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CN-121991361-A - Polyamide elastomer and preparation method thereof

CN121991361ACN 121991361 ACN121991361 ACN 121991361ACN-121991361-A

Abstract

The invention relates to the field of high polymer materials, in particular to a polyamide elastomer and a preparation method thereof. The polyamide elastomer comprises soft segments and hard segments, wherein the hard segments comprise polyamide structural unit blocks and the soft segments comprise diene-based liquid rubber structural unit blocks. The polyamide elastomer has the dual advantages of polyamide and liquid rubber, the microphase separation structure of the polymer is more obvious, the acid and alkali resistance and flexibility of the product are obviously improved, new product types are added for the polyamide copolymer, the product performance is improved, excess homogenization products are avoided, and the application field of the polyamide elastomer is widened.

Inventors

  • WEN JINGBIN
  • HUANG XUDONG
  • FENG YUZHI
  • HAN YAN
  • WANG YUCHAO
  • CHEN FEI
  • LIN FENG
  • ZHENG HONGBING
  • GONG GUANGBI
  • WU LIPING

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (17)

  1. 1. A polyamide elastomer characterized in that it comprises soft segments and hard segments, wherein the hard segments comprise polyamide building blocks and the soft segments comprise diene liquid rubber building blocks.
  2. 2. The polyamide elastomer of claim 1 wherein, The polyamide structural unit block is connected with a diene liquid rubber block through a connecting group A or a connecting group B containing a triazine ring, wherein the connecting group A is obtained by reacting R 1 、R 2 with isocyanate groups on diisocyanate, R 1 is selected from amino or carboxyl, and R 2 is selected from amino, carboxyl or hydroxyl.
  3. 3. The polyamide elastomer according to claim 2, wherein, The diisocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
  4. 4. The polyamide elastomer according to claim 2, wherein, The structure of the connecting group B is shown as a formula (B): In the formula (B), X 1 is- (CO) -, or-NH-, X 2 is- (CO) -, -O-, or-NH-, and X 3 is a chlorine atom, - (CO) -, -O-, or-NH-, and represents a connecting end of a triazine ring.
  5. 5. The polyamide elastomer of claim 1 wherein, The polyamide building block is selected from at least one of a polyamide 6 building block, a polyamide 9 building block, a polyamide 11 building block, a polyamide 12 building block, a polyamide 66 building block, a polyamide 610 building block, a polyamide 1010 building block, a polyamide 612 building block, a polyamide 1212 building block, a polyamide 46 building block, a polyamide 1313 building block, a polyamide 1011 building block, a polyamide 1012 building block, a polyamide 1211 building block, a polyamide 1013 building block, a polyamide 1110 building block, a polyamide 1111 building block, a polyamide 106 building block, a polyamide 126 building block, a polyamide 44 building block, a polyamide 1112 building block, and a polyamide 1210 building block.
  6. 6. The polyamide elastomer of claim 5 wherein, The polyamide structural unit block is selected from at least one of a polyamide 6 structural unit block, a polyamide 610 structural unit block, a polyamide 1010 structural unit block, a polyamide 1211 structural unit block, a polyamide 106 structural unit block, a polyamide 126 structural unit block, a polyamide 1012 structural unit block, a polyamide 612 structural unit block, a polyamide 1013 structural unit block and a polyamide 44 structural unit block, and/or The number average molecular weight of the polyamide building block is 400-20000.
  7. 7. The polyamide elastomer of claim 1 wherein, The diene liquid rubber structural unit block is selected from at least one of polybutadiene rubber structural unit block, polyisobutylene rubber structural unit block, polyisoprene rubber structural unit block, polychloroprene rubber structural unit block, styrene-butadiene rubber structural unit block, nitrile rubber structural unit block and butyl rubber structural unit block.
  8. 8. The polyamide elastomer of claim 7 wherein, The diene liquid rubber structural unit block is selected from at least one of polybutadiene liquid rubber structural unit block, nitrile rubber structural unit block, styrene-butadiene rubber structural unit block and polyisobutylene rubber structural unit block, and/or The number average molecular weight of the diene liquid rubber structural unit block is 200-20000.
  9. 9. The polyamide elastomer according to any one of claims 1 to 8, wherein, Based on the mass of the polyamide elastomer: the content of the hard segment is 10-90wt%, and/or The content of the soft segment is 10-90wt%.
  10. 10. The polyamide elastomer according to any one of claims 1 to 8, wherein, The polyamide elastomer has a number average molecular weight of 4000 to 80000, and/or The polyamide elastomer has a linear structure or has a star structure.
  11. 11. A process for the preparation of a polyamide elastomer, comprising: In the presence of polymerization inhibitor and solvent, the polyamide monomer and diene liquid rubber monomer are polymerized.
  12. 12. The preparation method according to claim 11, wherein, At least one end capping group in the diene liquid rubber monomer is a third monomer end capping, and the third monomer is selected from diisocyanate or a compound containing a triazine ring.
  13. 13. The preparation method according to claim 12, wherein, The diisocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and/or The triazine ring-containing compound is selected from chlorotriazine rings.
  14. 14. The preparation method according to claim 11, wherein, The polyamide monomer is selected from at least one of polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 1010, polyamide 612, polyamide 1212, polyamide 46, polyamide 1313, polyamide 1011, polyamide 1012, polyamide 1211, polyamide 1013, polyamide 1110, polyamide 1111, polyamide 106, polyamide 126, polyamide 44, polyamide 1112 and polyamide 1210, and/or The number average molecular weight of the polyamide monomer is 400-20000.
  15. 15. The preparation method according to claim 11, wherein, The diene liquid rubber monomer is at least one selected from polybutadiene rubber, polyisobutylene rubber, polyisoprene rubber, polychloroprene rubber, styrene-butadiene rubber, nitrile rubber and butyl rubber, and/or The number average molecular weight of the diene liquid rubber monomer is 200-20000.
  16. 16. The process according to any one of claims 11 to 15, wherein, The polymerization inhibitor is at least one of sodium nitrite, nitrosohydroxylammonium, p-benzoquinone and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide radical, and/or The solvent is selected from sulfolane, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and acetone, and/or The polymerization inhibitor is contained in an amount of 0.01 to 5% by weight, and/or the polyamide monomer is contained in an amount of 1 to 40% by weight, and/or the diene-based liquid rubber monomer is contained in an amount of 1 to 40% by weight, based on the total mass of the polymerization reaction system, and/or The polymerization conditions include a temperature of 50-300 ℃ and/or a time of 0.5-48 hours.
  17. 17. A polyamide elastomer prepared by the method of any one of claims 11-16.

