Grafted copolymer of polyisobutene and polyisoprene and preparation method thereof

A technology of polyisoprene and graft copolymer, applied in the field of graft copolymer, which can solve the problems of difficult post-processing separation, low molecular weight, slow polymerization reaction rate, etc.

Active Publication Date: 2019-01-04
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2011, Kostjuk S V etc. used 1-p-methoxyphenethyl alcohol as an initiator, and tripentafluorophenylborane (B(C 6 f 5 ) 3 ) is a co-initiator to initiate IP cationic polymerization, although the cyclization side reaction of the isoprene structural unit can be reduced to a certain extent, but the molecular weight of the polymerization product PIP is still very low (M n ≤18kg / mol), poor mechanical properties, can not be used as a material
In 2016, Kostjuk S V used tert-butyl chloride as the initiator and TiCl 4 As a co-initiator, the IP was initiated to carry out cationic polymerization at different temperatures of 20°C, -20°C and -78°C, although the conventional and cheap coinitiator TiCl was used 4 (current market unit price: 0.2 yuan / gram), but, its consumption is bigger, and polymerization rate is slow, and aftertreatment separation difficulty, the molecular weight (M n ) is also lower than 10kg / mol, and the cyclized structure content is still greater than 13%, see: Kostjuk S V, Rozentsvet V A, Kozlov V G, Sablina N A, Stotskaya OA, Peruuch F, Polym.Chem., 2017, 8: 926-935
Therefore, in the prior art, it is also difficult to simultaneously increase the molecular weight of polyisoprene and reduce the content of cyclized structures.
[0006] Regarding direct use of AlCl 3 , AlRCl 2 , FeCl 3 Common Lewis acids such as co-initiated cationic polymerization of monomer isoprene to prepare polyisobutylene and polyisoprene graft copolymers have not been reported so far.

Method used

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  • Grafted copolymer of polyisobutene and polyisoprene and preparation method thereof
  • Grafted copolymer of polyisobutene and polyisoprene and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0061] At -90°C under nitrogen protection, add 10 mL of brominated isobutylene and p-methylstyrene random copolymer (BIMS) / hexane solution (concentration: 0.1 g / mL, bromine content is 0.9 wt%) to the polymerization reactor ) and 10 mL of isoprene (IP), mix well. Under stirring, add anisole and ethyl aluminum dichloride solution to initiate IP polymerization. Among them, the molar ratio of BIMS to IP is 1.2×10 -4 , the molar ratio of anisole to IP is 3×10 -4 , the molar ratio of dichloroethylaluminum to IP is 3×10 -3 . After 30 minutes of polymerization reaction, 2 mL of NaOH / ethanol solution with a mass fraction of 2% NaOH was added to terminate the reaction; after termination, the reaction system was washed with lye and water in sequence, and repeated three times. After purification, the polymer was obtained and dried in vacuum at 40°C. Obtain PIB-g-PIP graft copolymer 0.5g, its absolute weight-average molecular weight is 1920kg / mol, molecular weight distribution index (M...

Embodiment 2

[0063] The experimental method and reaction conditions are the same as in Implementation 1, except that the amount of ethylaluminum dichloride is reduced so that the molar ratio of it to IP is 2×10 -3 . Obtain PIB-g-PIP graft copolymer 0.45g, its absolute weight-average molecular weight is 1991kg / mol, M w / M n is 2.5, and the PIP mass content is 15%; the absolute weight-average molecular weight of the main chain isobutylene-based polymer segment is 1470kg / mol; the M of the branched polyisoprene segment n It is 89kg / mol, the 1,4-structure content accounts for 93%, and there is no cyclic structure.

Embodiment 3

[0065] Under the protection of nitrogen at 0°C, add 1 mL of brominated isobutylene and p-methylstyrene random copolymer (BIMS) / hexane solution (concentration: 0.1 g / mL, bromine content: 1.6 wt%) to the polymerization reactor ), 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl and ethylaluminum dichloride solution, mixed for 1 min. Under stirring, 19 mL of isoprene (IP) / hexane solution was added to start the polymerization. Among them, the molar ratio of BIMS to IP is 2.0×10 -4 , the molar ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl to IP is 1.6×10 -3 , the molar ratio of dichloroethylaluminum to IP is 8.0×10 -3 . Polymerization was terminated after 120min, and the aftertreatment process was the same as in Example 1. Obtain PIB-g-PIP graft copolymer 0.8g, its absolute weight-average molecular weight is 1340kg / mol, M w / M n is 1.6, and the PIP mass content is 13%; the absolute weight-average molecular weight of the main chain isobutylene-based polymer s...

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Abstract

The invention relates to the field of grafted copolymers, and provides a grafted copolymer of polyisobutene and polyisoprene and a preparation method thereof. According to the grafted copolymer, isocrotyl polymer chain segments are adopted as a main chain, polyisoprene chain segments are adopted as a branch chain, and the main chain and the branch chain are bonded in a grafted mode. The absolute weight-average molecular weight Mw of the grafted copolymer ranges from 200 kg / mol to 3000 kg / mol, and the polydispersity index ranges from 1.3 to 4.0. On the basis that the total mass of the grafted copolymer is 100%, the mass content of polyisoprene chain segments ranges from 3% to 40%; the absolute weight-average molecular weight of the isocrotyl polymer chain segments as the main chain ranges from 100 kg / mol to 2000 kg / mol. By means of the method, grafted copolymer materials with different branch chain numbers and branch chain lengths are synthesized, and the problems that in isoprene cationic polymerization, the polymer molecular weight is low, and cyclizing isomerization is serious are effectively solved.

Description

technical field [0001] The invention relates to the field of graft copolymers, in particular to a graft copolymer of polyisobutylene and polyisoprene and a preparation method thereof. Background technique [0002] Cationic polymerization or cationic polymerization is one of the important components of polymer synthesis chemistry. There are also various types of monomers that can undergo cationic polymerization. For example, common monomers include isobutylene, isoprene, 1,3-pentane Alkene, cyclopentadiene, styrene, methyl styrene, tert-butyl styrene, vinyl methyl ether, vinyl isobutyl ether, etc. Isobutylene homopolymer (polyisobutylene) and its random copolymers (such as: butyl rubber) with other monomers (such as: isoprene) can only be synthesized by cationic polymerization, which is the largest output in the field of cationic polymerization Industrialized products. Isobutylene-based polymers generally have the characteristics of excellent air tightness, aging resistance...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F255/10C08F236/08
CPCC08F255/10C08F236/08
Inventor 吴一弦周琦王楠杜杰
Owner BEIJING UNIV OF CHEM TECH
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