CN105384859A - Aqueous suspension polymerization method for preparing poly(isobutylene-co-p-methylstyrene) random copolymer - Google Patents
Aqueous suspension polymerization method for preparing poly(isobutylene-co-p-methylstyrene) random copolymer Download PDFInfo
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- CN105384859A CN105384859A CN201510980659.2A CN201510980659A CN105384859A CN 105384859 A CN105384859 A CN 105384859A CN 201510980659 A CN201510980659 A CN 201510980659A CN 105384859 A CN105384859 A CN 105384859A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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Abstract
The invention relates to an aqueous suspension polymerization method for preparing a poly(isobutylene-co-p-methylstyrene) random copolymer. High-water-resistance Lewis acid such as Ga (C6F5) 3 and Al (C6F5) 3 is used as a co-initiator for positive ion polymerizing, and the poly(isobutylene-co-p-methylstyrene) random copolymer is successfully synthesized through positive ion copolymerizing and has the good molecular weight and good molecular weight distribution. The method for preparing the poly(isobutylene-co-p-methylstyrene) random copolymer is environmentally friendly.
Description
Technical field
The present invention relates to the synthetic method of the environmental protection of high-molecular copolymer.More particularly, relating to water is reaction medium, realizes iso-butylene and p-methylstyrene copolymerization by water phase suspension, preparation high molecular poly-(iso-butylene-
co-p-methylstyrene) method of random copolymers.
Background technology
At present; above-mentioned isobutylene homo and multipolymer; can only be prepared through cationoid polymerisation by isobutylene monomer; usual requirement is carried out under the condition of almost anaerobic, anhydrous and high purity inert gas protection in the organic reaction medium of drying; slurry polymerization and solution polymerization process flow process can be adopted; but reaction conditions requires extremely harsh, causes technical process extremely complicated.Water is a kind of conventional, cheap environment-friendly type medium, has been widely used in radical polymerization system, as suspension polymerization process, emulsion polymerization technique.Water is used to have obvious advantage as polymerisation medium: (1) is easy to get; (2) safety; (3) environmental protection; (4) specific heat of water holds large, heat transfer good heat dissipation effect.But; different from radical polymerization; for ionic polymerization system; then usually need just can carry out effective polyreaction under almost anhydrous, anaerobic and protection of inert gas; this mainly can carry out reacting with oxygen, water due to initiator system or catalyst system, active centre and be destroyed, and thus makes polyreaction to carry out.Therefore, the cationoid polymerisation system of the vinyl monomer since over half a century, is all that the reaction conditions, particularly water-content of requirement almost anhydrous, anaerobic and dry organic solvent must control in ppm level, otherwise polyreaction may be caused not occur.
Tradition isoprene-isobutylene rubber (IIR) has excellent resistance to air loss, lower second-order transition temperature, excellent damping and ageing-resistant performance, have a wide range of applications in the field such as automobile, biological medicine, but traditional isoprene-isobutylene rubber has a lot of deficiency, the consistency of tradition isoprene-isobutylene rubber and other rubber is poor, be unfavorable for other blend rubbers mixing, and molecular chain contains undersaturated double bond, be easily cross-linked in rubber post-production process, produce incipient scorch.Poly-(iso-butylene-co-p-methylstyrene) multipolymer is a kind of isobutylene-based polymers (in polymkeric substance iso-butylene structural unit content >90%), have the resistance to air loss similar to isoprene-isobutylene rubber and damping and amortization, but copolymerization employing p-methylstyrene replaces the isoprene in traditional isoprene-isobutylene rubber, and synthetic polymer molecule chain is full saturated structures.So poly-(iso-butylene-co-p-methylstyrene) has close to the heatproof air aging performance of ethylene-propylene rubber(EPR), ozone resistance, fatigue resistance and wear resistance, more excellent than traditional isoprene-isobutylene rubber performance.Also by the dynamic property that can improve tire in poly-(iso-butylene-co-p-methylstyrene) ubiquitous doughnut of multipolymer applied range, reduce rolling resistance and improve anti-slippery, also comprise cushioning material, the aspects such as tyre airtight layer, conveying belt and rubber hose.