Description

Polyamide elastomer and preparation method thereof Technical Field The invention relates to the field of high polymer materials, in particular to a polyamide elastomer and a preparation method thereof. Background Thermoplastic polyamide elastomer (Thermoplastic polyamide elastomer, TPAE) is a segmented block copolymer composed of high-melting point crystalline polyamide hard segment and amorphous polyester or polyether soft segment, has the characteristics of ultra-light weight, high strength, low temperature resistance, fatigue resistance, friction resistance, organic solvent resistance, static resistance and the like, and is widely applied to the fields of sports goods, medical equipment, automobile parts, electronic and electric appliances, aviation industry, daily necessities and the like. The foreign research on TPAE starts from the beginning of the 80 s of the last century, and S.Mumcu et al of Hu els, germany, produced the first generation of TPAE commodity by melt polymerization using sebacic acid, dodecalactam and polytetramethylene glycol as raw materials. Subsequently, the company Arkema, france, has proposed elastomer series of various hardness comprising polyamide 11 and polyamide 12 as matrix materials, XX33 series and Rnew series. XPA series polyamide elastomers with polyamide 12 (PA 12) as the hard segment and polyetheramine as the soft segment are proposed by the Ministry of Japan. The series of products comprise four varieties of 9044X2, 9055X1, 9055X2 and 9063X1, and the Shore hardness is 44D, 62D, 54D and 56D respectively. In addition, this company developed four varieties of TPAE, which are sold under the trade names PAE600, 601, 1200 and 1201, of similar rubbers. The series of products have the characteristics of 49-294MPa of flexural modulus, 20-29MPa of tensile strength, 150-170 ℃ of melting point, wide use temperature range, good wear resistance, cold resistance, good chemical resistance and the like. The research and development of TPAE are relatively late in China, and only few companies such as Xuanyang chemical industry, heart source technology and Baling petrochemical industry have mature products, but the product types are relatively few, and certain difference exists between the performance and foreign products. The general methods for preparing TPAE mainly include bulk melt polymerization and solution. Wherein, the bulk melt polymerization method firstly prepares a polyamide prepolymer with double carboxyl groups, and then carries out esterification reaction with hydroxyl-terminated polyether to prepare TPAE, and related documents mainly include ：CN109206613A、CN110003464A、CN104910377B、CN101747510A、CN104327266A、CN105566639B、CN109970971A、CN108752581A、CN106565953A、CN109705338A、CN111378124A、CN111004389A、CN108841002A、CN108794742A and the like. However, the esterification reaction has the advantages of high reaction temperature, long reaction time, high vacuum degree requirement of a reaction system and severe equipment requirement, and small reaction equilibrium constant and low reaction efficiency, so that the prepared elastomer has low molecular weight and poor performance, the equimolar ratio of soft and hard segment reaction groups is strictly ensured in the synthesis process, the polymerization degree cannot meet the required requirement if the deviation exists, and meanwhile, the excessively high reaction temperature and the excessively long reaction time not only increase the production energy consumption, but also can be accompanied with a large amount of side reactions in the reaction process, and the appearance and the performance of the product are influenced. The petrochemical Co.Ltd.in China discloses a process for preparing polyamide elastomers by reacting carboxylic acids with esters, comprising CN115477753A, CN115490850A, but during the polycondensation reaction, the transesterification reaction occurs between hydroxyl terminated polyesters, resulting in a very low degree of reaction between the polyamide prepolymer and the polyesters, due to the transesterification reaction rate being greater than the esterification rate. In addition, according to the research reports, the soft segment materials adopted by the TPAE researched and developed at home and abroad at present mainly comprise polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol and the like, but the polyether glycol has poor acid and alkali resistance and strong hygroscopicity, and the performance of the final product is affected to a certain extent. In conclusion, the method further strengthens the design development and preparation research of TPAE and has important significance. Disclosure of Invention The invention aims to solve the problems of harsh esterification reaction conditions, low reaction degree, small molecular weight, poor performance and the like of a synthesized polyamide elastomer in the synthesis process of the polyamide elastomer in the prior art, and provides a poly