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CN-118755083-B - Bio-based polyamide polyester, and preparation method and application thereof

CN118755083BCN 118755083 BCN118755083 BCN 118755083BCN-118755083-B

Abstract

The invention provides a bio-based polyamide polyester, a preparation method and application thereof. The invention synthesizes the bio-based polyamide polyester by adopting the dibasic acid containing an amide bond, a hydrophobic side chain and a biological carbon atom, wherein the hydrophobic side chain reduces the crystallinity of the polyamide polyester, improves the optical transparency of the polyamide polyester, the amide bond endows the polyamide polyester with excellent temperature resistance, wear resistance and mechanical property, and the ester bond endows the polyamide polyester with good impact resistance, higher modulus and strength. The bio-based polyamide polyester provided by the invention has the advantages of engineering plastic polyamide and general plastic polyester, is a novel bio-based high polymer material, and has potential application value in the fields of packaging materials or solar light panels and the like.

Inventors

  • ZHANG YAJIE
  • MA ZHONGSEN
  • LU YICHAO

Assignees

  • 中国科学院宁波材料技术与工程研究所

Dates

Publication Date
20260512
Application Date
20240607

Claims (10)

  1. 1. The bio-based polyamide polyester is characterized in that the bio-based polyamide polyester is an ordered copolymer with alternating amide bonds and ester bonds, and comprises a structure shown in a formula I: ; A formula I; in the formula I, Y is selected from p-benzene or m-benzene, R 1 、R 2 is independently selected from substituted or unsubstituted alkyl of C 1 ~C 4 , substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic group, R 3 is selected from substituted or unsubstituted alkyl of C 2 ~C 10 or substituted or unsubstituted phenyl, and n is an integer greater than 50; The preparation method of the bio-based polyamide polyester comprises the steps of carrying out polymerization reaction on a mixed reaction system containing diacid, dihydric alcohol and a catalyst under the condition of inert atmosphere, wherein the mixed reaction system firstly carries out first-stage reaction at the temperature of 100-130 ℃, then carries out second-stage reaction after heating to 150-180 ℃, then adjusts the vacuum degree to be below 500 Pa and carries out third-stage reaction after heating to 220-270 ℃, the diacid comprises the diacid with the structure shown in a formula II and contains 30-100 wt% of the diacid with the hydrophobic side chain; ; A formula II; in formula II, Y is selected from p-benzene or m-benzene, R 1 、R 2 is independently selected from substituted or unsubstituted alkyl of C 1 ~C 4 , substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic group; The crystallinity of the bio-based polyamide polyester is below 10%, the transparency is above 85%, and the glass transition temperature is 90-120 ℃.
  2. 2. The biobased polyamide polyester according to claim 1, wherein said biobased polyamide polyester satisfies at least one of the following conditions a-d: a. R 1 、R 2 is independently selected from methyl, propyl, isobutyl, sec-butyl, ethylmethyl sulfide, benzyl, or methylindole groups; b. R 3 is selected from ethyl, butyl, hexyl, decyl, neopentyl, 1, 4-cyclohexanedimethyl or 1, 4-di (ethoxy) phenyl; c. The intrinsic viscosity of the bio-based polyamide polyester is 0.4 dL/g-2.0 dL/g; d. The number average molecular weight of the bio-based polyamide polyester is more than 20000.
  3. 3. The bio-based polyamide polyester as claimed in claim 1, wherein the first stage reaction time is 1 to 3 hours, the second stage reaction time is 1 to 3 hours, and the third stage reaction time is 1 to 6 hours.
  4. 4. The bio-based polyamide polyester of claim 1, wherein the glycol comprises an aliphatic glycol and/or an aromatic glycol.
  5. 5. The bio-based polyamide polyester of claim 4, wherein the glycol comprises one or more of ethylene glycol, butylene glycol, propylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, hydroquinone bishydroxyethyl ether, resorcinol bishydroxyethyl ether, hexylene glycol, and decylene glycol.
  6. 6. The bio-based polyamide polyester of claim 1, wherein the diacid further comprises an aliphatic diacid and/or an aromatic diacid.
  7. 7. The bio-based polyamide polyester of claim 1, wherein the dibasic acid further comprises one or more of adipic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid.
  8. 8. The bio-based polyamide polyester of claim 1, wherein the catalyst comprises one or more of ethylene glycol antimony, antimony trioxide, tetrabutyl titanate, stannous octoate, germanium dioxide.
  9. 9. The bio-based polyamide polyester as claimed in claim 1, wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1:1.1-1:1.5.
  10. 10. Use of the biobased polyamide polyester of any one of claims 1-9 for the preparation of packaging materials or solar panels.

