mildewproof agents, antibacterial agents, foaming agents, etc. as other ingredients other than the above, within the range not impairing the effects of the present invention.
- other polymer materials and other resin compositions may also be added within the range not impairing the effects of the present invention.
- the polyester polymer composition of the present invention can be prepared into a molded body such as a sheet by extrusion molding or press molding; the obtained sheet can also be further thermoformed in a temperature range above the glass transition temperature (Tg) and below the melting point (Tm) of the polyester resin composition, for example, stretched into a film or fiber.
- Tg glass transition temperature
- Tm melting point
- the polymer, alloy thereof or composition or molded body of the present invention is suitable for use in food containers, food packaging films, disposable tableware such as spoons or straws, transparent boxes for daily necessities, cosmetics, home appliances, etc., transparent windows of cartons and other packaging containers, transparent folders, document holders and other stationery, industrial films or agricultural films, clothing or industrial chemical fibers, etc.
- the amino-containing diol in the present invention has the following structure: HO- R2 ( NH2 )-OH.
- the amino-containing diol can be selected from an alkanediolamine that is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or an alkyl-aryl-alkyldiolamine that is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro.
- the HOOC-R 1 -COOH is a dibasic acid that is easily cyclized, that is, a dibasic carboxylic acid that is easily formed into a cyclic anhydride in the absence of a catalyst or under a catalyst condition.
- Dibasic acids that are easily cyclized are known to those skilled in the art, for example, see CN110790906B.
- HOOC-R 1 -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, nadic 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
- the cyclic anhydride of -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, hexahydrobutyric anhydride, At least one of phthalic anhydride, nadic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, 2-methylglutaric anhydride, 3-methylglutaric anhydride, 3-phenylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric an
- HOOC-R 3 -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 with one or more O atoms interrupted, 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
- HOOC-R 3 -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 alkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro .
- -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-octadecanediol, maleic acid, methylmaleic acid, dimethylmaleic acid, At least one of diacid, phthalic acid, hexahydrophthalic acid, nadic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglu
- It can be preferably selected from at least one of 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.
- the polyester structural unit used in the present invention has a common meaning in the art, and is preferably formed by polycondensation of the above-mentioned dicarboxylic acid used for polymer synthesis and diol used for polymer synthesis.
- Step 3 After the esterification is completed, 200ppm tetrabutyl titanate is added as a catalyst to carry out polycondensation reaction, the vacuum degree in the kettle is slowly reduced, and the temperature is further raised to 230°C, and the vacuum degree is maintained below 50Pa for 4-6 hours before the reaction is terminated to obtain a modified product.
- u3 is an integer of 0 or greater than 0, and the average value of u3 in the polymer is preferably less than 2, and more preferably less than 1.
- Step 3 After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
- Step 3 After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
- Step 3 After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
- PES polyesters with different ratios of modified units were synthesized according to the method of polymer synthesis example 1 (Examples 1-1 to 1-6), and modified PES polyesters were synthesized according to polymer synthesis example 2 (Example 1-7). It can be seen from the nuclear magnetic data that there is no absorption peak near the chemical shift position 8, indicating that aspartic acid in the polymer has been completely ring-closed, and there are no exposed -NH- and -NH 2 - absorption peaks.
- Effect Example 2 Effect of different ratios of 3-amino-1,2-propanediol and 2-amino-1,3-propanediol modified units on PES polymerization performance
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Abstract
Description
本发明要求2024年1月16日递交的发明名称为“含有环酰亚胺结构的聚酯聚合物”、申请号为202410066595.4的在先申请优先权，上述在先申请的内容以引用的方式并入本文本中。The present invention claims priority to the prior application entitled “Polyester polymer containing cyclic imide structure” and application number 202410066595.4 filed on January 16, 2024. The contents of the above-mentioned prior application are incorporated into this text by reference.
本发明属于聚合物领域，具体涉及含有环酰亚胺结构的聚酯聚合物。The invention belongs to the field of polymers, and in particular relates to a polyester polymer containing a cyclic imide structure.
基于乙二醇的聚酯如PES(聚丁二酸乙二醇酯)作为脂肪族聚酯，具有类似于PBS(聚丁二酸丁二醇酯)的良好的可降解性，综合力学性能较好，价格相较PBS更低廉，且其聚合单体可全部实现生物来源，是一种具有较大应用前景的生物基可降解材料。但PES材料相较于目前市场应用较多的PBS，其熔融温度更低(Tm约为100℃)，限制了其在一些耐温制品方面的应用；由于更短的脂肪碳链，材料本身偏硬和脆，韧性也较差，导致其大规模应用较少。Polyesters based on ethylene glycol, such as PES (polyethylene succinate), as aliphatic polyesters, have good biodegradability similar to PBS (polybutylene succinate), good comprehensive mechanical properties, lower price than PBS, and all its polymer monomers can be biologically derived, making it a bio-based biodegradable material with great application prospects. However, compared with PBS, which is widely used in the market, PES has a lower melting temperature (Tm is about 100°C), which limits its application in some heat-resistant products; due to the shorter aliphatic carbon chain, the material itself is hard and brittle, and has poor toughness, resulting in less large-scale application.
CN103788379B公开了一种PES改性增韧的方法，使用超支化聚合物与PES接触反应制得具有高拉伸强度和断裂伸长率的改性PES；具体为使用2,2-二羟甲基丙酸与三及以上官能度多元醇反应制得的超支化聚合物与PES共同釜内反应，得到改性PES，该方法使用的改性功能单体为非生物来源且制备流程较长。CN113999373A通过聚乳酸与PES的共聚实现两种材料性能的互补，但聚乳酸成本较高，PES的成本优势会被大幅降低。CN103788379B discloses a method for modifying and toughening PES, using a hyperbranched polymer to react with PES to obtain a modified PES with high tensile strength and elongation at break; specifically, a hyperbranched polymer obtained by reacting 2,2-dimethylol propionic acid with a trifunctional or higher polyol is reacted with PES in a kettle to obtain a modified PES. The modified functional monomer used in this method is of non-biological origin and the preparation process is relatively long. CN113999373A achieves the complementary performance of polylactic acid and PES through copolymerization of the two materials, but the cost of polylactic acid is relatively high, and the cost advantage of PES will be greatly reduced.
