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CN-121991336-A - Functionalized perfluoropolyether in fluorinated chain, preparation method and application thereof, and modified perfluoroether rubber

CN121991336ACN 121991336 ACN121991336 ACN 121991336ACN-121991336-A

Abstract

The invention relates to the field of macromolecules, in particular to functionalized perfluoropolyether in a fluorinated chain, a preparation method and application thereof, and modified perfluoroether rubber. The perfluoropolyether has a structure represented by formula (I): Wherein A, B is independently selected from a substituted or unsubstituted ester group, rf is a perfluoropolyether segment, X 1 、X 2 is independently a hydroxyl group, a fluorine element or a fluorinated alkyl group, Y is a halogen or a hydrogen atom, and C is a carbon atom. The functionalized perfluoropolyether in the fluorinated chain has excellent thermal stability, and the functionalized perfluoropolyether can be self-crosslinked or can be compounded and crosslinked with fluororubber, perfluoroether rubber, fluorosilicone rubber and non-fluororubber to finally obtain a product with low temperature property and thermal stability.

Inventors

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

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
20241108

Claims (20)

  1. 1. A fluorinated in-chain functionalized perfluoropolyether, wherein the perfluoropolyether has a structure according to formula (I): The compound of formula (I), In formula (I): A. B are each independently selected from substituted or unsubstituted ester groups; Rf is a perfluoropolyether segment; X 1 、X 2 are each independently hydroxyl, fluorine or fluorinated alkyl; Y is halogen or hydrogen atom; c is a carbon atom.
  2. 2. A perfluoropolyether as recited in claim 1, characterized in that, In formula (I): A. b are each independently selected from substituted or unsubstituted C 1 -C 12 ester groups, and/or A. the substituents present in B are each independently selected from at least one of halogen, silicon-based and borane groups.
  3. 3. A perfluoropolyether as recited in claim 2, characterized in that, In formula (I): A is selected from substituted or unsubstituted C 1 -C 5 ester group, and/or B is selected from substituted or unsubstituted C 1 -C 3 ester group, and/or A. the substituents present in B are each independently selected from halogen.
  4. 4. A perfluoropolyether as recited in claim 1, characterized in that, In formula (I): At least one group in X 1 、X 2 is fluorine or fluorinated alkyl, and/or X 1 、X 2 is each independently hydroxy, fluorine or trifluoromethyl, and/or The perfluoropolyether chain segment is at least one selected from a K-type perfluoropolyether chain segment, a D-type perfluoropolyether chain segment, a Y-type perfluoropolyether chain segment and a Z-type perfluoropolyether chain segment.
  5. 5. A perfluoropolyether as recited in any one of claims 1 to 4, characterized in that, The perfluoropolyether has one of the following structures: In the formula (I), rf is a Z-type perfluoropolyether structural unit, A is a methyl ester group, B is an ethyl ester group, X 1 is a fluorine element, X 2 is a fluorine element and Y is a fluorine element; In the formula (I), rf is a Z-type perfluoropolyether structural unit, A is a methyl ester group, B is an ethyl ester group, X 1 is a hydroxyl group, X 2 is trifluoromethyl, and Y is a fluorine element; In the structure 3, rf is a Z-type perfluoropolyether structural unit, A is a methyl ester group, B is an ethyl ester group, X 1 is a fluorine element, X 2 is a trifluoromethyl group, and Y is a fluorine element.
  6. 6. A perfluoropolyether as recited in any one of claims 1 to 5, characterized in that, The average molecular weight of the perfluoropolyether is 1000-10000.
  7. 7. A process for preparing a functionalized perfluoropolyether in a fluorinated chain, the process comprising: The ketoperfluoropolyether of formula (I1) is subjected to a first fluorination reaction with a fluorination reagent A, followed by a first purification, optionally by a second fluorination reaction in the presence of a fluorination reagent B, optionally by a second purification; Formula (I1), A, B, rf, Y in formula (I1) is as defined in the perfluoropolyether of any one of claims 1 to 6, C is a carbon atom and O is an oxygen atom.