Elaboration detailed in U.S.5430118A and U.S.5162445A employing aluminum chloride and aluminum alkyls have synthesized poly-(iso-butylene-co-p-methylstyrene) multipolymer as initiator system at-80 ~-100 DEG C.In document, initiator adopts the mode of directly adding to add in reaction system, and not by ageing, the activity of initiator system is difficult to control, and initiator has only selected aluminum chloride and ethyl aluminum dichloride.In patent U.S.5430118A and U.S.5162445A, solution method synthetic polymer solvent for use is methyl chloride and hexane volume ratio is 6/4.Gelatin viscosity is large, and reaction poor heat transfer, glue wall cling phenomenon is serious, synthesizes with short production cycle.And not adding three components in the literature, polymeric reaction temperature is lower, and energy consumption is comparatively large, and molecular weight distribution is all greater than 2.
Elaboration detailed in C.N.1568335A has synthesized isoolefin copolymers under have employed zirconium halide and halogenation hafnium and organic acyl chlorides condition.In document, initiator collocation method is complicated, and need under-40 DEG C of conditions, zirconium chloride and the ageing in methyl chloride of organic acyl chlorides, stir 4 hours.
Above-mentioned research is all prepare isobutylene copolymers in organic solvent.
The J.Am.Chem.Soc. such as Collins, 2003,125 (48): 14686-14687; Organometallics, 2009,28 (1): 249-263 point out 1,2-C
6f
4[B (C
6f
5)
2]
2, 1,2-C
6f
4[9-B (C
12f
8)]
2with cumyl chlorine (CumCl) or cumyl ether (CumOCH
3) etc. coordinate and can form active centre Isobutylene Initiated and carry out aqueous polymerization.In non-polar solvent hexane (moisture), Isobutylene Initiated polymerization at-78 DEG C, the polymkeric substance of high molecular (Mn=100000-779000g/mol), MWD relatively wide (Mw/Mn=1.7-4.6) can be synthesized, and point out to add 2 in polymerization system, 6-di-t-butyl-4-picoline (DtBMP) can effectively suppress proton initiation reaction, improves molecular weight of product.In aqueous-phase suspending system, the discoveries such as Collins, by adding some strong electrolytic solutions (as LiCl(23wt%), H
2sO
4(38wt%), HBF
4(48wt%)) carry out the electrolysis degree of regulation system, can effectively improve monomer conversion and molecular weight of product.Lewis etc. report (JournalofPolymerSciencePartA:PolymerChemistry, 2012,50:1325-1332.), three (phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) be active higher coinitiator, can synthesize by aqueous polymerization the polystyrene or polyisobutene that Mw is higher, MWD is narrower, productive rate is higher.But above-mentioned research is the research method relating to aqueous-phase suspending and prepare iso-butylene and p-methylstyrene multipolymer, has not also added the hexahydropyridine of stabilizing active central role.
CN201010257:64.X is in aqueous polymerization research, and use coinitiator is traditional BF
3, BC1
3, AlCl
3, AlBr
3, SnCl
4, TiCl
4, TiBr
4, FeCl
3, SbCl
5, ZnCl
2deng at least one; Do not use water tolerance better three (phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3).
Summary of the invention
Object of the present invention overcomes the deficiency of current technology, using the three components of hexahydropyridine as the copolymerization of positive ion aqueous-phase suspending, stablizes positive ion active centre, adopts three (phenyl-pentafluoride base) gallium (Ga (C that water tolerance is strong
6f
5)
3) and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) be coinitiator, realize iso-butylene and the copolyreaction of p-methylstyrene aqueous-phase suspending, gathered (iso-butylene-co-p-methylstyrene) multipolymer preferably, reach the effect of environmental protection.