本发明首先提供一种聚酯，所述聚酯包含包含聚酯主体结构单元和改性单元，所述聚酯主体结构单元的部分(如大于30％、大于40％、大于50、大于60％、大于70％、大于90％)或全部包含乙二醇残基；所述改性单元包含第一改性单元或/和第二改性单元，所述第一改性单元包含式(I)结构：
The present invention first provides a polyester, which comprises a polyester main structural unit and a modification unit, wherein part (e.g., greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 90%) or all of the polyester main structural unit comprises ethylene glycol residues; the modification unit comprises a first modification unit and/or a second modification unit, and the first modification unit comprises a structure of formula (I):
R1选自碳原子数为1至7的亚烷基，优选为主链碳原子数为1或2或3或4的直链或支链亚烷基，6至12个碳原子数的亚芳基，5至11个碳原子数的亚杂基，3至12个碳原子数的亚环烷基，2至11个碳原子数的亚杂环烷基或其组合，任选包含如下取代基：卤素、硝基、C1-C4烷基、卤代C1-C4烷基、C6-C12芳基、C6-C12芳基-C1-C4烷基或卤代、C1-C4烷基取代的C6-C12芳基或C6-C12芳基-C1-C4烷基； R1 is selected from an alkylene group having 1 to 7 carbon atoms, preferably a straight or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain, an arylene group having 6 to 12 carbon atoms, a heteroalkylene group having 5 to 11 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms or a combination thereof, optionally containing the following substituents: halogen, nitro, C1 - C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl or C6 - C12 aryl or C6- C12 aryl- C1 - C4 alkyl substituted with halogenated or C1 - C4 alkyl ;
R2选自2至12个碳原子数的直链次烷基、3至12个碳原子数的支链次烷基、具有6至12个碳原子数的次芳基、3至12个碳原子数的次环烷基或三价C1-C5烷基-C6-C8芳基-C1-C5烷基，任选包含如下取代基：卤素、硝基、C1-C4烷基、卤代C1-C4烷基、C6-C12芳基、C6-C12芳基-C1-C4烷基或卤代、C1-C4烷基取代的C6-C12芳基或C6-C12芳基-C1-C4烷基； R2 is selected from a straight-chain alkylene group having 2 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1 - C5 alkyl- C6 - C8 aryl- C1 - C5 alkyl group, optionally containing the following substituents: halogen, nitro, C1 - C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl, or C6 - C12 aryl or C6-C12 aryl - C1- C4 alkyl substituted with halogenated or C1 - C4 alkyl;
所述第二改性单元包含式(II)结构：
The second modifying unit comprises a structure of formula (II):
其中Asp为天冬氨酸的残基；Where Asp is the residue of aspartic acid;
X选自-C＝C-、碳原子数为1至7的亚烷基，优选为主链碳原子数为1或2或3或4的直链或支链亚烷基，6至12个碳原子数的亚芳基，5至11个碳原子数的亚杂芳基，3至12个碳原子数的亚环烷基，2至11个碳原子数的亚杂环烷基或其组合，任选包含如下取代基：卤素、硝基、C1-C4烷基、卤代C1-C4烷基、C6-C12芳基、C6-C12芳基-C1-C4烷基或卤代、C1-C4烷基取代的C6-C12芳基或C6-C12芳基-C1-C4烷基；X is selected from -C=C-, an alkylene group having 1 to 7 carbon atoms, preferably a straight or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 5 to 11 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms or a combination thereof, optionally containing the following substituents: halogen, nitro, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 6 -C 12 aryl, C 6 -C 12 aryl-C 1 -C 4 alkyl, or C 6 -C 12 aryl or C 6 -C 12 aryl-C 1 -C 4 alkyl substituted with halogenated or C 1 -C 4 alkyl;
n为0或大于0的整数，优选地，n为0-7的任意整数；优选地，n大于0的第二改性单元含量大于0；n is an integer of 0 or greater than 0, preferably, n is any integer of 0-7; preferably, n is greater than 0 and the content of the second modifying unit is greater than 0;
优选地，所述第二改性单元进一步包含(式II)中部分酰亚胺开环后的结构。Preferably, the second modification unit further comprises a structure in which part of the imide in (Formula II) is ring-opened.
在本发明的具体实施方式中，本发明的聚酯中所述第一改性单元的结构为：
In a specific embodiment of the present invention, the structure of the first modified unit in the polyester of the present invention is:
其中R3为C2-C4的直链或支链亚烷基、1,4-亚环己基或1,4-亚苯基，*示出了与其他单元的连接位置；Wherein R 3 is a C 2 -C 4 straight chain or branched alkylene group, 1,4-cyclohexylene group or 1,4-phenylene group, and * indicates the connection position with other units;
优选地，R2为2-氨基-1,3-丙二醇或3-氨基-1,2-丙二醇的残基；Preferably, R 2 is the residue of 2-amino-1,3-propanediol or 3-amino-1,2-propanediol;
优选地，R1为丁二酸残基(即亚乙基)；Preferably, R 1 is a succinic acid residue (i.e., ethylene);
优选地，R3为二元酸残基，更优选为丁二酸残基。Preferably, R3 is a dibasic acid residue, more preferably a succinic acid residue.
在本发明的具体实施方式中，其中所述第一改性单元占聚酯聚合物总聚酯单元的比例为1-50mol％，优选地为5-50mol％。In a specific embodiment of the present invention, the ratio of the first modified unit to the total polyester units of the polyester polymer is 1-50 mol%, preferably 5-50 mol%.
在本发明的具体实施方式中，本发明的聚酯中所述第二改性单元的结构为：
In a specific embodiment of the present invention, the structure of the second modified unit in the polyester of the present invention is:
其中Asp为天冬氨酸的残基，X为亚乙基、1,2-亚环己基或1,2-亚苯基，R4为用于聚合物合成的二元醇残基，并包含乙二醇残基；优选为乙二醇残基，或乙二醇残基与丙二醇或丁二醇残基的组合，*示出了与其他单元的连接位置。n为0或大于0的整数；优选地，n大于0的第二改性单元含量大于0；Where Asp is an aspartic acid residue, X is ethylene, 1,2-cyclohexylene or 1,2-phenylene, R4 is a diol residue for polymer synthesis, and includes an ethylene glycol residue; preferably an ethylene glycol residue, or a combination of an ethylene glycol residue and a propylene glycol or a butylene glycol residue, and * indicates the connection position with other units. n is an integer of 0 or greater; preferably, the second modified unit content where n is greater than 0 is greater than 0;
优选地，X为-C＝C-、亚乙基；优选地，R4为亚乙基。Preferably, X is -C=C-, ethylene; preferably, R 4 is ethylene.
在本发明的具体实施方式中，本发明的聚酯中所述第二改性结构单元占聚合物总结构单元0.5-99.5mol％，优选为1-90mol％，进一步优选为5％-30mol％。In a specific embodiment of the present invention, the second modified structural unit in the polyester of the present invention accounts for 0.5-99.5 mol%, preferably 1-90 mol%, and more preferably 5%-30 mol% of the total structural units of the polymer.
在本发明的具体实施方式中，本发明的聚酯中所述聚酯主体结构单元包含用于聚合物合成的二元酸/酸酐/酯聚与乙二醇聚合得到的聚酯单元；优选地选自PES、PET、或聚己二酸乙二醇酯中一种或多种，进一步优选地为PES；In a specific embodiment of the present invention, the polyester main structural unit in the polyester of the present invention comprises a polyester unit obtained by polymerizing a dibasic acid/anhydride/ester used for polymer synthesis with ethylene glycol; preferably selected from one or more of PES, PET, or polyethylene adipate, and further preferably PES;
优选地，所述聚酯分别或同时包含第一改性单元和第二改性单元，优选地，所述聚酯聚合物还包含第三改性结构单元。Preferably, the polyester comprises a first modification unit and a second modification unit separately or simultaneously. Preferably, the polyester polymer further comprises a third modification structural unit.
第二，本发明提供一种聚合物合金，其中包含权本发明所述的聚酯。Secondly, the present invention provides a polymer alloy comprising the polyester described in the present invention.
第三，本发明提供一种聚合物组合物或成型体，其中包含本发明所述的聚酯。Thirdly, the present invention provides a polymer composition or a shaped article, which comprises the polyester described in the present invention.