  8. 8. The method according to claim 7, wherein, The ketoperfluoropolyether has an average molecular weight of 1000-10000, and/or The preparation method of the ketone-based perfluoropolyether comprises the steps of carrying out a first contact reaction between halogenated ester shown in a formula (I12) and a hydrogen drawing reagent in the presence of a solvent A, and then carrying out a second contact reaction between the halogenated ester and double-end ester-based perfluoropolyether shown in a formula (I11); Formula (I11), Formula (I12), In the formulae (I11) and (I12), A, rf and B are as defined in the perfluoropolyether according to any one of claims 1 to 7.
  9. 9. The method according to claim 8, wherein, The molar ratio of the double-end ester-based perfluoropolyether to the halogenated ester is 1.2-3:1, and/or The mol ratio of the halogenated ester to the hydrogen drawing reagent is 1:0.9-3.
  10. 10. The method according to claim 8, wherein, The average molecular weight of the double-end ester-based perfluoropolyether is 1000-10000, and/or The hydrogen extracting agent is at least one selected from sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, sodium hydride, potassium hydride, lithium diisopropylamide, n-butyllithium and sec-butyllithium, and/or The hydrogen extracting reagent is dissolved in an alcohol solvent to carry out the first contact reaction with halogenated ester, and/or The solvent A is selected from ether solvents.
  11. 11. The method according to claim 10, wherein, The alcohol solvent is selected from C 1 -C 3 alcohol, and/or The ether solvent comprises at least one of tetrahydrofuran, dioxane, methyl tertiary butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and tetraethylene glycol dimethyl ether.
  12. 12. The method according to claim 8, wherein, The conditions of the first contact reaction include a reaction temperature of 0-60 ℃ for 0.2-5 hours, and/or The conditions of the second contact reaction include a reaction temperature of 25-120 ℃ for 0.5-36h, and/or The preparation method of the ketone-based perfluoropolyether further comprises the steps of separating and purifying in the presence of fluorocarbon solvent and acid after the second contact reaction.
  13. 13. The method according to any one of the claim 7 to 12, wherein, The fluorinating agent A and the fluorinating agent B each independently comprise at least one of sulfur tetrafluoride, bis (2-methoxyethyl) amino sulfur trifluoride, diethylaminosulfur trifluoride, 4-tertiary butyl-2, 6-dimethylphenyl sulfur trifluoride, nonafluorobutylsulfonyl fluoride, trifluoromethyl trimethylsilane, difluoromethyl trimethylsilane and trifluoroacetic anhydride, and/or The first and second fluoro reactions are each independently performed in a catalyst and/or solvent.
  14. 14. The method of claim 13, wherein the process comprises, The catalyst comprises at least one of hydrogen fluoride, potassium fluoride, cesium fluoride, triethylamine hydrogen fluoride salt, sodium hydrogen fluoride and ammonium hydrogen fluoride, and/or The solvent is selected from fluorocarbon solvents and/or non-fluoroether solvents, and/or The molar ratio of the catalyst to the ketone-based perfluoropolyether is 0.5-5:1.
  15. 15. The method of claim 14, wherein the process comprises, The fluorocarbon solvent comprises at least one of nonafluorobutyl ether, nonafluorobutyl methyl ether, benzotrifluoride, m-benzotrifluoride, perfluorocyclic ether and perfluorohexane, and/or The non-fluoroether solvent comprises at least one of tetrahydrofuran, dioxane, methyl tertiary butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
  16. 16. The method according to claim 7, wherein, The molar ratio of the ketone-based perfluoropolyether to the fluorinating agent A to the fluorinating agent B is 1:1.5-10.
  17. 17. The method of preparing a composition according to claim 7-16, The conditions of the first fluoro reaction and the second fluoro reaction each independently comprise a reaction temperature of 0-100 ℃ and a reaction time of 1-72 h, and/or The first purification and the second purification method comprise the steps of extracting in the presence of an extractant and alkali, and removing the extractant in the liquid phase extract.
  18. 18. The method of claim 17, wherein the process comprises, The alkaline compound comprises at least one of potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide and ammonia water, and/or The extractant is selected from organic alcohol compounds.
  19. 19. The method of claim 18, wherein the process comprises, The organic alcohol compound comprises an alcohol of C 1 -C 4 and/or an alcohol of fluoro C 1 -C 4 .
  20. 20. A functionalized perfluoropolyether in a fluorinated chain, characterized in that said functionalized perfluoropolyether in a fluorinated chain is prepared by the preparation method of any one of claims 7 to 19.