The present invention seeks to be achieved by the following measures: add hexahydropyridine as three components, under 0 ~-100 DEG C of condition, main initiator and coinitiator is adopted to be initiator system, with iso-butylene and p-methylstyrene for raw material, in aqueous phase system, by poly-(iso-butylene-co-p-methylstyrene) random copolymers of cationic polymerization preparation.Wherein coinitiator can three (phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3), three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) etc. water tolerance strong Lewis acid one of them; Main initiator can be hydrogenchloride, cumyl chlorine, dicumyl chlorine (DCC), chloro-2,4, the 4-trimethylpentanes (TMPCl) of 2-one of them.
The preferred hexahydropyridine of present method concentration in cationic polymerization system is 1 × 10
-2~ 2 × 10
-4mol/L is 0.2-10 with ratio of initiator.
Present method preferred aqueous solutions, adds some strong electrolytic solutions LiCl or/and H in aqueous phase system
2sO
4or/and HBF
4carry out regulation system fusing point, meet the requirement of low temperature polymerization, wherein strong electrolyte content in water is 5 ~ 50wt%.
Present method preferred system monomer concentration is at 15wt%-50wt%, and in poly-(iso-butylene-co-p-methylstyrene) random copolymers, p-methylstyrene content is at 1-20wt%.The monomer droplet of mixing is suspended in water, and stablizes monomer droplet by adding tensio-active agent (as sodium lauryl sulphate, trifluoromethayl sulfonic acid, trimethyldodecane base brometo de amonio etc.), and wherein tensio-active agent addition is monomer mass 0.5 ~ 10wt%.
Present method may be used for interval 4L reactor synthetic rubber.Poly-(iso-butylene-co-p-methylstyrene) random copolymers of preferred solution method synthesis, synthetical glue fluid viscosity is less, and kiss-coating phenomenon is not obvious, with short production cycle.
Hexahydropyridine is as the three components of cationic polymerization, and energy stabilizing active center, monomer conversion improves.When hexahydropyridine is by monomer feed, add polymeric kettle with monomer material.
Aqueous suspension polymerization prepares multipolymer method:
(1) polymeric kettle charging: under 0 ~-100 DEG C of condition, adds the water of certain mass, main initiator, strong electrolyte, tensio-active agent, isobutylene monomer, p-methylstyrene, hexahydropyridine mixed solution, mixes in reactor;
(2) initiator system configuration: coinitiator hexane or water dilution;
(3) Macroscopic single crystal: under 0 ~-100 DEG C of condition, adds in polymeric kettle by coinitiator system, poly-(iso-butylene-co-p-methylstyrene) random copolymers of synthesis.
Poly-(iso-butylene-co-p-methylstyrene) random copolymers molecular weight is 50,000-500,000g/mol, and range of molecular weight distributions is 1.3 ~ 4.0.
Owing to adopting aforesaid method, the present invention, using the three components of hexahydropyridine as the copolymerization of positive ion aqueous-phase suspending, stablizes positive ion active centre, adopts three (phenyl-pentafluoride base) gallium (Ga (C that water tolerance is strong
6f
5)
3) and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) be coinitiator, realize iso-butylene and the copolyreaction of p-methylstyrene aqueous-phase suspending, gathered (iso-butylene-co-p-methylstyrene) multipolymer preferably, have good molecular weight and molecualr weight distribution, reach the effect of environmental protection.
Embodiment
Enumerate 6 embodiments below, further illustrated the present invention, the present invention is not only limited to this embodiment.
Embodiment 1
Under-100 DEG C of conditions, in polymeric kettle, add 100g water, LiCl15g, H
2sO
42ml, HBF
410ml, sodium lauryl sulphate l.0g, 100mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 10mol%), monomer concentration 36wt%.Sodium dialkyl sulfate is monomer mass 1.41wt%.Under agitation, add 2mL hydrogenchloride 0.4M, 2mL hexahydropyridine 0.4M and add system, add 32mL tri-(phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) solution 1M initiated polymerization, wherein hydrogenchloride, hexahydropyridine and three (phenyl-pentafluoride base) gallium mol ratio are 1:1:40.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 84%, and weight-average molecular weight is 4.4X10
5, molecular weight distributing index is 2.7.