第四，本发明提供一种本发明的聚酯、或聚合物合金、或聚合物组合物或成型体的用途，所述用途包括用于食品容器、食品包装用膜、一次性餐具如勺或吸管、日用品、化妆品、家电制品等的透明箱、纸箱的透明窗等包装容器、透明文件夹、证件套等文具类、工业用膜或农业用膜、服用或者工业用化学纤维。Fourthly, the present invention provides a use of the polyester, or polymer alloy, or polymer composition or molded body of the present invention, the uses including use in food containers, food packaging films, disposable tableware such as spoons or straws, daily necessities, cosmetics, transparent boxes for household appliances, transparent windows of cartons and other packaging containers, transparent folders, ID holders and other stationery, industrial films or agricultural films, and chemical fibers for clothing or industry.
第五，本发明提供一种本发明所述聚酯的制备方法，包括：Fifth, the present invention provides a method for preparing the polyester of the present invention, comprising:
1)提供：1) Provide:
式V所示的二元醇单体：
The diol monomer represented by formula V is:
其中：R1、R2的定义如前所述；Wherein: R 1 and R 2 are as defined above;
或/和or/and
式VI所示的天冬氨酸单体：
Aspartic acid monomer shown in formula VI:
其中Asp为天冬氨酸的残基，X的定义如前所述，n为0或大于0的整数，优选n为0-7的任意整数；优选地，n大于0的第二改性单元含量大于0；优选地，所述天冬氨酸单体进一步包含(式VI)中部分酰亚胺开环后的结构。Wherein Asp is an aspartic acid residue, X is defined as above, n is an integer of 0 or greater than 0, preferably n is any integer of 0-7; preferably, the content of the second modified unit where n is greater than 0 is greater than 0; preferably, the aspartic acid monomer further comprises a structure after the ring-opening of part of the imide in (Formula VI).
2)将上述二元醇单体或/和天冬氨酸单体、乙二醇和用于聚合物合成的二元酸/酯/酸酐，或将上述二元醇单体或/和天冬氨酸单体和预聚体(基于乙二醇和用于聚合物合成的二元酸/酯/酸酐通过酯化/酯交换反应得到的)进行酯化/酯交换反应，得到包含第一改性单元或/和第二改性单元的聚酯聚合物。2) subjecting the above-mentioned diol monomer or/and aspartic acid monomer, ethylene glycol and dibasic acid/ester/anhydride for polymer synthesis, or subjecting the above-mentioned diol monomer or/and aspartic acid monomer and prepolymer (obtained by esterification/ester exchange reaction based on ethylene glycol and dibasic acid/ester/anhydride for polymer synthesis) to esterification/ester exchange reaction to obtain a polyester polymer containing the first modified unit or/and the second modified unit.
有益技术效果Beneficial technical effects
本发明提供了含有环酰亚胺结构的聚酯聚合物，通过二酸单体或二醇单体在聚酯聚合物中引入环酰亚胺侧基或侧链，从而改善聚酯硬而脆的缺点，提高其韧性等综合力学性能，并提高了聚酯的耐热性能。The invention provides a polyester polymer containing a cyclic imide structure, wherein a cyclic imide side group or side chain is introduced into the polyester polymer through a diacid monomer or a diol monomer, thereby improving the hard and brittle disadvantages of the polyester, improving its comprehensive mechanical properties such as toughness, and improving the heat resistance of the polyester.
图1：聚合物合成例1中天冬氨酸单体的1HNMR。Figure 1: 1 H NMR of aspartic acid monomer in polymer synthesis example 1.
图2：聚合物合成例3中二元醇单体的1HNMR。Figure 2: 1 H NMR of diol monomer in polymer synthesis example 3.
I.包含第一改性单元的聚酯聚合物I. Polyester polymer containing the first modifying unit
包含第一改性单元的聚酯聚合物合成方法可以参考中国专利申请(CN202311583766.2)，包括：The synthesis method of the polyester polymer containing the first modified unit can refer to the Chinese patent application (CN202311583766.2), including:
步骤1、将伯氨基二元醇(如2-氨基-1,3-丙二醇或3-氨基-1,2-丙二醇)与易成环二元酸(如丁二酸或戊二酸)和/或其所对应的酸酐进行酰胺化反应，得到单体组合物；所述单体组合物包括含有酰亚胺环状结构的二元醇单体如式(V)所示：
Step 1: A primary amino diol (such as 2-amino-1,3-propanediol or 3-amino-1,2-propanediol) is subjected to an amidation reaction with a cyclic dibasic acid (such as succinic acid or glutaric acid) and/or an acid anhydride corresponding thereto to obtain a monomer composition; the monomer composition comprises a diol monomer containing an imide ring structure as shown in formula (V):
其中：R1独立选自碳原子数为1至7的亚烷基，优选为主链碳原子数为1或2或3或4的直链或支链亚烷基，6至12个碳原子数的亚芳基，5至11个碳原子数的亚杂基，3至12个碳原子数的亚环烷基，2至11个碳原子数的亚杂环烷基或其组合，任选包含如下取代基：卤素、硝基、C1-C4烷基、卤代C1-C4烷基、C6-C12芳基、C6-C12芳基-C1-C4烷基或卤代、C1-C4烷基取代的C6-C12芳基或C6-C12芳基-C1-C4烷基；Wherein: R1 is independently selected from an alkylene group having 1 to 7 carbon atoms, preferably a straight or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain, an arylene group having 6 to 12 carbon atoms, a heteroalkylene group having 5 to 11 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms or a combination thereof, optionally containing the following substituents: halogen , nitro, C1- C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl or C6 - C12 aryl or C6- C12 aryl- C1 - C4 alkyl substituted with halogenated or C1 - C4 alkyl;
R2选自选自2至12个碳原子数的直链次烷基、3至12个碳原子数的支链次烷基、具有6至12个碳原子数的次芳基、3至12个碳原子数的次环烷基或三价C1-C5烷基-C6-C8芳基-C1-C5烷基，任选包含如下取代基：卤素、硝基、C1-C4烷基、卤代C1-C4烷基、C6-C12芳基、C6-C12芳基-C1-C4烷基或卤代、C1-C4烷基取代的C6-C12芳基或C6-C12芳基-C1-C4烷基。 R2 is selected from a straight-chain alkylene group having 2 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1 - C5 alkyl- C6 - C8 aryl- C1 - C5 alkyl group, optionally containing the following substituents: halogen, nitro, C1 - C4 alkyl, halogenated C1 - C4 alkyl, C6 - C12 aryl, C6 - C12 aryl- C1 - C4 alkyl, or C6 - C12 aryl or C6-C12 aryl - C1- C4 alkyl substituted with halogenated or C1 - C4 alkyl.
典型的制备过程包括：The typical preparation process includes:
将真空干燥后的911.1g(10mol)的2-氨基-1,3-丙二醇与1180.1g(10mol)的1,4-丁二酸投入反应釜中，同时投入亚磷酸三苯酯(热稳定剂)和四[3-(3,5-二叔丁基-4-羟苯基)丙酸]季戊醇酯(抗氧化剂)各100ppm(相较于整个反应体系的重量，下同)，室温搅拌，并同时使用氮气充分置换釜内空气，之后在氮氛中缓慢升温至120℃，氮气流量150mL/min，并恒温搅拌3h，得到二元醇组合物。911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reaction kettle, and 100 ppm each (compared to the weight of the entire reaction system, the same below) of triphenyl phosphite (heat stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added, stirred at room temperature, and nitrogen was used to fully replace the air in the kettle. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL/min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.