Description

Functionalized perfluoropolyether in fluorinated chain, preparation method and application thereof, and modified perfluoroether rubber Technical Field The invention relates to the field of macromolecules, in particular to functionalized perfluoropolyether in a fluorinated chain, a preparation method and application thereof, and modified perfluoroether rubber. Background In recent years, with rapid development of intelligent equipment, intelligent wearing, AI operation, AI house, intelligent express sorting and the like, the demand of high-sophisticated AI chips is increasing. Chip manufacturing (etching, printing, editing) equipment requires a sealing material with high solvent resistance and high corrosion resistance, which is mainly perfluoro ether rubber (FFKM). Since FFKM has a glass transition temperature (Tg) of about-30 ℃, it has poor rebound resilience under low temperature use conditions and is expensive, and its application in various fields has been restricted. Therefore, it is desirable to add polymers having Tg values less than-30 ℃ and good compatibility with FFKM to improve the low temperature service performance of FFKM. Because of the specificity of FFKM, the FFKM is initially used in the fields of military industry, aerospace and petroleum, and most of research on FFKM is secret and has little public information, so that no solution for definitely improving the low-temperature performance of FFKM is available to date. Recently, a perfluoropolyether (PFPE) -based elastomer, which is a fluoroelastomer having excellent low-temperature properties, has become a hot spot of research. Obviously, the PFPE with low Tg (-110 ℃ to-50 ℃) can effectively improve the low-temperature performance of the FFKM, and the PFPE has high compatibility with the FFKM and can be mixed and processed in any proportion. EP 0195946A2 discloses a process for the preparation of terminal-bromo PFPE and finds that this substance can be co-vulcanized with fluororubber under the action of peroxides. As a result, it was found that the modified fluororubber became easier to process, the releasability and thermal stability of the article were improved, and the mechanical properties, compression set and solvent resistance were hardly changed. This means that the PFPE can be co-vulcanized with the FFKM as long as it contains crosslinkable groups on the molecular chain. However, the molecular weight of PFPE has a large influence on the performance of FFKM, and when the molecular weight is lower than 2000 Da, the PFPE easily migrates to the surface in the FFKM compound, and the thermal decomposition temperature of the modified FFKM is also reduced. Disclosure of Invention The applicant of the present invention studied a new ketone group-containing perfluoropolyether molecular chain in the early stage, and further studied to find that the active groups on the perfluoropolyether molecular chain, such as ketone groups, are easy to break under the continuous high temperature effect, and the product is likely to fail in the use process, so that accidents are caused. Based on this, the applicant of the present invention has studied to find a novel functionalized perfluoropolyether having crosslinking functional groups, in particular, a first aspect of the present invention provides a functionalized perfluoropolyether in fluorinated chain, said perfluoropolyether having a structure represented by formula (I): The compound of formula (I), Wherein A, B is independently selected from a substituted or unsubstituted ester group, rf is a perfluoropolyether segment, X 1、X2 is independently a hydroxyl group, a fluorine element or a fluorinated alkyl group, Y is a halogen or a hydrogen atom, and C is a carbon atom. In a second aspect, the present invention provides a process for preparing a functionalized perfluoropolyether in the fluorinated chain, comprising: The ketoperfluoropolyether of formula (I1) is subjected to a first fluorination reaction with a fluorination reagent A, followed by a first purification, optionally by a second fluorination reaction in the presence of a fluorination reagent B, optionally by a second purification; Formula (I1), A, B, rf, Y in formula (I1) is as defined for the perfluoropolyether of the first aspect of the invention, C is a carbon atom and O is an oxygen atom. In a third aspect the present invention provides a fluorinated in-chain functionalized perfluoropolyether prepared by the preparation method of the second aspect of the present invention. In a fourth aspect the invention provides the use of a functionalized perfluoropolyether in the fluorinated chain according to the first aspect of the invention or the third aspect of the invention in the modification of rubber. In a fifth aspect, the present invention provides a modified perfluoroether rubber obtained by vulcanization of a perfluoroether rubber with a functionalized perfluoropolyether in the fluorinated chain of the first aspect or the third aspect of