Description

Bio-based polyamide polyester, and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer chemistry, and particularly relates to a bio-based polyamide polyester, and a preparation method and application thereof. Background Polyamide polyester is a polymer containing amide and ester linkages in the molecular chain segment structure. Therefore, the polyester has the impact resistance, higher modulus and strength of polyester, and also has the temperature resistance, wear resistance and mechanical property of polyamide. The polyamide polyester is easy to process due to the existence of ester bonds, can be processed into various profiles in a molten state, and is widely applied to the industries of medicines, biomedicine, telecommunication cables, automobiles and the like. Meanwhile, the existence of the ester bond endows the polyamide polyester with biodegradability, so that the polyamide polyester has wide application prospect. Although the polyester amide has excellent performance and wide applicable range, the market development at the present stage is limited, and the technical process, the production cost and the application field of the polyester amide have a large progress space in the future. For example, the temperature resistance, mechanical properties, etc. of the existing polyamide polyesters still need to be improved, and related polymer materials having higher optical transparency are less developed, thus limiting the wide application of polyamide polyesters in some fields. Disclosure of Invention The main object of the present invention is to provide a novel low-crystallinity bio-based polyamide polyester and a preparation method thereof, wherein the diacid monomer used in the polymerization process comprises a novel diacid monomer (diacid containing hydrophobic side chains and having a structure shown in formula II) synthesized by benzene ring diacid and a compound containing at least one amino group and one carboxyl group with side chain groups, and the polyamide polyester synthesized by the novel low-crystallinity bio-based polyamide polyester has higher mechanical strength and temperature resistance due to the amide bonds, and the transparency of the polymer is improved due to the side chain groups, and the ester bonds are provided for the polyamide polyester with good impact resistance, higher modulus and strength. In order to achieve the aim of the invention, the invention adopts the following technical scheme: in a first aspect, the present invention provides a biobased polyamide polyester comprising a structure of formula I: wherein Y is selected from p-benzene or m-benzene, R 1、R2、R3 is independently selected from substituted or unsubstituted alkyl or substituted or unsubstituted aryl, and n is an integer greater than 50. The alkyl group may be a linear alkyl group, a branched alkyl group or a cycloalkyl group. In some embodiments, R 1、R2 is independently selected from substituted or unsubstituted C 1～C4 alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted aromatic heterocyclic groups. In some embodiments, R 1、R2 is independently selected from methyl, propyl, isopropyl, isobutyl, sec-butyl, ethylmethyl sulfide, benzyl, or methylindole groups. In some embodiments, R 3 is selected from substituted or unsubstituted alkyl of C 2～C10 or substituted or unsubstituted phenyl. In some embodiments, R 3 is selected from ethyl, butyl, hexyl, decyl, neopentyl, 1, 4-cyclohexanedimethyl, or 1, 4-di (ethoxy) phenyl. In some embodiments, the bio-based polyamide polyester has an intrinsic viscosity of 0.4dL/g to 2.0dL/g In some embodiments, the bio-based polyamide polyester has a crystallinity of 10% or less. In some embodiments, the biobased polyamide polyester has a transparency of 85% or greater. In some embodiments, the bio-based polyamide polyester has a glass transition temperature of 90-120 ℃. In some embodiments, the bio-based polyamide polyester has a number average molecular weight greater than 20000. The second aspect of the invention provides a preparation method of bio-based polyamide polyester, comprising the steps of carrying out polymerization reaction on a mixed reaction system containing dibasic acid, dihydric alcohol and a catalyst to obtain the bio-based polyamide polyester, wherein the dibasic acid comprises dibasic acid with a hydrophobic side chain and shown in a formula II; wherein Y is selected from p-benzene or m-benzene, and R 1、R2 is independently selected from substituted or unsubstituted alkyl or substituted or unsubstituted aryl. The dibasic acid with the structure of the formula II contains a hydrophobic side chain and an amide bond, and the polyamide polyester synthesized by the dibasic acid has lower crystallinity, higher transparency and improved water resistance. In some embodiments, the polymerization reaction specifically includes performing a first-stage reaction of the mixed reaction