Embodiment 2
Under-60 DEG C of conditions, in polymeric kettle, add 100g water, trimethyldodecane base brometo de amonio 2.5g, LiCl10g, HBF
45ml, 50mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 5mol%), monomer concentration 22.5wt%.Trimethyldodecane base brometo de amonio is monomer mass 7wt%.Under agitation, add chloro-2,4,4-trimethylpentane 0.4M, 4mL hexahydropyridine 0.4M of 2mL2-and add system, add 16mL tri-(phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) solution 1M initiated polymerization, wherein chloro-2,4, the 4-trimethylpentane TMPCl of 2-, hexahydropyridine and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) mol ratio is 1:2:20.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 90%, and weight-average molecular weight is 2.1X10
5, molecular weight distributing index is 2.1.
Embodiment 3
Under-40 DEG C of conditions, in polymeric kettle, add 100g water, trifluoromethayl sulfonic acid 2.5g, LiCl10g, HBF
410ml, 35mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 2mol%), monomer concentration 15wt%.Trifluoromethayl sulfonic acid is monomer mass 10wt%.Under agitation, add 2mL cumyl chlorine 0.4M, 1mL hexahydropyridine 0.4M and add system, add 4mL tri-(phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) solution 1M initiated polymerization, wherein cumyl chlorine, hexahydropyridine and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) mol ratio is 1:0.5:5.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 48%, and weight-average molecular weight is 5.8X10
5, molecular weight distributing index is 1.9.
Embodiment 4
Under-20 DEG C of conditions, in polymeric kettle, add 100g water, trifluoromethayl sulfonic acid 5g, LiCl10g.150mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 6mol%), monomer concentration 50wt%.Trifluoromethayl sulfonic acid is monomer mass 4wt%.Under agitation, add 1mL dicumyl chlorine 0.4M, 10mL hexahydropyridine 0.4M and add system, add 4mL tri-(phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) solution 1M initiated polymerization, wherein dicumyl chlorine, hexahydropyridine and three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) mol ratio is 1:10:10.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 37%, and weight-average molecular weight is 3.1X10
5, molecular weight distributing index is 2.3.
Embodiment 5
Under 0 DEG C of condition, in polymeric kettle, add 100g water, trimethyldodecane base brometo de amonio 5g, LiCl10g.150mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 1mol%), monomer concentration 50wt%.Trifluoromethayl sulfonic acid is monomer mass 4wt%.Under agitation, add chloro-2,4,4-trimethylpentane TMPCl0.4M, 10mL hexahydropyridine 0.4M of 1mL2-and add system, add 2mL tri-(phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) 1M initiated polymerization, wherein chloro-2,4, the 4-trimethylpentane TMPCl of 2-, hexahydropyridine and three (phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) mol ratio is 1:10:5.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 30%, and weight-average molecular weight is 1.5X10
5, molecular weight distributing index is 1.4.
Embodiment 6
Under 0 DEG C of condition, in polymeric kettle, add 100g water, trifluoromethayl sulfonic acid 2.5g, LiCl10g, HBF
410ml, 35mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 8mol%), monomer concentration 15wt%.Trifluoromethayl sulfonic acid is monomer mass 10wt%.Under agitation, add 2mL hydrogenchloride 0.4M, 2mL hexahydropyridine 0.4M and add system, add 0.8mL tri-(phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) solution 1M initiated polymerization, wherein hydrogenchloride, hexahydropyridine and three (phenyl-pentafluoride base) gallium mol ratio are 1:1:1.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 30%, and weight-average molecular weight is 7.4X10
5, molecular weight distributing index is 1.7.
