Search

CN-121975122-A - Polythioester with main chain containing carbon-carbon double bonds, and preparation method and application thereof

CN121975122ACN 121975122 ACN121975122 ACN 121975122ACN-121975122-A

Abstract

The invention discloses polythioester with a main chain containing carbon-carbon double bonds, which is of a full alternating copolymerization structure, each repeating unit contains sulfur element and carbon-carbon double bonds, and has a structural general formula shown in the following formula (I) or (II), wherein n is selected from 1-500, R 1 is selected from hydrogen, methyl or isobutyl, R 2 、R 3 、R 4 is independently selected from hydrogen or methyl, R 5 is selected from hydrogen, methyl, ethyl or phenyl, R 6 is selected from hydrogen or methyl. (I); (II).

Inventors

  • ZHANG XINGHONG
  • LIN SHIQI
  • ZHANG CHENGJIAN
  • ZHANG XUN
  • ZHANG XUYANG

Assignees

  • 浙江大学

Dates

Publication Date
20260505
Application Date
20260121

Claims (10)

  1. 1. The polythioester with carbon-carbon double bonds in the main chain is characterized by having a fully alternating copolymerization structure, wherein each repeating unit contains sulfur and carbon-carbon double bonds, and the structural general formula is shown as the following formula (I) or (II): (I); (II); wherein n is selected from 1 to 500; R 1 is selected from hydrogen, methyl or isobutyl; r 2 、R 3 、R 4 is independently selected from hydrogen or methyl; R 5 is selected from hydrogen, methyl, ethyl, or phenyl; R 6 is selected from hydrogen or methyl.
  2. 2. The polythioester having a main chain containing carbon-carbon double bonds according to claim 1, wherein the number average molecular weight is 1 to 100 kg/mol and the PDI is 1.2 to 3.5.
  3. 3. The polythioester with a main chain containing carbon-carbon double bonds according to claim 1, wherein the structural formula is shown as the following formulas (1) - (11): (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)。
  4. 4. a method for producing the polythioester having a main chain containing carbon-carbon double bonds according to any one of claims 1 to 3, characterized by: taking conjugated aldehyde and thiocyclic anhydride as raw materials, and taking Lewis base as a catalytic system to perform alternating copolymerization; The conjugated aldehyde is selected from one or more of acrolein, crotonaldehyde, pentenal, 2-methylacrylic aldehyde, cinnamaldehyde and 3-methyl-2-butenal; the thiocyclic anhydride is selected from five-membered thiocyclic anhydride and/or six-membered thiocyclic anhydride.
  5. 5. The method for producing a polythioester having a main chain containing carbon-carbon double bonds according to claim 4, wherein: The thiocyclic anhydride is selected from one or more of thiosuccinic anhydride, thioglutaric anhydride, thio 3-methyl glutaric anhydride, thio 3, 3-dimethyl glutaric anhydride, thio 2, 2-dimethyl glutaric anhydride and thio 3-isobutyl glutaric anhydride; The Lewis base is selected from one or more of triethylamine, tetraethylethylenediamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, pyridine, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylboron/bis (triphenylphosphine) ammonium chloride, tripropylphosphorus, tri-tert-butylphosphorus, potassium tert-butoxide, sodium tert-butoxide and phosphazene base catalysts.
  6. 6. The method for producing a polythioester having a main chain containing carbon-carbon double bonds according to claim 4, wherein: the molar ratio of the conjugated aldehyde to the thiocyclic anhydride is (0.1-10): 1; the mol ratio of the catalyst to the thiocyclic anhydride is 1 (5-100000); The alternating copolymerization is carried out at a reaction temperature of 0-100 ℃ and under autogenous pressure for 0.1-24 hours.
  7. 7. The method for producing a polythioester having a main chain containing carbon-carbon double bonds according to claim 4, wherein: The conjugated aldehyde is selected from acrolein and/or 2-methylacrolein; The thiocyclic anhydride is selected from thioglutaric anhydride; the lewis base is selected from triethylamine and/or 4-dimethylaminopyridine.
  8. 8. The method for producing a polythioester having a main chain containing carbon-carbon double bonds as recited in claim 7, wherein: The reaction temperature is 0-40 ℃; the molar ratio of the conjugated aldehyde to the thiocyclic anhydride is (1-3): 1; The molar ratio of the Lewis base to the thiocyclic anhydride is 1 (100-100000).
  9. 9. A method for preparing conjugated aldehyde and thiocyclic anhydride by recycling degradation, which is characterized in that the polythioester with main chain containing carbon-carbon double bonds according to any one of claims 1-3 is mixed with a catalyst, and the conjugated aldehyde and the thiocyclic anhydride are recycled by heating degradation.
  10. 10. The method for preparing conjugated aldehyde and thiocyclic anhydride by recycling and degradation according to claim 9, characterized in that: The catalyst is selected from organotin catalysts; the dosage of the catalyst is 2-5% of the mass of polythioester with carbon-carbon double bonds in the main chain; the temperature of heating degradation is 150-180 ℃; the liquid conjugated aldehyde is recovered by distillation and the solid thiocyclic anhydride is recovered by sublimation.

