WO2025108372A1 - Polymère thermorésistant et son procédé de préparation, et utilisation d'un composé diol imide cyclique - Google Patents

Polymère thermorésistant et son procédé de préparation, et utilisation d'un composé diol imide cyclique Download PDF

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WO2025108372A1
WO2025108372A1 PCT/CN2024/133508 CN2024133508W WO2025108372A1 WO 2025108372 A1 WO2025108372 A1 WO 2025108372A1 CN 2024133508 W CN2024133508 W CN 2024133508W WO 2025108372 A1 WO2025108372 A1 WO 2025108372A1
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alkyl
group
aryl
substituted
halogen
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张科春
陈汐
雷腾飞
刘胜阳
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Mint Biotechnologies Co Ltd
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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
    • 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

Definitions

  • the invention relates to the field of polymer materials, and in particular to a temperature-resistant polymer and a preparation method thereof, and application of a cyclic imide diol compound.
  • Polyester materials such as polyethylene terephthalate (PET) have good mechanical properties, processing properties, and wear and corrosion resistance due to their structural regularity and symmetry, and are widely used in various fields of daily life.
  • PET polyethylene terephthalate
  • polyester materials containing alkyl alcohol segments usually have poor heat resistance and cannot be used in high temperature environments.
  • the main way to improve the heat resistance of polyester materials is to use diols with cyclic structures such as 1,4-cyclohexanediol to replace alkyl alcohols.
  • diols with cyclic structures such as 1,4-cyclohexanediol
  • this method is costly, and only using diols with aliphatic cyclic structures to modify polyester materials will lead to reduced mechanical properties of the materials at room temperature. Therefore, providing a polyester material with improved heat resistance and stable mechanical properties is an urgent problem to be solved.
  • the present invention provides a temperature-resistant polymer and a preparation method thereof, and application of a cyclic imide diol compound to solve the problems involved in the background technology.
  • the present invention provides a temperature-resistant polymer.
  • the polymer comprises: a segment (I) containing a cyclic imide, a segment (II) containing a cyclic compound and an optional third segment (III), wherein the segment (I) containing a cyclic imide comprises the following repeating units:
  • n is any integer from 1 to 300;
  • R1 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 or a heterocycloalkyl 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
  • the alkylene group in the definition of R 1 is C1-C10 alkylene group, preferably C1-C6 alkylene group, more preferably C1-C5 alkylene group, and most preferably methylene, 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;
  • R The alkenylene in the definition of R1 is C2-
  • R2 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 at least one of 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 in the definition of R2 is a trivalent C1-C10 alkyl-C6-C10 aryl-C1-C10 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,
  • R2 is selected from at least one of the following structures:
  • * represents the connection site with the O atom
  • ** represents the connection site with the N atom
  • 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 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, C1-C4 alkyl, halogenated C1-C4 alkyl, C6-C12 aryl, C6-C12 aryl-C1-C4 alkyl or halogenated, C1-C4 alkyl-substituted C6-C12 aryl or C6-C12 aryl-C1-C4 alkyl;
  • 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 halogenated, C1-C4 alkyl-substituted C6-C12 aryl-C6-C12 aryl-C1-C4 alkyl;
  • the segment (II) containing a cyclic compound comprises the following repeating units:
  • n is any integer from 1 to 500;
  • Cy is a residue of a cyclic diacid, selected from at least one of C5-C12 arylene groups, alicyclic groups, or heterocyclic groups containing at least one N, O, or S atom; preferably, Cy is C6-C12 arylene groups, which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl, or alkylaryl, C5-C10 cycloalkylene groups, which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl, or alkylaryl, or C5-C10 heteroaryl groups, which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl, or alkylaryl, and contain at least one oxygen atom;
  • the third segment (III) comprises the following repeating units:
  • p and q are any integers from 1 to 150;
  • R3 is the residue of any dibasic acid, preferably the residue of a dibasic acid used for polymer synthesis, for example, the residue of an easily cyclizable dibasic acid as described in R1 ; or R3 is the residue of a dibasic acid that is not easily cyclizable, for example, terephthalic acid, sebacic acid; preferably, R 3 is at least one of a chemical bond, 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 cycloalky
  • R3 is selected from a chemical bond, a straight or branched alkylene or alkenylene group having 2 to 12 carbon atoms optionally interrupted by O atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 5 to 11 carbon atoms, a cycloalkylene group, a cycloalkenyl group or a bridged cycloalkyl group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms, or a combination of the above groups, optionally containing the following substituents: halogen, C1-C4 alkyl, halogenated C1-C4 alkyl, C6-C12 aryl, C6-C12 aryl-C1-C4 alkyl, or a halogenated, C1-C4 alkyl-substituted C6-C12 aryl or C6-C12 aryl-C1-C4 alkyl
  • R4 is selected from C1-C12 alkylene groups which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, alicyclic groups, or heterocyclic groups containing at least one N, O or S atom; preferably, R4 is selected from at least one of C2-C8 alkylene groups which are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, alicyclic groups of C4-C8, or heterocyclic groups containing oxygen atoms of C5-C8.
  • the temperature-resistant polymer further comprises the following repeating unit (IV):
  • m:n is (1-99):(99-1); if the heat-resistant polymer contains a third segment (III), (p+q):(m+n) is (1-80):(99-20).
  • R1 is selected from at least one of C1-C7 alkylene, phenylene, and cycloalkylene; preferably at least one of ethylene, propylene, butylene, pentylene, phenylene, cyclobutylene, cyclopentylene, and cyclohexylene.