代表性的二元醇单体包括：
Representative diol monomers include:
步骤2、将所述单体组合物和二元醇和二元酸/酯/酸酐，或将所述单体组合物和聚酯主体预聚体进行酯化/酯交换反应，得到包含第一改性单元的聚酯聚合物，其中含有酰亚胺环状结构的二元醇单体与二元酸聚合的结构为：Step 2: subjecting the monomer composition and diol and dibasic acid/ester/anhydride, or subjecting the monomer composition and polyester main prepolymer to esterification/ester exchange reaction, to obtain a polyester polymer containing the first modified unit, wherein the structure of the diol monomer containing an imide ring structure and the dibasic acid polymerization is:
R3为用于聚合物合成的二元酸或易成环二元酸残基或为两者的组合；在本发明具体实施方式中，R3为用于聚合物合成的二元酸残基，优选为丁二酸残基。 R3 is a dibasic acid used for polymer synthesis or a dibasic acid residue that is easily cyclized, or a combination of the two. In a specific embodiment of the present invention, R3 is a dibasic acid residue used for polymer synthesis, preferably a succinic acid residue.
II.包含第二改性单元的聚酯聚合物II. Polyester polymer containing a second modifying unit
包含第二改性单元的聚酯聚合物的合成可以参考中国专利申请(CN202311738254.9)，包括：The synthesis of the polyester polymer containing the second modified unit can refer to the Chinese patent application (CN202311738254.9), including:
步骤1、含有酰亚胺环状结构的天冬氨酸单体的合成：Step 1, synthesis of aspartic acid monomer containing imide ring structure:
通过一定的比例混合天冬氨酸和易成环二元酸进行酰胺化反应即可以获得上述单体，反应条件本领域技术人员可以根据天冬氨酸和易成环二元酸进行选择，例如无氧热熔融条件下反应。The above monomer can be obtained by mixing aspartic acid and an easily cyclized dibasic acid in a certain ratio and performing an amidation reaction. The reaction conditions can be selected by those skilled in the art according to the aspartic acid and the easily cyclized dibasic acid, such as reacting under anaerobic hot melt conditions.
典型的制备步骤例如将天冬氨酸：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应。再如将将天冬氨酸：1，2-环己烷二甲酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应，得到包含酰亚胺杂环的天冬氨酸单体：
Typical preparation steps include reacting aspartic acid: succinic acid in a molar ratio of 1:3 in a reactor, adding 200 ppm of antioxidant and heat stabilizer, heating and melting under nitrogen protection to react. Another example is reacting aspartic acid: 1,2-cyclohexanedicarboxylic acid in a molar ratio of 1:3 in a reactor, adding 200 ppm of antioxidant and heat stabilizer, heating and melting under nitrogen protection to react, to obtain an aspartic acid monomer containing an imide heterocycle:
代表性的单体包括：
Representative monomers include:
在另一些实施方案中，含有酰亚胺环状结构的天冬氨酸单体结构如式VI所示，其中：In other embodiments, the aspartic acid monomer structure containing an imide ring structure is as shown in Formula VI, wherein:
X为-C＝C-；X is -C=C-;
n为0或大于0的整数；优选地，n为0-7中的任意整数；和/或，所述天冬氨酸单体包括一个或多个(式VI)所示的含有酰亚胺环状结构的单体中部分环酰亚胺开环后的结构，例如：
n is an integer of 0 or greater than 0; preferably, n is any integer between 0 and 7; and/or, the aspartic acid monomer comprises one or more monomers containing an imide cyclic structure shown in (Formula VI) after the ring-opening of some cyclic imides, for example:
步骤2、将上述天冬氨酸单体和二元醇和二元酸/酯/酸酐，或将上述天冬氨酸单体和聚酯主体预聚体进行酯化/酯交换反应，得到包含第一改性单元的聚酯聚合物，其中含有酰亚胺环状结构的二元酸单体与二元醇聚合的结构为：
Step 2: subjecting the aspartic acid monomer and diol to esterification/ester exchange reaction, or subjecting the aspartic acid monomer to polyester main body prepolymer, to obtain a polyester polymer containing the first modified unit, wherein the structure of the dibasic acid monomer containing an imide ring structure and the diol polymerized is:
其中Asp为天冬氨酸的残基，X优选地为-C＝C-、亚乙基、1,2-亚环己基或1,2-亚苯基，R4为用于聚合物合成的二元醇残基并包含乙二醇残基，优选为乙二醇残基，或乙二醇残基与丙二醇或丁二醇残基的组合。n为0或大于0的整数，优选地，n为0-7中的任意整数；优选地，n大于0的第二改性单元含量大于0；优选地，n的均值小于2，进一步优选地小于1。优选地，所述包含第二改性单元的聚酯聚合物包含(式IV)所述聚合物中部分环酰亚胺开环后的结构。Wherein Asp is an aspartic acid residue, X is preferably -C=C-, ethylene, 1,2-cyclohexylene or 1,2-phenylene, R4 is a diol residue used for polymer synthesis and comprises an ethylene glycol residue, preferably an ethylene glycol residue, or a combination of an ethylene glycol residue and a propylene glycol or butylene glycol residue. n is an integer of 0 or greater than 0, preferably, n is any integer from 0 to 7; preferably, the content of the second modified unit where n is greater than 0 is greater than 0; preferably, the average value of n is less than 2, and further preferably less than 1. Preferably, the polyester polymer comprising the second modified unit comprises a structure after the ring opening of part of the cyclic imide in the polymer (Formula IV).
III.包含第三改性结构单元的聚合物III. Polymers containing a third modifying structural unit
本发明的聚合物可任选包括耐温、透明或高阻隔的第三改性单元，第三改性单元可以由二元酸或二元胺或氨基酸(间苯二甲酸、呋喃二甲酸、樟脑酸己二酸、脯氨酸、间苯二甲胺中的一种或几种)和二元醇(乙二醇、丁二醇、1,4环己烷二甲醇中的一种或几种)组成的聚合重复单元组成。The polymer of the present invention may optionally include a third modified unit that is heat-resistant, transparent or has a high barrier property. The third modified unit may be composed of a polymerized repeating unit composed of a dibasic acid, a diamine or an amino acid (one or more of isophthalic acid, furandicarboxylic acid, camphoric acid, adipic acid, proline, and meta-xylylenediamine) and a diol (one or more of ethylene glycol, butanediol, and 1,4-cyclohexanedimethanol).
IV.包含改性单元的聚酯聚合物IV. Polyester polymers containing modified units
本发明所述包含改性单元的聚酯制备方法，包括：The method for preparing the polyester containing the modified unit of the present invention comprises:
1)提供：1) Provide:
式V所示的二元醇单体：
The diol monomer represented by formula V is:
其中：R1、R2的定义如前所述；Wherein: R 1 and R 2 are as defined above;
或/和or/and
式VI所示的天冬氨酸单体：
Aspartic acid monomer shown in formula VI:
其中Asp为天冬氨酸的残基，X的定义如前所述，n为0或大于0的整数，优选地，n为0-7中的任意整数；优选地，n大于0的第二改性单元含量大于0；优选地，所述天冬氨酸单体进一步包含(式VI)中部分酰亚胺开环后的结构。Wherein Asp is an aspartic acid residue, X is defined as above, n is an integer of 0 or greater than 0, preferably, n is any integer from 0 to 7; preferably, the content of the second modified unit where n is greater than 0 is greater than 0; preferably, the aspartic acid monomer further comprises a structure after the ring-opening of a portion of the imide in (Formula VI).
