Cationic polymerization initiation system and cationic polymerization method

A technology of cationic polymerization and initiating system, applied in the field of initiating system and its polymerization, can solve the problems of low molecular weight of polystyrene products, slow polymerization reaction rate, low polymerization reaction efficiency, etc.

Active Publication Date: 2012-04-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] JP 10-130315A discloses a trifluorosulfonic acid metal salt (such as: ytterbium salt) to initiate alkoxy-substituted highly active monomers, such as vinyl ethers and alkoxystyrenes, in the reaction containing water Cationic polymerization is carried out in the medium, but the polymerization reaction efficiency is low, and the reaction time is as long as 100 hours or longer, and the molecular weight of the polymerization product is low, and the weight average molecular weight (M w )4 , similar reports can also be found in Chemical Communication, 2005, p2713-2715
Here, the used trifluorosulfonic acid metal salt is expensive, and the amount used in the polymerization reaction is large
[0006] In 2006, the article "Cationic Polymerization of Styrene in Solution and Aqueous Suspension Using B(C 6 f 5 ) 3 as a Water-Tolerant Lewis Acid", mentions the use of water-resistant Lewis acid B (C 6 f 5 ) 3 , can cause styrene to carry out cationic polymerization in aqueous reaction medium, but the molecular weight of gained polystyrene product is low, and its weight-average molecular weight (M w ) is only around 3000
In 2008, in "Journal of Polymer Science, Part A: Polymer Chemistry" Volume 46 "Controlled Cationic Polymerization of Cyclopentadiene with B(C 6 f 5 ) 3 as a Coinitiator in the Presence of Water" mentioned again, using B(C 6 f 5 ) 3 Cationic polymerization of cyclopentadiene can be initiated in a reaction system containing water, but the polymerization reaction rate is slow, and only a polymerization conversion rate of less than 40% can be obtained after tens of hours of reaction, and only low molecular weight polymerization can be obtained product, its M w <2500
As for the direct use of AlCl 3 , AlRCl 2 , BF 3 、TiCl 4 , FeCl 3 , SnCl 4 , ZnCl 2 Common Lewis acid co-initiated vinyl monomers carry out cationic polymerization initiation system and polymerization method in the reaction medium containing water or even completely in the reaction medium of water, so far there is no report

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] At -60°C, add water, 5g LiCl, 0.26g NaCl n-hexane and isobutylene (IB) to the polymerization reactor, the total volume is 40mL, the volume fraction of the water phase in the reaction medium is 57%, the volume of n-hexane The fraction is 43%, and the concentration of IB in the reaction system is 1.5mol / L. Under stirring, from water, HCl, triphenylphosphine, AlCl 3 A system composed of dichloromethane initiates a polymerization reaction. Initiator water, HCl, triphenylphosphine and AlCl 3 The molar ratio to IB is 2×10 -4 : 1.0×10 -4 : 9.4×10 -3 : 1.0×10 -2 : 1. Polymerize for 2 minutes, then add 20 mL of NaOH / ethanol solution with a mass fraction of NaOH of 2% to terminate the reaction; the reaction system after termination is washed and flashed with lye and water in sequence, repeated several times to remove residual monomers, additives, reaction Medium, Lewis acid, etc., the polymer can be obtained, and vacuum-dried at 40°C, the dried polymer product can be obtai...

Embodiment 2

[0057] The monomer of polymerization reaction, reaction medium and polymerization temperature condition are the same as embodiment 1, just by water, triphenylphosphine, AlCl 3 The system composed of toluene solution initiates the polymerization reaction. Initiator water, triphenylphosphine and AlCl 3 The molar ratio to IB is 1.2×10 -4: 5×10 -3 : 5×10 -3 : 1. A homogeneously dispersed polymerization system is formed. Reaction 1min, termination and aftertreatment method are the same as embodiment 1. M of the polymerization product w 5.6×10 5 ,M w / M n is 3.5.

Embodiment 3

[0059] At -20°C, add styrene, water, 2.5g LiCl and 0.13g NaCl to the polymerization reactor, the total volume is 20mL, the reaction medium is all water, and the styrene concentration in the reaction system is 4.4mol / L. Under stirring, from water, 1-chlorophenylethane (addition product of hydrogen chloride and styrene), triphenylphosphine, AlCl 3 And the system composed of dichloromethane, initiates the polymerization reaction of styrene. Initiator water, 1-chlorophenylethane, triphenylphosphine and AlCl 3 The molar ratio to styrene is 2.0×10 -4 : 0.4×10 -5 : 7.7×10 -3 : 7×10 -3 : 1. Reaction 1min, termination and aftertreatment method are the same as embodiment 1. Polymerization product yield is 7%, M w 6.9×10 4 ,M w / M n is 2.6.

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Abstract

The invention discloses a cationic polymerization initiation system and a cationic polymerization method. The cationic polymerization initiation system comprises at least one initiator, at least one Lewis acid and at least one additive. The initiator is a compound capable of providing protons or carbocations, wherein a mole ratio of the initiator to monomers is (5.0*10<-5> to 1.2*10<-2>): 1. The Lewis acid is a metal halide or an organic metal halide, wherein a mole ratio of the Lewis acid to the monomers is (5.0*10<-4> to 4.0*10<-1>): 1. The at least one additive is selected from sulfur-containing organic compounds, phosphorus-containing organic compounds and organic compounds containing sulfur and phosphorus, wherein a mole ratio of the at least one additive to the monomers is (1.0*10<-3> to 5.0*10<-2>): 1. The cationic polymerization initiation system has high activity, a low price and stable properties, is convenient for use, has high polymerization efficiency, and can greatly improve polymerization product molecular weight, wherein weight-average molecular weight of polymerization products obtained at a temperature of -60 DEG C is 1*10<6>.

Description

technical field [0001] The invention relates to an initiating system for cationic polymerization of cationically polymerizable monomers, in particular to an initiating system for preparing corresponding polymers from vinyl monomers by cationic polymerization in an aqueous reaction medium and a polymerization method thereof. Background technique [0002] Cationic polymerization is an important part of macromolecule synthesis chemistry. Usually, Lewis acids containing tin, aluminum, titanium, boron, and iron halides are used to co-initiate vinyl monomers for cationic polymerization to prepare polymers, which can be used for cationic polymerization. There are many kinds of monomers, such as common isobutylene, isoprene, 1,3-pentadiene, cyclopentadiene, styrene, methylstyrene, isobutyl vinyl ether, etc., among which isobutylene is Polymers and copolymers with second monomers are the largest commercial products in the field of cationic polymerization. Isobutylene polymer is a ki...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/14C08F110/10C08F112/08C08F4/16C08F4/54C08F236/08C08F4/72C08F212/06C08F4/26C08F116/18
Inventor 吴一弦周晗黄强何平
Owner CHINA PETROLEUM & CHEM CORP
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