  • R1 is most preferably ethylene and propylene.
  • R 2 is at least one selected from a C2-C12 straight-chain alkylene group, a C3-C12 branched alkylene group, a C6-C12 arylene group, and a C3-C12 cycloalkylene group, preferably at least one selected from a propylene group, a butylene group, a pentylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
  • Cy is selected from phenylene, cyclohexylene and furanylene.
  • R3 is at least one selected from phenylene and cyclohexylene.
  • R4 is at least one selected from ethylene, 1,2-dimethylenecyclohexane, 1,3-dimethylenecyclohexane, 1,4-dimethylenecyclohexane, 1,3-diyl-2,2,4,4-tetramethylcyclobutane, (3S,3AR,6R,6AR)-hexahydro-[3,2-B]furan-3,6-diyl).
  • the temperature-resistant polymer has a 14 C/ 12 C ratio greater than 0; or the polymer is synthesized using monomers derived from petroleum.
  • the heat-resistant polymer of the present invention has the following performance parameters:
  • the heat-resistant polymer has the following performance parameters: According to GB/T 19466.2-2004, the Tg of the heat-resistant polyester material is greater than 30°C, preferably greater than 50°C, 70°C, 80°C, 90°C, 100°C, or 110°C.
  • the heat-resistant polymer of the present invention may comprise, according to the combination of the aforementioned segments:
  • Polyester segment containing cyclic imide (I-2) (1) Polyester segment containing cyclic imide (I-2):
  • m2 is any integer from 1 to 300.
  • R 1 , R 2 and R 3 are as defined above.
  • n2 is any integer from 1 to 500.
  • Cy and R 4 are as defined above.
  • R 3 and R 4 are defined as above, preferably, R 3 in formula I-2 is the same as Cy in formula II-2; preferably, R 3 in III-3 is different from Cy in formula II-2, or R 4 in III-3 is different from R 4 in formula II-2.
  • the present invention provides a method for preparing a temperature-resistant polymer, the method comprising the following steps:
  • the temperature-resistant polymer is obtained by esterifying or transesterifying the cyclic imide diol (V), the cyclic diacid (VI) and its esterified product or oligomer, and the optional third monomer or its oligomer (VII);
  • the cyclic imide diol has the following structural formula (V):
  • R 1 and R 2 have the meanings as described above;
  • the cyclic diacid has the following structural formula (VI): HOOC-Cy-COOH (VI);
  • the ester is an ester of the cyclic diacid and a monoalkyl alcohol whose C1-C8 is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl
  • the oligomer is a prepolymer having a degree of polymerization of 1-100 obtained by polycondensation of the cyclic diacid and a polyol whose C1-C8 is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl;
  • the optional third monomer is selected from one or more of the following monomers (1) to (3):
  • R 1 and R 2 in the formula have the meanings as described above, and the precursor or precursor composition thereof is a primary amino diol and a dibasic acid and/or an acid anhydride corresponding to the dibasic acid;
  • the esters are esters of Formula VII-2 and monoalkyl alcohols whose C1-C6 groups are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl or alkylaryl groups
  • the oligomers are prepolymers having a degree of polymerization of 1 to 100 obtained by polycondensation of Formula VII-2 and polyols whose C1-C8 groups are unsubstituted or substituted with substituents selected from halogen, alkyl, aryl, arylalkyl or alkylaryl groups;
  • the cyclic imide diol is prepared from a primary amino diol and a dibasic acid and/or an anhydride corresponding thereto;
  • the primary amino diol is one or more of 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, 4-amino-1,2-butanediol, 3,4-dihydroxyaniline, and 4-(2-aminoethyl)benzene-1,2-ethanediol;
  • R 1 has the meaning as described above, preferably succinic acid, glutaric acid, phthalic acid, 1,2-cyclohexanedicarboxylic acid.
  • the present invention provides a cyclic imide diol compound (V), an amide-containing diol compound (VII-1), a precursor composition of a compound of formula (V) or formula (VII-1), or a prepolymer formed by a compound of formula (V) or formula (VII-1) and a dicarboxylic acid for polymer synthesis, such as a hydroxyl-terminated or carboxyl-terminated prepolymer, in the preparation of a heat-resistant polyester material, wherein the cyclic imide diol monomer has a structural formula as shown in formula (V):
  • the precursor composition is a primary amino diol and a dibasic acid that is easily cyclic and/or an acid anhydride corresponding to the dibasic acid, or a diol monomer containing an amide bond, wherein the primary amino diol is HOR 2 (NH 2 )OH.
  • R1 and R2 are as described above.
  • the content of the cyclic imide diol compound in the heat-resistant polyester material is 0.01-99.9%, preferably 0.01-25%, 5-80%, 10-70%, 20-50% or 75-99.9%.
  • the heat-resistant polyester material also includes a chain segment unit obtained by polymerization of a polyol, and/or a polyacid and an anhydride or ester or oligomer thereof, wherein the polyacid has the following structural formula: HOOC-Cy-COOH (VI) or HOOC-R 3 -COOH (Formula VII-2); the polyol has the following structural formula: H0-R 4 -OH (Formula VII-3).
  • the ester is an ester of a monoalkyl alcohol of formula (VI) or (VII-2) and C1-C8 unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl
  • the oligomer is a prepolymer having a degree of polymerization of 1-100 obtained by condensation of a polyol of formula (VI) or (VII-2) and C1-C8 unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl.