2)将上述二元醇单体或/和天冬氨酸单体、乙二醇(任选地包含一种或多种其他用于聚合物合成的二醇如丁二醇)和用于聚合物合成的二元酸/酯/酸酐进行酯化/酯交换反应，或将上述二元醇单体或/和天冬氨酸单体和预聚体(基于乙二醇和用于聚合物合成的二元酸/酯/酸酐通过酯化/酯交换反应得到的)进行酯化/酯交换反应，得到包含第一改性单元或/和第二改性单元的聚酯聚合物。2) subjecting the above-mentioned diol monomer or/and aspartic acid monomer, ethylene glycol (optionally containing one or more other diols for polymer synthesis such as butanediol) and dibasic acid/ester/anhydride for polymer synthesis to esterification/transesterification reaction, or subjecting the above-mentioned diol monomer or/and aspartic acid monomer and prepolymer (obtained by esterification/transesterification reaction based on ethylene glycol and dibasic acid/ester/anhydride for polymer synthesis) to esterification/transesterification reaction to obtain a polyester polymer containing the first modified unit or/and the second modified unit.
V.合金V. Alloy
本发明的聚合物之间或任选地与其他聚合物形成合金。The polymers of the present invention may form alloys with each other or optionally with other polymers.
VI.组合物与成型体VI. Composition and Molded Article
本发明还提供上述聚合物的组合物或成型体，各类型的聚合物加工或成型的方法为本领域已知。The present invention also provides a composition or a molded body of the above polymer, and the methods for processing or molding various types of polymers are known in the art.
本发明中的聚酯聚合物组合物还可以包含增塑剂、晶核剂或水解抑制剂。The polyester polymer composition of the present invention may further contain a plasticizer, a crystal nucleating agent or a hydrolysis inhibitor.
在本发明中的聚酯聚合物组合物中，作为上述以外的其他成分，在不破坏本发明的效果的范围内可以含有填充剂(无机填充剂、有机填充剂)、阻燃剂、抗氧化剂、烃系蜡类或阴离子型表面活性剂即润滑剂、紫外线吸收剂、抗静电剂、防晕剂、光稳定剂、颜料、防霉剂、抗菌剂、发泡剂等。另外，同样地在不妨碍本发明的效果的范围内还可以添加其他高分子材料、其他树脂组合物。The polyester polymer composition of the present invention may contain fillers (inorganic fillers, organic fillers), flame retardants, antioxidants, hydrocarbon waxes or anionic surfactants, i.e., lubricants, ultraviolet absorbers, antistatic agents, anticorona agents, light stabilizers, pigments, mildewproof agents, antibacterial agents, foaming agents, etc. as other ingredients other than the above, within the range not impairing the effects of the present invention. In addition, other polymer materials and other resin compositions may also be added within the range not impairing the effects of the present invention.
本发明的聚酯聚合物组合物可以通过挤出成型、加压成型来制备成型体如片；还可以进一步将得到的片在聚酯树脂组合物的玻璃化转变温度(Tg)以上、且低于熔点(Tm)的温度范围内进行热成型，例如拉伸为膜或纤维。The polyester polymer composition of the present invention can be prepared into a molded body such as a sheet by extrusion molding or press molding; the obtained sheet can also be further thermoformed in a temperature range above the glass transition temperature (Tg) and below the melting point (Tm) of the polyester resin composition, for example, stretched into a film or fiber.
VII.制品与用途VII. Products and Applications
本发明的聚合物、其合金或其组合物或成型体适宜用于食品容器、食品包装用膜、一次性餐具如勺或吸管、日用品、化妆品、家电制品等的透明箱、纸箱的透明窗等包装容器、透明文件夹、证件套等文具类、工业用膜或农业用膜、服用或者工业用化学纤维等。The polymer, alloy thereof or composition or molded body of the present invention is suitable for use in food containers, food packaging films, disposable tableware such as spoons or straws, transparent boxes for daily necessities, cosmetics, home appliances, etc., transparent windows of cartons and other packaging containers, transparent folders, document holders and other stationery, industrial films or agricultural films, clothing or industrial chemical fibers, etc.
含氨基的二元醇Amino-containing diols
本发明中含氨基的二元醇具有如下结构：HO-R2(NH2)-OH。所述含氨基的二元醇可选自未被取代或被选自卤素、烷基或硝基的取代基取代的链烷二醇胺，或未被取代或被选自卤素、烷基或硝基的取代基取代的链烷基-芳基-链烷基二醇胺。优选地，所述含氨基的二元醇可选自3-氨基-1,2-丙二醇、2-氨基-1,3-丙二醇、2-氨基-1,3-丁二醇、2-氨基-1,4-丁二醇、2-氨基-1,5-戊二醇、3-氨基-1,5-戊二醇、5-氨基-1,3-苯二甲醇和2-氨基-1,3-苯基二甲醇中的至少一种。The amino-containing diol in the present invention has the following structure: HO- R2 ( NH2 )-OH. The amino-containing diol can be selected from an alkanediolamine that is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or an alkyl-aryl-alkyldiolamine that is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. Preferably, the amino-containing diol can be selected from at least one of 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-phenylenedimethanol.
易环化的二元羧酸HOOC-R1-COOHDicarboxylic acids that are easily cyclized HOOC-R 1 -COOH
所述HOOC-R1-COOH是易环化的二元酸，即在无催化剂或催化剂条件下容易形成环状酸酐的二元羧酸。易环化的二元酸是本领域技术人员所已知的，例如参见CN110790906B。HOOC-R1-COOH可选自未被取代或被选自卤素、烷基、芳基、芳基烷基或烷基芳基的取代基取代的链烷二羧酸，间隔有一个或多个O原子的未被取代或被选自卤素、烷基、芳基、芳基烷基或烷基芳基的取代基取代的链烷二羧酸，未被取代或被选自卤素或烷基的取代基取代的链烯烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的环烷烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的环烯烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的芳族二羧酸，或未被取代或被选自卤素、烷基或硝基的取代基取代的桥环二羧酸。优选地，HOOC-R1-COOH可选自丁二酸、2-甲基丁二酸、2-苯基丁二酸、2-苯甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、2,3-二苯基丁二酸、1,2-环丁二酸、2,2,3,3-四甲基丁二酸、甲基顺丁烯二酸、二甲基顺丁烯二酸、邻苯二甲酸、六氢邻苯二甲酸、降冰片烯二酸、四氢化邻苯二甲酸、戊二酸、2-甲基戊二酸、3-甲基戊二酸、3-苯基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、二甘醇酸、2,3-呋喃二甲酸、3,4-呋喃二甲酸、2,3-吡啶二甲酸、3,4-吡啶二羧酸中的至少一种。所述HOOC-R1-COOH的环状酸酐可优选选自丁二酸酐、2-甲基丁二酸酐、2-苯基丁酸酐、2-苯甲基丁二酸酐、2,2-二甲基丁二酸酐、2,3-二甲基丁二酸酐、2,3-二苯基丁二酸酐、1,2-环丁二酸酐、2,2,3,3-四甲基丁二酸酐、甲基顺丁烯二酸酐、二甲基顺丁烯二酸酐、邻苯二甲酸酐、六氢邻苯二甲酸酐、降冰片烯二酸酐、四氢化邻苯二甲酸酐、戊二酸酐、2-甲基戊二酸酐、3-甲基戊二酸酐、3-苯基戊二酸酐、2,2-二甲基戊二酸酐、3,3-二甲基戊二酸酐和二甘醇酸酐、2,3-呋喃二甲酸酐、3,4-呋喃二甲酸酐、2,3-吡啶二甲酸酐、3,4-吡啶二羧酸酐中的至少一种。The HOOC-R 1 -COOH is a dibasic acid that is easily cyclized, that is, a dibasic carboxylic acid that is easily formed into a cyclic anhydride in the absence of a catalyst or under a catalyst condition. Dibasic acids that are easily cyclized are known to those skilled in the art, for example, see CN110790906B. HOOC- R1 -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 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-R 1 -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, nadic 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 -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, hexahydrobutyric anhydride, At least one of phthalic 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.