Embodiment 7
Under-80 DEG C of conditions, in polymeric kettle, add 100g water, trimethyldodecane base brometo de amonio 2.5g, LiCl10g, 35mL iso-butylene and p-methylstyrene mixed solution (wherein p-methylstyrene 2mol%), monomer concentration 15wt%.Trifluoromethayl sulfonic acid is monomer mass 10wt%.Under agitation, add 2mL hydrogenchloride 0.4M, 10mL hexahydropyridine 0.4M and add system, add 0.8mL tri-(phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3) solution 1M initiated polymerization, wherein hydrogenchloride, hexahydropyridine and three (phenyl-pentafluoride base) gallium mol ratio are 1:5:1.Polymerization reaction system is creamy white homogeneously dispersed state.Polyreaction 20min, adds NaOH/ ethanolic soln termination reaction.Successively through alkali lye and water washing repeatedly, removing residual monomer, dispersion agent, additive, reaction medium etc., can obtain polymkeric substance, and vacuum-drying, to constant weight, can obtain dried polymerisate to reaction system under 40 DEG C of conditions.Polymer yield is 30%, and weight-average molecular weight is 12X10
5, molecular weight distributing index is 1.4.
Claims (9)
1. poly-(iso-butylene-co-p-methylstyrene) random copolymers of aqueous suspension polymerization method preparation, it is characterized in that: under 0 ~-100 DEG C of condition, adopt main initiator and water tolerance coinitiator to be initiator system, adding hexahydropyridine is three components, with iso-butylene and p-methylstyrene for raw material, in an aqueous medium, by poly-(iso-butylene-co-p-methylstyrene) random copolymers of positive ion suspension polymerization preparation.
2. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: when hexahydropyridine is by monomer feed, add polymerization system with monomer; Hexahydropyridine concentration is 0 ~ 2 × 10
-3mol/L, hexahydropyridine and main initiator molar ratio: 0 ~ 10.
3. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: coinitiator is three (phenyl-pentafluoride base) gallium (Ga (C
6f
5)
3), three (phenyl-pentafluoride base) aluminium (Al (C
6f
5)
3) water tolerance strong Lewis acid one of; Main initiator is water, cumyl chlorine, dicumyl chlorine (DCC), chloro-2,4, the 4-trimethylpentanes (TMPCl) of 2-one of them, coinitiator and main initiator molar ratio 1:1 ~ 1:40.
4. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: add strong electrolytic solution LiCl in aqueous phase system or/and H
2sO
4or/and HBF
4carry out regulation system fusing point, strong electrolyte content in water is 5 ~ 50wt%.
5. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: iso-butylene and p-methylstyrene monomer are mixed in proportion, both molar ratio 99:1 ~ 90:10; The monomer droplet of mixing is suspended in water, and by adding tensio-active agent, as monomer droplet stablized by sodium lauryl sulphate, trifluoromethayl sulfonic acid, trimethyldodecane base brometo de amonio, wherein tensio-active agent addition is monomer mass 0.5 ~ 10wt%.
6. poly-(iso-butylene-co-p-methylstyrene) random copolymers of aqueous suspension polymerization method preparation according to claim 1, it is characterized in that: poly-(iso-butylene-co-p-methylstyrene) random copolymers of synthesis by this method, iso-butylene structural unit content scope is 80 ~ 99wt%.
7. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: polymerizing condition temperature is at 0 ~-100 DEG C.
8. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: the number-average molecular weight of poly-(iso-butylene-co-p-methylstyrene) random copolymers is 50,000-500,000g/mol, molecular weight distribution is 1.3 ~ 4.0.
9. the preparation of aqueous suspension polymerization method gathers (iso-butylene-co-p-methylstyrene) random copolymers according to claim 1, it is characterized in that: iso-butylene and p-methylstyrene monomer conversion are 30 ~ 99%.
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CN106519096A (en) * | 2016-11-09 | 2017-03-22 | 北京石油化工学院 | Method used for preparing isobutene and alkyl styrene and/or isoprene random copolymer via water phase cationic suspension polymerization |
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