  • the heat-resistant polyester material of the present invention has the following performance parameters: According to GB/T19466.2-2004, the Tg of the heat-resistant polyester material is greater than 30°C, preferably greater than 50°C, 70°C, 80°C, 90°C, 100°C, or 110°C.
  • the invention introduces a cyclic imide structure into the polyester material, thereby promoting the crystallization of the polyester, improving the heat resistance of the polyester material, and maintaining the stability of various mechanical properties of the polymer at room temperature.
  • the present invention first provides a diol monomer containing an imide ring structure, wherein the monomer has the following structure:
  • the cyclic imide diol is prepared from a primary amino diol and a dibasic acid and/or an anhydride corresponding thereto, and the definitions of R 1 and R 2 are as described above.
  • the reaction temperature is determined according to the physicochemical properties of the raw materials and the common technical knowledge in the field. For example, considering the melting points of different dibasic acids, the reaction temperature can be 70-230°C, 80-200°C, 90-160°C, 100-140°C, 110-120°C, etc.
  • reaction time is determined according to the common technical knowledge in the art to maximize the yield of formula (V), such as 1-24 h, 2-15 h, 3-12 h, 4-8 h, 5-6 h, etc.
  • the obtained cyclic imide diol (V) is preferably selected from the following structures:
  • the polymer comprises: a segment (I) containing a cyclic imide, a segment (II) containing a cyclic compound, and optionally a third segment (III) and optionally other segments (IV).
  • the cyclic imide-containing segment (I) comprises a segment obtained by polymerization of the cyclic imide diol (V):
  • m is any integer from 1 to 150, preferably any integer from 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the cyclic imide segment (I) in the temperature-resistant polymer is 0.1-99%, preferably 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
  • the segment (II) containing a cyclic compound is a segment obtained by polymerization of a cyclic diacid HOOC-Cy-COOH (VI) monomer or its ester, or its oligomer:
  • n is any integer from 1 to 150, preferably any integer from 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the segment (II) containing the cyclic compound in the temperature-resistant polymer is 10-99.9%, preferably 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
  • the cyclic diacid (VI) is selected from the following structures:
  • the ester of the cyclic diacid (VI) is selected from the reaction product of the cyclic diacid (VI) and at least one of ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol.
  • the oligomer of the cyclic diacid (VI) is selected from the reaction product of the cyclic diacid (VI) and at least one of ethylene glycol, propylene glycol, butanediol, cyclopentanediol and cyclohexanediol.
  • the third segment (III) is a segment obtained by polymerization of any dibasic acid HOOC-R 3 -COOH (Formula VII-2) and its esters or oligomers:
  • p and q are any integer of 1-150, preferably any integer of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the third segment (III) in the temperature-resistant polymer is 1-80%, preferably 10%, 20%, 30%, 40%, 50%, 60%, 70%.
  • HOOC-R 3 -COOH is selected from oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid.
  • the other segment (IV) is a product of the reaction of a primary amino diol with a dibasic acid and/or an acid anhydride corresponding to the dibasic acid (without forming an imide ring):
  • the polymerized segments :
  • s is any integer from 1 to 150, preferably any integer from 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the other segment (IV) in the temperature-resistant polymer is 0-40%, preferably 1%, 10%, 20%, 30%.
  • the aforementioned primary amino diol is one or more of 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, 4-amino-1,2-butanediol, 3,4-dihydroxyaniline, and 4-(2-aminoethyl)benzene-1,2-ethanediol.
  • the aforementioned dibasic acid is selected from: succinic acid, glutaric acid, adipic acid, pimelic acid, glutaric acid, cyclohexanedicarboxylic acid, phthalic acid and the like.
  • m:n in the temperature-resistant polymer is (1-99):(99-1), preferably (1-75):(75-1), (1-50):(50-1), (1-25):(25-1), (1-10):(10-1), (1-2):(2-1).
  • the temperature-resistant polymer contains a third segment (III), (p+q):(m+n) is (1-80):(99-20), preferably (5-60):(95-40), (10-40):(90-60), (20-30):(80-70).
  • the heat-resistant polymer of the present invention may comprise, according to the combination of the aforementioned segments:
  • Polyester segment containing cyclic imide (I-2) (1) Polyester segment containing cyclic imide (I-2):
  • m2 is any integer from 1 to 300.
  • R 1 , R 2 and R 3 are as defined above.
  • m2 is any integer of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the polyester segment (I-2) containing cyclic imide in the temperature-resistant polymer is 0.1-99%, preferably 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
  • the heat-resistant polymer of the present invention may comprise, according to the combination of the aforementioned segments:
  • n2 is any integer from 1 to 500.
  • Cy and R 4 are as defined above.
  • n2 is any integer of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the polyester segment (II-2) containing cyclic compounds in the temperature-resistant polymer is 10-99.9%, preferably 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
  • the heat-resistant polymer of the present invention may comprise, according to the combination of the aforementioned segments:
  • R 3 and R 4 are as defined above, and R 3 and Cy are different.
  • p2 is any integer of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140.
  • the molar percentage of the third polyester segment (III-3) in the temperature-resistant polymer is 1-80%, preferably 10%, 20%, 30%, 40%, 50%, 60%, 70%.
  • the temperature for preparing the heat-resistant polymer is determined according to the physical and chemical properties of the raw materials and the general technical knowledge of esterification reactions in the art.
  • the reaction temperature can be 100-300°C, 120-260°C, 150-230°C, 180-200°C, etc.