用于聚合物合成的二元羧酸Dicarboxylic acids for polymer synthesis
本发明中用于聚合物合成的二元羧酸可以用于聚合物本体结构单元的合成，也可以用于提高聚合物强度结构单元的合成，在用于提高聚合物强度结构单元的合成时，即本发明中定义的HOOC-R3-COOH，其可以是不同于HOOC-R1-COOH的任何二元酸，例如其可为上文对HOOC-R1-COOH所述的易环化二元酸；或者为不易环化二元酸，例如对苯二甲酸、2,5-呋喃二甲酸、草酸、丙二酸、1,6-己二酸、1,10-癸二酸、1,18-十八烷二酸。优选地，HOOC-R3-COOH可选自未被取代或被选自卤素、烷基、芳基、芳基烷基或烷基芳基的取代基取代的链烷二羧酸，间隔有一个或多个O原子的未被取代或被选自卤素、烷基、芳基、芳基烷基或烷基芳基的取代基取代的链烷二羧酸，未被取代或被选自卤素或烷基的取代基取代的链烯烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的环烷烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的环烯烃二羧酸，未被取代或被选自卤素、烷基或硝基的取代基取代的芳族二羧酸，或未被取代或被选自卤素、烷基或硝基的取代基取代的桥环二羧酸。优选地，HOOC-R3-COOH可选自丁二酸、2-甲基丁二酸、2-苯基丁二酸、2-苯甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、2,3-二苯基丁二酸、1,2-环丁二酸、2,2,3,3-四甲基丁二酸、草酸、丙二酸、1,6-己二酸、1,10-癸二酸、1,18-十八烷二酸、顺丁烯二酸、甲基顺丁烯二酸、二甲基顺丁烯二酸、邻苯二甲酸、六氢邻苯二甲酸、降冰片烯二酸、四氢化邻苯二甲酸、戊二酸、2-甲基戊二酸、3-甲基戊二酸、3-苯基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、二甘醇酸、2,3-呋喃二甲酸、3,4-呋喃二甲酸、2,3-吡啶二甲酸、3,4-吡啶二羧酸、对苯二甲酸、2,5-呋喃二甲酸中的至少一种。The dicarboxylic acid used for polymer synthesis in the present invention can be used for the synthesis of polymer main structural units, and can also be used for the synthesis of structural units for improving polymer strength. When used for the synthesis of structural units for improving polymer strength, that is, HOOC-R 3 -COOH defined in the present invention, it can be any dicarboxylic acid different from HOOC-R 1 -COOH, for example, it can be the easily cyclized dicarboxylic acid described above for HOOC-R 1 -COOH; or it can be a dicarboxylic acid that is not easily cyclized, such as terephthalic acid, 2,5-furandicarboxylic acid, oxalic acid, malonic acid, 1,6-hexanoic acid, 1,10-decanedioic acid, and 1,18-octadecane dioic acid. Preferably, HOOC-R 3 -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 with one or more O atoms interrupted, 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-R 3 -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 alkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro . -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-octadecanediol, maleic acid, methylmaleic acid, dimethylmaleic acid, At least one of diacid, phthalic acid, hexahydrophthalic acid, nadic 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.
用于聚合物合成的二元醇Diols for polymer synthesis
用于聚合物合成的二元醇可选自未被取代或被选自卤素、烷基或硝基的取代基取代的亚烷基二醇，未被取代或被选自卤素、烷基或硝基的取代基取代的HO-亚烷基-亚环烷基-亚烷基-OH，聚醚二醇，或间隔有一个或多个N原子的亚烷基二醇；优选选自含2～18个碳的亚烷基二醇、聚乙二醇、聚丙二醇、聚四氢呋喃二醇、N-甲基二乙醇胺、N-乙基二乙醇胺中的至少一种。可优选选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇，1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,18-十八烷二醇、聚乙二醇、1,4-环己烷二甲醇中的至少一种。The diol used for polymer synthesis can be selected from alkylene glycols that are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, HO-alkylene-cycloalkylene-alkylene-OH that are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro, polyether glycol, or alkylene glycols interrupted by one or more N atoms; preferably selected from at least one of alkylene glycols containing 2 to 18 carbon atoms, polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, N-methyldiethanolamine, and N-ethyldiethanolamine. It can be preferably selected from at least one of 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.
聚酯结构单元Polyester structural unit
本发明中使用的聚酯结构单元具有本领域通常的含义，优选地由上述用于聚合物合成的二元羧酸和用于聚合物合成的二元醇缩聚形成。The polyester structural unit used in the present invention has a common meaning in the art, and is preferably formed by polycondensation of the above-mentioned dicarboxylic acid used for polymer synthesis and diol used for polymer synthesis.
实施例Example
聚合物合成例1将天冬氨酸：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应，所得产物1HNMR谱图见图1；在功能单体合成的同时在另一反应釜中加入丁二酸与乙二醇，控制丁二酸：乙二醇＝1:1.2，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行酯化反应。Polymer Synthesis Example 1 Aspartic acid: succinic acid = 1:3 molar ratio was reacted in a reactor, and 200 ppm of antioxidant and heat stabilizer were added, and the temperature was raised to melt under nitrogen protection for reaction. The 1 HNMR spectrum of the obtained product is shown in Figure 1; while the functional monomer was synthesized, succinic acid and ethylene glycol were added to another reactor, and the succinic acid: ethylene glycol was controlled to be 1:1.2, and 200 ppm of antioxidant and heat stabilizer were added, and the temperature was raised to melt under nitrogen protection for esterification reaction.
第二步：将两釜物料共混，升温至160℃，加入200ppm的无水醋酸锌，补加乙二醇，控制体系的二醇：二酸＝1.2:1，酯化1h-2h。Step 2: Blend the materials from the two kettles, heat to 160°C, add 200ppm of anhydrous zinc acetate, add ethylene glycol, control the system's glycol:diacid = 1.2:1, and esterify for 1h-2h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应，获得改性产物。其结构为如下图所示，其中u1范围为100-300之间，u1:u2＝19:1～1:1；u3为0或大于0的整数，聚合物中u3的均值优选地小于2，进一步优选地小于1。
Step 3: After the esterification is completed, 200ppm tetrabutyl titanate is added as a catalyst to carry out polycondensation reaction, the vacuum degree in the kettle is slowly reduced, and the temperature is further raised to 230°C, and the vacuum degree is maintained below 50Pa for 4-6 hours before the reaction is terminated to obtain a modified product. Its structure is shown in the figure below, wherein u1 ranges from 100 to 300, u1:u2=19:1 to 1:1; u3 is an integer of 0 or greater than 0, and the average value of u3 in the polymer is preferably less than 2, and more preferably less than 1.