Description

Polythioester with main chain containing carbon-carbon double bonds, and preparation method and application thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to polythioester with a main chain containing carbon-carbon double bonds, and a preparation method and application thereof. Background Polyesters are a common polymer material and generally classified into two major classes, namely aromatic polyesters and aliphatic polyesters. Aromatic polyesters, such as polyethylene terephthalate (PET), are widely used in the manufacture of fibers, blow molded bottles and other packaging materials due to their good mechanical strength and barrier properties, and are produced in large quantities. Aliphatic polyesters have better biocompatibility and relatively easy hydrolysis, and can be degraded into small molecules in the environment, so that the aliphatic polyesters are environment-friendly high polymer materials, and meanwhile, the aliphatic polyesters are widely focused in recent years as synthetic raw materials of various renewable chemicals and potential substitutes of petroleum-based polymers. Sulfur is a rich nonmetallic element on earth, and is widely found in natural minerals (e.g., pyrite) and biological compounds (e.g., allicin, cysteine). With intensive research into sulfur utilization, various types of sulfur-containing compounds having special properties have been gradually discovered. Wherein the introduction of sulfur atoms into the polymer chain can significantly alter the properties of the material. Aliphatic polythioester (APPTE) is used as a sulfur-containing analogue of aliphatic polyester, has the characteristics of high refractive index, better mechanical property, good chemical resistance, excellent heavy metal adsorption capacity, chemical recoverability and the like, and is a promising high-performance polymer material. These excellent properties make it show great potential for applications in the fields of optical devices, biomedical materials and daily materials. APPTE is a polycondensation process, but this process is generally energy intensive and the product molecular weight is relatively low. Subsequently, the study turned to the preparation of high molecular weight APPTE by ring-opening polymerization of thiolactones, S-carboxylic anhydrides or 1, 2-dithiolanes under mild conditions. However, the types of monomers currently available are still very limited, resulting in polymers based on thiolactone derivatives that are difficult to achieve in a wide range of regulation in physical and chemical properties. In order to enrich the structural and functional diversity of polythioesters, research has developed the ring-opening copolymerization (ROCOP) method of episulfide anhydride and epoxide/episulfide. The episulfide anhydride and episulfide (derived from anhydride and epoxide, respectively) are widely available, partly from biomass, which makes it possible to build more diverse polymer structures. It is reported in literature （Tian-Jun Yue, Ming-Chao Zhang, Ge-Ge Gu, Li-Yang Wang, Wei-Min Ren, and XiaoBing Lu. Precise Synthesis of Poly(Thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts. Angew. Chem. Int. Ed. 2019, 58 (2), 618–623.） that polythioesters of completely alternating structure, of controlled molecular weight and of narrow polydispersity are obtained by copolymerization of thiocyclic anhydrides and cyclic thioether anions. The cyclic thioacid anhydride and the cyclic thioether used in the system are prepared from common acid anhydride and cyclic ether in the market, so that the cost is low, the operation is simple, the subsequent industrialized development is facilitated, but the primary structure of the polymer is single, the physical properties are relatively fixed, and the regulation and control cannot be realized. Literature （Naruki Tanaka,Eriko Sato,Akikazu Matsumoto. A. Thermally Stable Polysulfones Obtained by Regiospecific Radical Copolymerization of Various Acyclic and Cyclic 1,3-Diene Monomers with Sulfur Dioxide and Subsequent Hydrogenation. Macromolecules 2011, 44 (23), 9125–9137） reports that conjugated diene and sulfur dioxide undergo free radical copolymerization through a Michael addition reaction to prepare polysulfone with double bonds in the main chain, and the double bonds in the chain provide adjustable space stereo repeat units, thereby adjusting macroscopic physical properties of the polymer. However, sulfur dioxide used in the system has high toxicity, harsh reaction conditions and poor polymer solubility. However, the synthesis of polythioesters having carbon-carbon double bonds in the main chain has been recently reported. Disclosure of Invention Aiming at the problems existing in the prior art, the invention discloses polythioester with carbon-carbon double bonds in a main chain, which is alternating copolymer