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CN-121991322-A - Cycloolefin block copolymer and preparation method thereof

CN121991322ACN 121991322 ACN121991322 ACN 121991322ACN-121991322-A

Abstract

The invention provides a cycloolefin block copolymer and a preparation method thereof, and relates to the technical field of block copolymers, wherein the preparation method comprises the following steps of sequentially adding monocyclic olefin, cycloolefin containing a rigid structure, an inert solvent, a molecular weight regulator and a cocatalyst into a reaction kettle to be mixed to obtain a mixed solution, and simultaneously adding a solution of a catalyst I and a solution of a catalyst II in the inert solvent to carry out ring-opening polymerization reaction; and after the reaction is finished, removing the catalyst I and the catalyst II, filtering to obtain supernatant, introducing a hydrogen source into the supernatant, adding a hydrogenation catalyst into the supernatant, carrying out hydrogenation reaction, and filtering and separating after the reaction is finished to obtain the cycloolefin block copolymer. The cycloolefin block copolymer prepared by the invention has better thermal stability, higher elongation at break, higher glass transition temperature, good transparency and excellent processability.

Inventors

  • TAO RUOYUAN
  • WU LIPING
  • Ma Fengboda
  • GAN QUAN
  • SHEN SHAOCHUN

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
20241105

Claims (10)

  1. 1. A process for the preparation of a cyclic olefin block copolymer, comprising the steps of: S1, sequentially adding monocyclic olefin, cycloolefin containing a rigid structure, an inert solvent, a molecular weight regulator and a cocatalyst into a reaction kettle, mixing to obtain a mixed solution, and simultaneously adding a solution of a catalyst I and a solution of a catalyst II in the inert solvent to carry out ring-opening polymerization reaction; S2, removing the catalyst I and the catalyst II after the reaction is finished, filtering to obtain supernatant, introducing a hydrogen source into the supernatant, adding a hydrogenation catalyst into the supernatant, carrying out hydrogenation reaction, and filtering and separating after the reaction is finished to obtain a cycloolefin block copolymer; wherein, the structural formulas of the catalyst I and the catalyst II are shown as follows: Wherein M is tungsten, molybdenum, nickel or palladium, X is independently selected from halogen, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20 , wherein the substituent is a group containing oxygen atom, nitrogen atom, sulfur atom and silicon atom; Ra 1-Ra 2 are independently selected from hydrogen atoms, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20 , ra 3-Ra 8 are independently selected from hydrogen atoms, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20 , wherein the substituent is a group containing oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms; m' is tungsten, molybdenum, nickel or palladium; L is independently selected from halogen, aliphatic alkyl of C 1～30 , alicyclic alkyl of C 1～30 , and aryl of substituted or unsubstituted C 1～20 , wherein the substituent is isopropoxy, ethoxy, bromomethoxy, and carboxamide; Rb 1-Rb 2 are independently selected from hydrogen atom, aliphatic alkane of C 1～30 , aryl of substituted C 1～20 , rb 3-Rb 4 are neutral double electron donor; n is an integer of 0 to 6.
  2. 2. The method for preparing a cycloolefin block copolymer according to claim 1, characterized in that the structural formula of the cycloolefin having a rigid structure is shown in the following formula III: Formula III Wherein R1 to R10 each independently represent a hydrogen atom, a C1-30 alkyl group, a substituted or unsubstituted C6-20 aryl group, wherein the substituents are groups containing a silicon atom, a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, R1 and R4 are bonded to each other to form a ring; m is an integer of 0 to 3.
  3. 3. The process for preparing cycloolefin block copolymers according to claim 1 or 2, characterized in that the molar ratio of catalyst I, catalyst II, monocycloolefins, cycloolefins containing rigid structures is from 1:2 to 5 (100 to 4000): from 100 to 4000.
  4. 4. The method for producing a cycloolefin block copolymer according to claim 1 or 2, characterized in that the mass fraction of the total amount of the monocyclic olefin and the cycloolefin having a rigid structure in the inert solvent is 1% by weight to 50% by weight, and the mass ratio of the monocyclic olefin to the cycloolefin having a rigid structure is 1 (0.1 to 10).
  5. 5. The method for producing a cycloolefin block copolymer according to claim 1 or 2, characterized in that the reaction temperature of the ring-opening polymerization is 20 to 300 ℃ and the reaction temperature of the hydrogenation reaction is-10 to 200 ℃.
  6. 6. The method for producing a cycloolefin block copolymer according to claim 1 or2, wherein the molecular weight regulator is one or more selected from compounds having a carbon-carbon double bond of 3 to 30 carbon atoms, and the ratio of the total of the monocyclic olefin and the cycloolefin having a rigid structure to the amount of the substance of the molecular weight regulator is (10 to 1000): 1.
  7. 7. The method for preparing the cycloolefin block copolymer according to claim 1 or 2, wherein the cocatalyst is one or more of alkyl lithium, alkyl zinc, alkyl aluminum and alkyl magnesium.
  8. 8. The method for producing a cycloolefin block copolymer according to claim 1 or 2, characterized in that the hydrogen source is hydrogen gas or a hydrazine compound.
  9. 9. The method for preparing a cycloolefin block copolymer according to claim 2, wherein the cycloolefin having a rigid structure includes one or more of norbornene, 2-phenyl-5-norbornene, tetracyclododecene, 2-benzoyl-5-norbornene, 5-norbornene-2, 3-dicarboximide, 5-norbornene-2, 3-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride.
  10. 10. A cycloolefin block copolymer prepared by the preparation method according to any one of claims 1 to 9.