聚合物合成例2将天冬氨酸：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应。在单体合成结束后，补加剩余的丁二酸和乙二醇，控制天冬氨酸改性链段占比例为10％。控制体系的二醇：二酸＝1.2:1。加入200ppm的醋酸锌后在160℃下进行酯化反应2-4h。Polymer Synthesis Example 2: Aspartic acid: succinic acid = 1:3 molar ratio is reacted in a reactor, and 200ppm of antioxidant and heat stabilizer are added, and the temperature is raised to melt and react under nitrogen protection. After the monomer synthesis is completed, the remaining succinic acid and ethylene glycol are added to control the proportion of aspartic acid modified segments to 10%. The diol: diacid ratio of the control system is 1.2:1. After adding 200ppm of zinc acetate, the esterification reaction is carried out at 160°C for 2-4h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应。Step 3: After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
聚合物合成例3将3-氨基-1,2丙二醇：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应，所得产物1HNMR谱图见图2；在功能单体合成的同时在另一反应釜中加入丁二酸与乙二醇，控制丁二酸：乙二醇＝1:1.2，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行酯化反应。Polymer Synthesis Example 3: 3-amino-1,2-propanediol: succinic acid = 1:3 molar ratio was reacted in a reactor, and 200 ppm of antioxidant and heat stabilizer were added, and the temperature was raised to melt under nitrogen protection for reaction. The 1 HNMR spectrum of the obtained product is shown in Figure 2; while the functional monomer was being synthesized, succinic acid and ethylene glycol were added to another reactor, and the succinic acid: ethylene glycol was controlled to be 1:1.2, and 200 ppm of antioxidant and heat stabilizer were added, and the temperature was raised to melt under nitrogen protection for esterification reaction.
第二步：将两釜物料共混，升温至160℃，加入200ppm的无水醋酸锌，补加乙二醇，控制体系的二醇：二酸＝1.2:1，酯化1h-2h。Step 2: Blend the materials from the two kettles, heat to 160°C, add 200ppm of anhydrous zinc acetate, add ethylene glycol, control the system's glycol:diacid = 1.2:1, and esterify for 1h-2h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应，获得改性产物。其结构为如下所示，其中u1:u4＝19:1～1:1。
Step 3: After the esterification is completed, 200ppm tetrabutyl titanate is added as a catalyst to carry out polycondensation reaction, the vacuum degree in the kettle is slowly reduced, and the temperature is further raised to 230°C, and the vacuum degree is maintained below 50Pa for 4-6 hours before the reaction is terminated to obtain a modified product. Its structure is as shown below, wherein u 1 :u 4 =19:1 to 1:1.
聚合物合成例4将3-氨基-1,2丙二醇：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应。在单体合成结束后，补加剩余的丁二酸和乙二醇，控制功能单体改性链段占比例为10％。控制体系的二醇：二酸＝1.2:1。加入200ppm的醋酸锌后在160℃下进行酯化反应2-4h。Polymer Synthesis Example 4: 3-amino-1,2-propanediol: succinic acid = 1:3 molar ratio was reacted in a reactor, and 200ppm antioxidant and heat stabilizer were added, and the temperature was raised to melt and reacted under nitrogen protection. After the monomer synthesis was completed, the remaining succinic acid and ethylene glycol were added to control the functional monomer modified segment to account for 10%. The diol: diacid of the control system was 1.2:1. After adding 200ppm zinc acetate, the esterification reaction was carried out at 160°C for 2-4h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应。Step 3: After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
聚合物合成例5将2-氨基-1,3丙二醇：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应；在功能单体合成的同时在另一反应釜中加入丁二酸与乙二醇，控制丁二酸：乙二醇＝1:1.2，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行酯化反应。Polymer Synthesis Example 5: 2-amino-1,3-propanediol: succinic acid = 1:3 molar ratio is reacted in a reactor, and 200 ppm of antioxidant and heat stabilizer are added, and the temperature is raised to melt under nitrogen protection for reaction; while the functional monomer is being synthesized, succinic acid and ethylene glycol are added to another reactor, and the succinic acid: ethylene glycol is controlled to be 1:1.2, and 200 ppm of antioxidant and heat stabilizer are added, and the temperature is raised to melt under nitrogen protection for esterification reaction.
第二步：将两釜物料共混，升温至160℃，加入200ppm的无水醋酸锌，补加乙二醇，控制体系的二醇：二酸＝1.2:1，酯化1h-2h。Step 2: Blend the materials from the two kettles, heat to 160°C, add 200ppm of anhydrous zinc acetate, add ethylene glycol, control the system's glycol:diacid = 1.2:1, and esterify for 1h-2h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应，获得改性产物。其结构为如下所示，其中u1:u5＝19:1～1:1。
Step 3: After the esterification is completed, 200ppm tetrabutyl titanate is added as a catalyst to carry out polycondensation reaction, the vacuum degree in the kettle is slowly reduced, and the temperature is further raised to 230°C, and the vacuum degree is maintained below 50Pa for 4-6 hours before the reaction is terminated to obtain a modified product. Its structure is as shown below, wherein u 1 :u 5 =19:1 to 1:1.
聚合物合成例6将2-氨基-1,3丙二醇：丁二酸＝1:3的摩尔比在反应釜中进行反应，并加入200ppm的抗氧剂和热稳定剂，在氮气保护下升温熔融进行反应。在单体合成结束后，补加剩余的丁二酸和乙二醇，控制功能单体改性链段占比例为10％。控制体系的二醇：二酸＝1.2:1。加入200ppm的醋酸锌后在160℃下进行酯化反应2-4h。Polymer Synthesis Example 6: 2-amino-1,3-propanediol: succinic acid = 1:3 molar ratio was reacted in a reactor, and 200ppm antioxidant and heat stabilizer were added, and the temperature was raised to melt and reacted under nitrogen protection. After the monomer synthesis was completed, the remaining succinic acid and ethylene glycol were added to control the functional monomer modified segment to account for 10%. The diol: diacid of the control system was 1.2:1. After adding 200ppm zinc acetate, the esterification reaction was carried out at 160°C for 2-4h.
第三步：酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应。Step 3: After the esterification is completed, add 200ppm tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the kettle, and further increase the temperature to 230°C, maintain the vacuum degree below 50Pa for 4-6 hours before completing the reaction.
对比例Comparative Example
在反应釜中加入丁二酸和乙二醇，控制体系的二醇：二酸＝1.2:1。加入200ppm的醋酸锌后在160℃下进行酯化反应2-4h。在酯化结束后加入200ppm钛酸四丁酯作为催化剂，进行缩聚反应，缓慢降低釜内的真空度，并进一步升温至230℃，维持真空度在50pa以下反应4-6h后结束反应，得到PES树脂。Add succinic acid and ethylene glycol to the reactor, and control the system diol: diacid = 1.2:1. Add 200ppm of zinc acetate and carry out esterification reaction at 160℃ for 2-4h. After the esterification is completed, add 200ppm of tetrabutyl titanate as a catalyst to carry out polycondensation reaction, slowly reduce the vacuum degree in the reactor, and further increase the temperature to 230℃, maintain the vacuum degree below 50Pa for 4-6h, and then terminate the reaction to obtain PES resin.