  • the reaction time for preparing the temperature-resistant polymer is determined according to the polymer conversion rate required and based on common technical knowledge in the art, such as 1-24h, 2-15h, 3-12h, 4-8h, 5-6h, etc.
  • the heat-resistant polymer of the present invention has good heat resistance, specifically, it can be reflected in having an increased glass transition temperature (Tg).
  • Tg glass transition temperature
  • the increased Tg means that the Tg of the heat-resistant polymer of the present invention after copolymerization with the addition of the cyclic imide diol monomer is increased relative to the polymer without the cyclic imide diol repeating unit, and specifically can be increased by 1-100%, 5-75%, 10-50%, 15-30%, or 20-25%.
  • the heat-resistant polymer of the present invention can have a Tg greater than 30°C, 50°C, 70°C, 80°C, 90°C, 100°C, or 110°C, and the upper limit of Tg can be any value, preferably less than 300°C, 250°C, 200°C, 150°C, 120°C, etc.
  • the structural unit also known as the monomer unit, is the smallest indivisible structural unit included in the polymer. It has the same structure as the monomer except for the functional group that undergoes polymerization.
  • the binary copolymer contains two different structural units and can be divided into random copolymers, alternating copolymers or block copolymers, etc.
  • the polymer of the present invention is preferably a random copolymer.
  • the amino-containing diol in the present invention has the following structure: OH- 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 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.
  • 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 dicarbox
  • 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
  • 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 promoting the synthesis of biodegradable structural units.
  • it can be any dicarboxylic acid different from HOOC-R 2 -COOH, for example, it can be the easily cyclized dicarboxylic acid described above for HOOC-R 2 -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.
  • 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 oxalic acid, 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 enedioic acid, phthalic acid, hexahydrophthalic acid, enedioic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglu
  • 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, OH-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.
  • C 1-6 alkyl includes C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 1-6 , C 1-5 , C 1-4 , C 1-3 , C 1-2 , C 2-6 , C 2-5 , C 2-4 , C 2-3, C 3-6 , C 3-5 , C 3-4 , C 4-6 , C 4-5 , and C 5-6 alkyl.
  • alkyl refers to a linear or branched saturated hydrocarbon group having a corresponding number of carbon atoms
  • C 1-6 alkyl refers to a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms.
  • C 1-4 alkyl and C 1-2 alkyl are preferred.
  • C 1-6 alkyl examples include: methyl (C 1 ), ethyl (C 2 ), n-propyl (C 3 ), isopropyl (C 3 ), n-butyl (C 4 ), tert-butyl (C 4 ), sec-butyl (C 4 ), isobutyl (C 4 ), n-pentyl (C 5 ), 3-pentyl (C 5 ), pentyl (C 5 ), neopentyl (C 5 ), 3-methyl-2-butyl (C 5 ), tert-pentyl (C 5 ) and n-hexyl (C 6 ).
  • C 1-6 alkyl also includes heteroalkyl groups in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus).
  • the alkyl group may be optionally substituted by one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
  • C6-24 alkyl is preferred, such as C6 , C7, C8 , C9 , C10 , C11 , C12 , C13 , C14 , C15, C16, C17, C18 , C19 , C20 , C21 , C22 , C23 , C24 , and preferably a straight chain alkyl.
  • alkenyl refers to a straight or branched hydrocarbon group having corresponding carbon atoms and at least one carbon-carbon double bond
  • C2-6 alkenyl refers to a straight or branched hydrocarbon group having 2 to 6 carbon atoms and at least one carbon-carbon double bond.
  • C2-4 alkenyl is preferred.
  • C2-6 alkenyl examples include: vinyl ( C2 ), 1-propenyl ( C3 ), 2-propenyl ( C3 ), 1-butenyl ( C4 ), 2-butenyl ( C4 ), butadienyl ( C4 ), pentenyl ( C5 ), pentadienyl ( C5 ), hexenyl ( C6 ), and the like.
  • the term " C2-6 alkenyl” also includes heteroalkenyl, wherein one or more (e.g., 1, 2, 3 or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus).
  • the alkenyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents or 1 substituent.
  • "C 6-24 alkenyl” is preferred, such as C 6 , C 7 , C 8 , C 9, C 10 , C 11 , C 12, C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , and preferably a straight-chain alkenyl, preferably containing multiple olefinic bonds.
  • C 2-6 alkynyl refers to a straight or branched hydrocarbon group having 2 to 6 carbon atoms, at least one carbon-carbon triple bond, and optionally one or more carbon-carbon double bonds. In some embodiments, C 2-4 alkynyl is preferred. Examples of C 2-6 alkynyl include, but are not limited to, ethynyl (C 2 ), 1-propynyl (C 3 ), 2-propynyl (C 3 ), 1-butynyl (C 4 ), 2-butynyl (C 4 ), pentynyl (C 5 ), hexynyl (C 6 ), and the like.
  • C 2-6 alkynyl also includes heteroalkynyl groups, in which one or more (e.g., 1, 2, 3 or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus).
  • Alkynyl groups may be optionally substituted by one or more substituents, for example, by 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
  • C6-24 alkenyl is preferred, such as C6 , C7, C8 , C9 , C10 , C11 , C12, C13, C14 , C15 , C16 , C17 , C18 , C19 , C20 , C21 , C22 , C23 , C24 , and preferably a straight chain alkynyl.
  • C 1-10 alkylene refers to a divalent group formed by removing another hydrogen of a C 1-10 alkyl group, and may be substituted or unsubstituted. In some embodiments, C 1-4 alkylene, C 2-4 alkylene, and C 1-3 alkylene are preferred.