Description

Cycloolefin block copolymer and preparation method thereof Technical Field The invention relates to the technical field of block copolymers, in particular to a cycloolefin block copolymer and a preparation method thereof. Background Cycloolefin polymer, COP for short, is a non-crystalline polyolefin material, has good transparency and water vapor barrier property, and has wide application prospect in the fields of optics, medical packaging and the like. In the process of preparing the cycloolefin copolymer, the insertion rate of cycloolefin with a rigid structure can directly influence the thermal stability and mechanical strength of the cycloolefin copolymer, the too low insertion rate can lead to the reduction of the glass transition temperature, the thermal stability is poor, and the too high insertion rate can lead to the deterioration of the toughness of a finished product and the easy breakage. Non-patent document 1 discloses a method for alternately copolymerizing norbornene with cyclopentene or cyclooctene, which can improve the flexibility of a polymer and reduce the processing difficulty, but which adopts an expensive ruthenium-based catalyst, so that the industrial application is limited. In view of the foregoing, those skilled in the art are highly in need of finding catalysts of specific structures to solve the problems of poor thermal stability and brittleness of COP materials. [ Non-patent document 1] Kong Yong, yang Xiaohua, wang Lin, et al, progress of the research on ring-opening metathesis polymerization [ J ]. Scientific techniques and engineering 2015,15 (30): 71-78 Disclosure of Invention The invention aims to provide a cycloolefin block copolymer and a preparation method thereof, and the cycloolefin block copolymer with higher elongation at break, higher glass transition temperature and good thermal stability and toughness is obtained by selecting a catalyst with a specific structure. The object of the present invention is to provide a cycloolefin block copolymer which has both hard segments and soft segments. The technical scheme adopted for solving the technical problems is as follows: The invention provides a preparation method of a cycloolefin block copolymer, which comprises the following steps: S1, sequentially adding monocyclic olefin, cycloolefin containing a rigid structure, an inert solvent, a molecular weight regulator and a cocatalyst into a reaction kettle, mixing to obtain a mixed solution, and simultaneously adding a solution of a catalyst I and a solution of a catalyst II in the inert solvent to carry out ring-opening polymerization reaction; S2, removing the catalyst I and the catalyst II after the reaction is finished, filtering to obtain supernatant, introducing a hydrogen source into the supernatant, adding a hydrogenation catalyst into the supernatant, carrying out hydrogenation reaction, and filtering and separating after the reaction is finished to obtain a cycloolefin block copolymer; wherein, the structural formulas of the catalyst I and the catalyst II are shown as follows: Wherein M is tungsten, molybdenum, nickel or palladium, X is independently selected from halogen, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20, wherein the substituent is a group containing oxygen atom, nitrogen atom, sulfur atom and silicon atom; Ra 1-Ra 2 are independently selected from hydrogen atoms, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20, ra 3-Ra 8 are independently selected from hydrogen atoms, aliphatic alkane of C 1～30 and aryl of substituted or unsubstituted C 1～20, wherein the substituent is a group containing oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms; m' is tungsten, molybdenum, nickel or palladium; L is independently selected from halogen, aliphatic alkyl of C 1～30, alicyclic alkyl of C 1～30, and aryl of substituted or unsubstituted C 1～20, wherein the substituent is isopropoxy, ethoxy, bromomethoxy, and carboxamide; Rb 1-Rb 2 are independently selected from hydrogen atom, aliphatic alkane of C 1～30, aryl of substituted C 1～20, rb 3-Rb 4 are neutral double electron donor; n is an integer of 0 to 6. The preparation method of the cycloolefin block copolymer comprises the following steps of: Formula III Wherein R1 to R10 each independently represent a hydrogen atom, a C1-30 alkyl group, a substituted or unsubstituted C6-20 aryl group, wherein the substituents are groups containing a silicon atom, a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, R1 and R4 are bonded to each other to form a ring; m is an integer of 0 to 3. The preparation method of the cycloolefin block copolymer comprises the steps of preparing a catalyst I, a catalyst II, monocyclic olefin and cycloolefin containing a rigid structure, wherein the molar ratio of the catalyst I to the catalyst II to the monocyclic olefin is 1:2-5 (100-4000) to (100-4000). The preparation method of the cycloolefin block copolymer compr