效果例：Effect example:
效果例1：不同天冬氨酸改性单元比例对PES聚合性能的影响Effect Example 1: Effect of different aspartic acid modified unit ratios on PES polymerization performance
参照聚合物合成例1的方法合成不同改性单元比例的PES聚酯(实施例1-1至实施例1-6)，参照聚合物合成例2合成改性PES聚酯(实施例1-7)。从核磁数据可以看出在化学位移位置8附近无吸收峰，说明聚合物中天冬氨酸已被完全关环，没有裸露的-NH-和-NH2-吸收峰。参见表1实施例1-7，其中，当天冬氨酸改性单元含量为5％时，材料耐热温度为105.2℃(实施例1-1)；当天冬氨酸改性单元占10％时，材料耐热性能达到最佳为110.1℃(实施例1-2)，同时拉伸强度也显著提高。随着改性添加量增加，材料的规整度破坏较大，耐热性有所降低但能在保持较高的拉伸强度下保持较高的断裂伸长率(＞300％)，半结晶时间更长且可通过配比调控，更适合于制备膜材，并且由于减少了丁二酸用量，可以有效降低成本。在天冬氨酸改性单元含量＞70％后，材料规整度提升，但分子量难上升，聚合困难。更多的酰亚胺环可以提供更好的亲水性能，在成本降低的同时可以拓展在亲水性高分子材料领域方面的应用。分步嵌段聚合法比一锅混聚法的性能更佳，这也是规整度更高性能更好的体现。此外探索了当天冬氨酸：丁二酸＝1:1时的改性效果，此时天冬氨酸自聚组分变多且不容易控制，聚合后材料的规整度有所下降，材料热力学性能稍有下降。PES polyesters with different ratios of modified units were synthesized according to the method of polymer synthesis example 1 (Examples 1-1 to 1-6), and modified PES polyesters were synthesized according to polymer synthesis example 2 (Example 1-7). It can be seen from the nuclear magnetic data that there is no absorption peak near the chemical shift position 8, indicating that aspartic acid in the polymer has been completely ring-closed, and there are no exposed -NH- and -NH 2 - absorption peaks. See Table 1 Example 1-7, where when the content of aspartic acid modified units is 5%, the heat resistance temperature of the material is 105.2°C (Example 1-1); when the aspartic acid modified units account for 10%, the heat resistance of the material reaches the best 110.1°C (Example 1-2), and the tensile strength is also significantly improved. With the increase of the amount of modified addition, the regularity of the material is greatly damaged, the heat resistance is reduced, but it can maintain a high elongation at break (>300%) while maintaining a high tensile strength, the half-crystallization time is longer and can be adjusted by ratio, which is more suitable for preparing membrane materials, and because the amount of succinic acid used is reduced, the cost can be effectively reduced. When the content of aspartic acid modified units is greater than 70%, the regularity of the material is improved, but the molecular weight is difficult to increase and polymerization is difficult. More imide rings can provide better hydrophilic properties, which can reduce costs and expand applications in the field of hydrophilic polymer materials. The step-by-step block polymerization method performs better than the one-pot polymerization method, which is also a reflection of higher regularity and better performance. In addition, the modification effect when aspartic acid: succinic acid = 1:1 was explored. At this time, the self-polymerization components of aspartic acid become more and are not easy to control. The regularity of the material after polymerization decreases, and the thermodynamic properties of the material decrease slightly.
效果例2：不同3-氨基-1,2-丙二醇和2-氨基-1,3丙二醇改性单元比例对PES聚合性能的影响Effect Example 2: Effect of different ratios of 3-amino-1,2-propanediol and 2-amino-1,3-propanediol modified units on PES polymerization performance
参照聚合物合成例3和合成例5的方法分别合成不同改性单元比例的PES聚酯(实施例2-1至实施例2-5与实施例3-1至3-5)，参照聚合物合成例4和合成例6合成改性PES聚酯(实施例2-6与实施例3-6)。从核磁数据可以看出在化学位移位置8附近不吸收峰，说明聚合物中的-NH2、-NH-已被完全关。参见表2实施例，其中，当3-氨基-1,2-丙二醇改性单元含量为5％时，材料耐热温度为105.1℃(实施例2-1)；当3-氨基-1,2-丙二醇改性单元占10％时，材料耐热性能达到最佳为108.6℃(实施例2-2)，同时拉伸强度也显著提高。在表三中显示了2-氨基-1,3丙二醇改性的树脂的热力学性能，相较与3-氨基-1,2-丙二醇改性而言，材料的热性能有所下降，这可能是因为3-氨基-1,2-丙二醇改性的聚合物的主链结构和PES一样，这使其主链规整度得到一定的保障，结晶度更高。相较于天冬氨酸改性单元，这两种氨基二醇在热性能的改善上均未超越天冬氨酸改性体系，但在合适添加量下在断裂伸长率方面对材料有一定的增强作用。
PES polyesters with different modified unit ratios were synthesized by referring to the methods of polymer synthesis examples 3 and 5 (Examples 2-1 to 2-5 and Examples 3-1 to 3-5), and modified PES polyesters were synthesized by referring to polymer synthesis examples 4 and 6 (Examples 2-6 and 3-6). It can be seen from the nuclear magnetic resonance data that there is no absorption peak near the chemical shift position 8, indicating that -NH 2 and -NH- in the polymer have been completely closed. See Table 2 for examples, where when the content of 3-amino-1,2-propanediol modified units is 5%, the heat resistance temperature of the material is 105.1°C (Example 2-1); when the 3-amino-1,2-propanediol modified units account for 10%, the heat resistance of the material reaches the best 108.6°C (Example 2-2), and the tensile strength is also significantly improved. Table 3 shows the thermodynamic properties of the resin modified with 2-amino-1,3-propanediol. Compared with the 3-amino-1,2-propanediol modified resin, the thermal properties of the material have decreased. This may be because the main chain structure of the polymer modified with 3-amino-1,2-propanediol is the same as that of PES, which ensures the regularity of the main chain and has a higher crystallinity. Compared with the aspartic acid modified unit, these two amino diols have not surpassed the aspartic acid modified system in improving thermal properties, but they have a certain enhancement effect on the material in terms of elongation at break when added in appropriate amounts.
Claims (10)
A polyester, comprising a polyester main structural unit and a modification unit, wherein the polyester main structural unit comprises a polyester unit obtained by polymerizing a dibasic acid/anhydride/ester used for polymer synthesis and ethylene glycol; the modification unit comprises a first modification unit and/or a second modification unit, wherein the first modification unit comprises a structure of formula (I):
The second modifying unit comprises a structure of formula (II):
The polyester according to claim 1, wherein the structure of the first modifying unit is:
The polyester according to claim 1, wherein the structure of the second modifying unit is:
The diol monomer represented by formula V is:
Aspartic acid monomer shown in formula VI:
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| CN1082065A (en) * | 1992-07-10 | 1994-02-16 | 罗姆和哈斯公司 | Method with preparing polysuccinimides from aspartic acid |
| CN1133047A (en) * | 1993-08-09 | 1996-10-09 | 生物测量公司 | Therapeutic peptide derivatives |
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| CN101193979A (en) * | 2005-06-17 | 2008-06-04 | 伊士曼化工公司 | Transparent oxygen scavenging compositions containing polyesters including cyclobutanediol and articles made therefrom |
| US9403784B1 (en) * | 2015-08-01 | 2016-08-02 | Mark Quang Nguyen | Fumarate compounds, pharmaceutical compositions thereof, and methods of use |
| CN111448231A (en) * | 2017-11-29 | 2020-07-24 | 科思创德国股份有限公司 | Imide-containing polyesters |
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| CN1082065A (en) * | 1992-07-10 | 1994-02-16 | 罗姆和哈斯公司 | Method with preparing polysuccinimides from aspartic acid |
| CN1133047A (en) * | 1993-08-09 | 1996-10-09 | 生物测量公司 | Therapeutic peptide derivatives |
| US20060211843A1 (en) * | 2001-02-06 | 2006-09-21 | Graham Swift | Methods of synthesis of poly(succinimide-aspartate) polysuccinimide or polyaspartate by end capping polymerization |
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