  • the unsubstituted alkylene includes, but is not limited to, methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), butylene (-CH 2 CH 2 CH 2 CH 2 -), pentylene (-CH 2 CH 2 CH 2 CH 2 CH 2 -), hexylene (-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -), and the like.
  • substituted alkylene groups for example, substituted alkylene groups with one or more alkyl(methyl) groups, include, but are not limited to, substituted methylene groups (—CH(CH 3 )—, —C(CH 3 ) 2 —), substituted ethylene groups (—CH(CH 3 )CH 2 —, —CH 2 CH(CH 3 )—, —C(CH 3 ) 2 CH 2 —, —CH 2 C(CH 3 ) 2 — ), substituted propylene groups (—CH(CH 3 )CH 2 CH 2 —, —CH 2 CH(CH 3 )CH 2 —, —CH 2 CH 2 CH(CH 3 )—, —C(CH 3 ) 2 CH 2 CH 2 —, —CH 2 C(CH 3 ) 2 CH 2 —, —CH 2 CH 2 C(CH 3 ) 2 —), and the like.
  • substituted methylene groups —CH(CH 3 )—, —C(CH 3 ) 2 —
  • alkenylene groups substituted with one or more alkyl(methyl) groups include, but are not limited to, substituted ethylene groups (—C(CH 3 ) ⁇ CH—, —CH ⁇ C(CH 3 )—), substituted propenylene groups (—C(CH 3 ) ⁇ CHCH 2 —, —CH ⁇ C(CH 3 )CH 2 —, —CH ⁇ CHCH(CH 3 )—, —CH ⁇ CHC(CH 3 ) 2 —, —CH(CH 3 )—CH ⁇ CH—, —C(CH 3 ) 2 —CH ⁇ CH—, —CH 2 —C(CH 3 ) ⁇ CH—, —CH 2 —CH ⁇ C(CH 3 )—), and the like.
  • C 2-10 alkynylene refers to a divalent group formed by removing another hydrogen of a C 2-10 alkynyl group, and may be substituted or unsubstituted. In some embodiments, C 2-4 alkynylene is particularly preferred. Exemplary alkynylene groups include, but are not limited to, ethynylene (-C ⁇ C-), substituted or unsubstituted propynylene (-C ⁇ CCH 2 -), and the like.
  • C 0-6 alkylene means a chemical bond as well as the above-mentioned “C 1-6 alkylene”
  • C 0-4 alkylene means a chemical bond as well as the above-mentioned “C 1-4 alkylene”.
  • Halo or "halogen” refers to fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
  • C 1-6 haloalkyl refers to the above-mentioned "C 1-6 alkyl” substituted by one or more halogen groups.
  • C 1-4 haloalkyl is particularly preferred, more preferably C 1-2 haloalkyl.
  • Exemplary haloalkyls include, but are not limited to: -CF 3 , -CH 2 F, -CHF 2 , -CHFCH 2 F, -CH 2 CHF 2 , -CF 2 CF 3 , -CCl 3 , -CH 2 Cl, -CHCl 2 , 2,2,2-trifluoro-1,1-dimethyl-ethyl, and the like.
  • the haloalkyl group may be substituted at any available attachment point, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
  • C 3-10 cycloalkyl refers to a non-aromatic cyclic hydrocarbon group having 3 to 10 ring carbon atoms and zero heteroatoms, optionally containing 1, 2 or 3 double bonds or triple bonds. In some embodiments, C 5-10 cycloalkyl, C 3-7 cycloalkyl and C 3-6 cycloalkyl are particularly preferred, more preferably C 5-7 cycloalkyl and C 5-6 cycloalkyl.
  • Cycloalkyl also includes a ring system in which the above cycloalkyl ring is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the cycloalkyl ring, and in such a case, the number of carbons continues to represent the number of carbons in the cycloalkyl system. Cycloalkyl also includes the above cycloalkyl rings in which the substituents on any non-adjacent carbon atoms are connected to form a bridged ring, together forming a polycycloalkane sharing two or more carbon atoms.
  • Cycloalkyl also includes the above cycloalkyl rings in which the substituents on the same carbon atom are connected to form a ring, together forming a polycycloalkane sharing one carbon atom.
  • Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl (C 3 ), cyclopropenyl (C 3 ), cyclobutyl (C 4 ), cyclobutenyl (C 4 ), cyclopentyl (C 5 ), cyclopentenyl (C 5 ) , cyclohexyl (C 6 ), cyclohexenyl (C 6 ), cyclohexadienyl (C 6 ), cycloheptyl (C 7 ), cycloheptenyl (C 7 ), cycloheptadienyl (C 7 ), cycloheptatrienyl (C 7 ), etc.
  • the cycloalkyl group may be optionally substitute
  • C 3-10 cycloalkylene refers to a divalent group formed by removing another hydrogen of a C 3-10 cycloalkyl group, and may be substituted or unsubstituted.
  • C 3-6 cycloalkylene and C 3-4 cycloalkylene are particularly preferred, and cyclopropylene is particularly preferred.
  • 3--10 membered heterocyclyl refers to a saturated or unsaturated radical of a 3- to 10-membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, sulfur, boron, phosphorus and silicon, and optionally containing 1, 2 or 3 double or triple bonds.
  • the point of attachment may be a carbon or nitrogen atom as long as valence permits.
  • a 5-10 membered heterocyclyl is preferred, which is a 5-10 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms; in some embodiments, a 3-7 membered heterocyclyl is preferred, which is a 3-7 membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms; a 5-7 membered heterocyclyl is preferred, which is a 5-7 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; a 3-6 membered heterocyclyl is preferred, which is a 3-6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; a 4-6 membered heterocyclyl is preferred, which is a 4-6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; and a 5-6
  • Heterocyclyl also includes a ring system in which the above-mentioned heterocyclyl ring is fused with one or more cycloalkyl groups, wherein the point of attachment is on the heterocyclyl ring, or a ring system in which the above-mentioned heterocyclyl ring is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring; and in such a case, the number of ring members continues to represent the number of ring members in the heterocyclyl ring system.
  • Heterocyclyl also includes the above-mentioned heterocyclyl ring, wherein the substituents on any non-adjacent carbon or nitrogen atoms are connected to form a bridge ring, together forming a polycyclic heteroalkane sharing two or more carbon or nitrogen atoms.
  • Heterocyclyl also includes the above-mentioned heterocyclyl ring, wherein the substituents on the same carbon atom are connected to form a ring, together forming a polycyclic heteroalkane sharing one carbon atom.
  • Exemplary 3-membered heterocyclyls containing one heteroatom include, but are not limited to: aziridine, oxadiazine, thiorenyl.
  • Exemplary 4-membered heterocyclyls containing one heteroatom include, but are not limited to: azetidinyl, oxadiazine and thiazine.
  • Exemplary 5-membered heterocyclic groups containing one heteroatom include, but are not limited to, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione.
  • Exemplary 5-membered heterocyclic groups containing two heteroatoms include, but are not limited to, pyrazolidinyl, dioxolanyl, oxasulfuranyl, disulfuranyl, and oxazolidin-2-one.
  • Exemplary 5-membered heterocyclic groups containing three heteroatoms include, but are not limited to, triazolinyl, oxadiazolinyl, and thiadiazolinyl.
  • Exemplary 6-membered heterocyclic groups containing one heteroatom include, but are not limited to, piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl.
  • Exemplary 6-membered heterocyclic groups containing two heteroatoms include, but are not limited to, piperazinyl, morpholinyl, dithianyl, and dioxanyl.
  • Exemplary 6-membered heterocyclic groups containing three heteroatoms include, but are not limited to, hexahydrotriazine (triazinanyl).
  • Exemplary 7-membered heterocyclic groups containing one heteroatom include, but are not limited to, azepanyl, oxepane and thiepanyl.
  • Heterocyclic groups also include the above heterocyclic groups sharing one or two atoms with a cycloalkyl, heterocyclic, aryl or heteroaryl group to form a bridged ring or spirocycle, and the shared atoms may be carbon or nitrogen atoms as long as the valence permits.
  • Heterocyclyl also includes the above-mentioned heterocyclyl and heterocyclyl groups which may be optionally substituted by one or more substituents, for example, substituted by 1 to 5 substituents, 1 to 3 substituents or 1 substituent.
  • C 6-10 aryl refers to a monocyclic or polycyclic (e.g., bicyclic) 4n+2 aromatic ring system (e.g., having 6 or 10 ⁇ electrons shared in a cyclic arrangement) having 6-10 ring carbon atoms and zero heteroatoms.
  • the aryl group has six ring carbon atoms ("C 6 aryl”; e.g., phenyl).
  • the aryl group has ten ring carbon atoms ("C 10 aryl”; e.g., naphthyl, e.g., 1-naphthyl and 2-naphthyl).
  • Aryl also includes ring systems in which the above aryl ring is fused to one or more cycloalkyl or heterocyclic groups, and the point of attachment is on the aryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the aryl ring system.
  • the aryl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
  • 5-14 membered heteroaryl refers to a group of a 5-14 membered monocyclic or bicyclic 4n+2 aromatic ring system (e.g., having 6, 10, or 14 ⁇ electrons shared in a cyclic arrangement) having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur.
  • the point of attachment may be a carbon or nitrogen atom as long as the valence permits.
  • Heteroaryl bicyclic ring systems may include one or more heteroatoms in one or both rings.
  • Heteroaryl also includes a ring system in which the above-mentioned heteroaryl ring is fused to one or more cycloalkyl or heterocyclic groups, and the point of attachment is on the heteroaryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the heteroaryl ring system.
  • a 5-10 membered heteroaryl is preferred, which is a 5-10 membered monocyclic or bicyclic 4n+2 aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms.
  • 5-6 membered heteroaryls are particularly preferred, which are 5-6 membered monocyclic or bicyclic 4n+2 aromatic ring systems having ring carbon atoms and 1-4 ring heteroatoms.
  • Exemplary 5-membered heteroaryls containing one heteroatom include, but are not limited to, pyrrolyl, furanyl, and thienyl.
  • Exemplary 5-membered heteroaryls containing two heteroatoms include, but are not limited to, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl.
  • Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to, triazinyl and tetrazinyl, respectively.
  • Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to, azacycloheptatrienyl, oxacycloheptatrienyl, and thiacycloheptatrienyl.
  • Exemplary 5,6-bicyclic heteroaryl groups include, but are not limited to, indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothienyl, isobenzothienyl, benzofuranyl, benzisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, indazinyl, and purinyl.
  • Exemplary 6,6-bicyclic heteroaryl groups include, but are not limited to, naphthyridinyl, pteridinyl, quinolyl, isoquinolyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.
  • a heteroaryl group can be optionally substituted with one or more substituents, for example, with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
  • Hydroalkyl refers to an alkyl group substituted with one or more hydroxy groups.
  • Alkoxy refers to the oxygen ether form of a straight or branched chain alkyl group, ie, -O-alkyl. Similarly, “methoxy” refers to -O- CH3 .
  • the divalent groups formed by removing another hydrogen from the above-defined alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl groups are collectively referred to as "subunits".
  • the ring-forming groups such as cycloalkyl, heterocyclyl, aryl and heteroaryl groups are collectively referred to as "cyclyls”.
  • Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl groups and the like as defined herein are optionally substituted groups.
  • each of Raa is independently selected from alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two Ra groups combine to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rdd groups;
  • each of R cc is independently selected from hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R cc groups combine to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently substituted with 0, 1, 2, 3, 4 or 5 R dd groups;
  • Each of R ee is independently selected from alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, and heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R gg groups;
  • each of Rff is independently selected from hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two Rff groups combine to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently substituted with 0, 1, 2, 3, 4 or 5 Rgg groups;
  • the repeating unit of the present invention refers to an atomic group, which is a residue of a reaction product after polymerization of one or more monomers.
  • the brackets in the repeating unit indicate that there are multiple residues of the reaction products in the brackets in the polymer, which may be connected or not connected, and the numbers outside the brackets, such as m, n, p, q, s, indicate the number of the residues of the reaction products in the brackets present on an average polymer chain in the temperature-resistant polymer.
  • the percentage (%) in the present invention refers to molar percentage.
  • the fully vacuum-dried terephthalic acid and ethylene glycol 1 are added to the reactor B at a molar ratio of 1:1.2, the materials are mixed at room temperature, and the air in the reactor is fully replaced with nitrogen. The mixture is stirred and heated to melt in a nitrogen atmosphere. When the temperature reaches 170°C, 100ppm zinc acetate is added, and the reaction is maintained at 190°C and 300KPa until the fraction reaches 97% of the theoretical distillate.
  • the pressure is restored to normal, and ethylene glycol 2 is added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 is 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the temperature is raised to 250°C, and pre-condensed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the pressure is restored to normal, and ethylene glycol 2 is added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 is 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the temperature is raised to 250°C, and pre-condensed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • Phthalic acid and ethylene glycol 1 which were fully vacuum dried were added into reactor B at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen, and the temperature was stirred and melted in a nitrogen atmosphere. When the temperature reached 170°C, 100ppm zinc acetate was added, and the temperature was kept at 190°C and 300KPa for reaction until the fraction reached 97% of the theoretical distillation amount.
  • the pressure was restored to normal, and ethylene glycol 2 was added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 was 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate were added at the same time, the temperature was raised to 250°C, and pre-condensed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the pressure is restored to normal, and ethylene glycol 2 is added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 is 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the temperature is raised to 250°C, and pre-condensed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the pressure is restored to normal, and ethylene glycol 2 is added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 is 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the temperature is raised to 250°C, and pre-condensed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the fully vacuum-dried terephthalic acid and 1,3-propylene glycol 1 were added to the reactor B at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen. The mixture was stirred and heated to melt in a nitrogen atmosphere. When the temperature reached 170°C, 100ppm zinc acetate was added, and the reaction was maintained at 190°C and 300KPa until the fraction reached 97% of the theoretical distillate.
  • the pressure was restored to normal, and ethylene glycol 2 was added (the molar ratio of ethylene glycol 1 to ethylene glycol 2 was 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate were added at the same time.
  • the temperature was raised to 250°C, and the pre-condensation was performed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the fully vacuum-dried terephthalic acid and 1,4-butanediol1 were added to the reactor B at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen. The mixture was stirred and heated to melt in a nitrogen atmosphere. When the temperature reached 170°C, 100ppm zinc acetate was added, and the reaction was maintained at 190°C and 300KPa until the fraction reached 97% of the theoretical distillate.
  • the pressure was restored to normal, and ethylene glycol2 was added (the molar ratio of ethylene glycol1 to ethylene glycol2 was 1:0.2), and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate were added at the same time.
  • the temperature was raised to 250°C, and the pre-condensation was performed at -0.08MPa for 1h to obtain a cyclic polyester oligomer.
  • the fully vacuum-dried isophthalic acid and ethylene glycol were preheated and melted, and then added into the reactor C at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen, and the temperature was stirred and melted in a nitrogen atmosphere.
  • the temperature reached 170°C, 200ppm zinc acetate was added, and the temperature was maintained at 230°C and 300KPa pressure until the fraction reached 97% of the theoretical distillate.
  • the fully vacuum-dried phthalic acid and ethylene glycol were preheated and melted, and then added into the reactor C at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen, and the temperature was stirred and melted in a nitrogen atmosphere.
  • the temperature reached 170°C, 200ppm zinc acetate was added, and the temperature was maintained at 230°C and 300KPa pressure until the fraction reached 97% of the theoretical distillate.
  • the fully vacuum-dried terephthalic acid and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were preheated and melted, and then added into the reactor C at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen, and the temperature was stirred and melted in a nitrogen atmosphere. When the temperature reached 170°C, 200ppm zinc acetate was added, and the temperature was maintained at 230°C and 300KPa for reaction until the fraction reached 97% of the theoretical distillate.
  • the fully vacuum-dried terephthalic acid and 1,4-cyclohexanedimethanol were preheated and melted, and then added into the reactor C at a molar ratio of 1:1.2, the materials were mixed at room temperature, and the air in the reactor was fully replaced with nitrogen, and the temperature was stirred and melted in a nitrogen atmosphere.
  • the temperature reached 170°C, 200ppm zinc acetate was added, and the temperature was maintained at 230°C and 300KPa pressure until the fraction reached 97% of the theoretical distillate.
  • Example 1 On the basis of Example 1, the types of raw materials and feed ratios were changed, and polymers H-2 to H-22 were prepared in the same manner, as shown in Table 1.
  • ethylene glycol (BD-1)2 Normal pressure is restored, 0.24 mole portions of ethylene glycol (BD-1)2 are added, and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the mixture is heated to 250°C and pre-condensed at -0.08MPa for 1h. The temperature is then continued to be raised, and the vacuum degree is continuously and slowly increased. Finally, the mixture is subjected to condensation reaction for 6h at a temperature of 260°C and a vacuum degree of ⁇ 100Pa to obtain a non-heat-resistant polymer.
  • ethylene glycol (BD-1)2 Normal pressure is restored, 0.24 molar portions of ethylene glycol (BD-1)2 are added, and 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the temperature is raised to 220°C, and pre-condensation is performed at -0.08MPa for 1h; the temperature is further raised to 260°C, and the vacuum is slowly evacuated to ⁇ 100Pa, and the condensation reaction is performed for 6h to obtain a non-heat-resistant polymer.
  • BD-2 1,4-butanediol
  • 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate are added at the same time.
  • the mixture is heated to 250°C and pre-condensed at -0.08MPa for 1h.
  • the temperature is then continued to be raised, and the vacuum degree is continuously and slowly increased.
  • the polycondensation reaction is carried out at 260°C and the vacuum degree is less than 100Pa for 6h to obtain a non-heat-resistant polymer.
  • the pressure was restored to normal, 500ppm n-butyl titanate, 100ppm tetraethyl silicate and 100ppm triphenyl phosphate were added, the temperature was raised to 250°C, and pre-condensation was carried out at -0.08MPa for 1h; the temperature was then continued to be raised, and the vacuum degree was continuously and slowly increased. Finally, the polycondensation reaction was carried out at a temperature of 270°C and a vacuum degree of ⁇ 100Pa for 6h to obtain a non-heat-resistant polymer.
  • the heat-resistant polymer of the present invention has good heat resistance and substantially unreduced mechanical properties relative to polymers that do not contain cyclic imide repeating units.
  • H-10 and N-2, H-12 and N-3, H-21 and N-4 it can be seen that for different polymer materials, after adding cyclic imide, their heat resistance is improved, and the material still has good mechanical properties to meet the needs of various application scenarios.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention divulgue un polymère thermorésistant et son procédé de préparation, et une utilisation d'un composé diol imide cyclique, appartenant au domaine des matériaux macromoléculaires. Le polymère comprend un segment (I) contenant un imide cyclique, un segment (II) contenant un composé cyclique et un troisième segment (III) facultatif ; le segment (I) contenant un imide cyclique peut améliorer la résistance à la chaleur du polymère, et sa structure est telle que R1 est un résidu d'un acide dibasique facilement cyclisé et que R2 est un résidu d'un diol contenant un groupe amino. Le polymère thermorésistant de la présente invention présente une meilleure résistance à la chaleur et de bonnes propriétés mécaniques.
PCT/CN2024/133508 2023-11-24 2024-11-21 Polymère thermorésistant et son procédé de préparation, et utilisation d'un composé diol imide cyclique Pending WO2025108372A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760124A (en) * 1985-07-25 1988-07-26 Teijin Limited Crystalline polyester-imide, process for production thereof, and use thereof
US4861861A (en) * 1986-08-19 1989-08-29 Ciba-Geigy Corporation Saturated polyesters containing imide groups and terminal carboxyl groups
JP2005314601A (ja) * 2004-04-30 2005-11-10 Toyobo Co Ltd 共重合ポリエステルならびに共重合ポリエステルの製造方法
JP2005336413A (ja) * 2004-05-31 2005-12-08 Mitsui Chemicals Inc ポリヒドロキシカルボン酸共重合体
CN113631632A (zh) * 2019-01-24 2021-11-09 Isp投资有限公司 基于二羟基内酰胺的聚合物、其组合物及其应用
CN115028819A (zh) * 2022-05-13 2022-09-09 大连大学 一种衣康酸基双吡咯烷酮二羧酸及其有关聚酯的制备方法
CN116199873A (zh) * 2021-12-01 2023-06-02 中国科学院大连化学物理研究所 一种共聚酯及其制备方法与应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760124A (en) * 1985-07-25 1988-07-26 Teijin Limited Crystalline polyester-imide, process for production thereof, and use thereof
US4861861A (en) * 1986-08-19 1989-08-29 Ciba-Geigy Corporation Saturated polyesters containing imide groups and terminal carboxyl groups
JP2005314601A (ja) * 2004-04-30 2005-11-10 Toyobo Co Ltd 共重合ポリエステルならびに共重合ポリエステルの製造方法
JP2005336413A (ja) * 2004-05-31 2005-12-08 Mitsui Chemicals Inc ポリヒドロキシカルボン酸共重合体
CN113631632A (zh) * 2019-01-24 2021-11-09 Isp投资有限公司 基于二羟基内酰胺的聚合物、其组合物及其应用
CN116199873A (zh) * 2021-12-01 2023-06-02 中国科学院大连化学物理研究所 一种共聚酯及其制备方法与应用
CN115028819A (zh) * 2022-05-13 2022-09-09 大连大学 一种衣康酸基双吡咯烷酮二羧酸及其有关聚酯的制备方法

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