CN110272514A - A kind of brominated isobutylene-p-methylstyrene copolymer and preparation method thereof - Google Patents
A kind of brominated isobutylene-p-methylstyrene copolymer and preparation method thereof Download PDFInfo
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- CN110272514A CN110272514A CN201910604970.5A CN201910604970A CN110272514A CN 110272514 A CN110272514 A CN 110272514A CN 201910604970 A CN201910604970 A CN 201910604970A CN 110272514 A CN110272514 A CN 110272514A
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2323/22—Copolymers of isobutene; butyl rubber
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
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Abstract
The present invention provides a kind of brominated isobutylene-p-methylstyrene copolymer preparation methods.The present invention has good dissolubility to isobutene-p-methylstyrene copolymer as bromination solvent using low pole aliphatic hydrocarbon, and can improve the mass transfer and heat-transfer capability of system, improves bromination reaction rate；Meanwhile the present invention improves the conversion ratio and utilization rate of bromating agent bromo element using oxidant, reduces bromating agent usage amount, reduces the discharge of Br element；Finally, the present invention improves neutralization efficiency using sour promotor is tied up, byproduct residue is reduced, guarantees product quality.
Description
Technical field
The invention belongs to technical field of rubber preparation, and in particular to a kind of brominated isobutylene-p-methylstyrene copolymer
And preparation method thereof.
Background technique
Brominated isobutylene-p-methylstyrene random copolymer (BIMS) is the bullet of new generation prepared by cationic polymerization
Property body also show the heat resistance, excellent better than ethylene propylene diene rubber other than the air-tightness and damping and amortization excellent with IIR
Ozone resistance and weatherability can improve dynamic property in tyre stock and with BIMSM, reduce rolling resistance and raising
Wet-sliding resistant performance.
BIMSM carries out cationic copolymerization conjunction by isobutene and p-methylstyrene (p-MS), then carries out bromination reaction,
Bromination reaction occurs on main chain on the methyl position of p-MS segment and generates vulcanizable benzyl bromo functional groups.Due to benzyl bromide function
It rolls into a ball perpendicular to main polymer chain, and sulfurate activity with higher, therefore stable crosslinked can be formed with a variety of vulcanizing systems
System, such as zinc oxide/zinc stearate vulcanizing system.The feature of BIMSM maximum be easily with other polymers blending and modifying.
Waddell etc. reports the butadiene-styrene rubber replaced in the tire tread compound of part with BIMSM, can significantly improve winter and wet and slippery road
Tractive force on face simultaneously reduces rolling resistance.Therefore, BIMSM can improve the dynamic mechanical of tire, can substitute halogenation IIR use
In tire sidewall, tyre surface and carcass, and the quality and safety of automobile tire can be significantly improved.
Among the application of BIMSM is gradually being expanded, wherein focusing on the exploitation of tire art, including tubeless tyre gas
Close layer, sidewall, curing bag, special tread rubber etc..In terms of non-tire product, be mainly used for vehicle damping (shock mount,
Air spring), medicinal bottle stopper, hose, conveyer belt, waterproof roll and adhesive etc., wherein the purposes in terms of damping most has development
Future.Studies have shown that BIMSM is ultrapure object, it is most clean elastomer in the product for be suitble to pharmacy application.
Patent US5077345 illustrates a kind of free radical halogenation method for halogenated isobutylene and ring-alkylated styrenes, mainly
The disadvantage is that the methyl substituents halogen theoretical content on phenyl ring only has 50%, remaining halogen generates halogen in conjunction with the H displaced
Change hydrogen by-product, the by-product is not involved in halogenation.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of brominated isobutylene-p-methylstyrene total
The conversion ratio and utilization rate of bromating agent bromo element can be improved in polymers and preparation method thereof, preparation method provided by the invention, drop
Low bromating agent usage amount, reduces the discharge of Br element, and neutralization efficiency can be improved, and reduces byproduct residue, guarantees product
Quality.
The present invention provides a kind of brominated isobutylene-p-methylstyrene copolymer preparation methods, comprising the following steps:
A isobutene-p-methylstyrene copolymer is mixed with low pole aliphatic hydrocarbon), obtains glue；
B it after) oxidant, radical initiator, bromating agent and the glue are mixed, is reacted, is obtained anti-
Glue after answering；
C acid binding agent) is sequentially added into the glue after the reaction and ties up sour promotor and is reacted, and is reacted
Liquid；
D) by after reaction solution washing, stabilizer mixing is added, then flash removing solvent, obtains sizing material；
E) by after the sizing material extrusion dehydration, drying, brominated isobutylene-p-methylstyrene copolymer is obtained.
Preferably, the low pole aliphatic hydrocarbon is selected from the low pole aliphatic hydrocarbon of C5~C8.
Preferably, the viscosity of the glue is 250~650cp, isobutene-p-methylstyrene copolymer in the glue
Mass percentage be 5wt%~25wt%.
Preferably, the oxidant is one of hydrogen peroxide, hypochlorite, bromate or a variety of；
It is (0.7~2) to the molar ratio of methyl group in the oxidant and isobutene-p-methylstyrene copolymer:
1。
Preferably, the radical initiator is azobisisoheptonitrile, azodiisobutyronitrile, azo two (2- methyl fourth)
One of nitrile, 2,2- azo two (trimethylpentane nitrile) and azo two (2,4- dimethyl-penten) nitrile are a variety of；
Radical initiator and isobutene-p-methylstyrene copolymer mass ratio are (0.2~5): 100.
Preferably, the bromating agent is selected from Br2, HBr, cross pyridinium bromide hydrobromide, C5H6Br2N2O2, tetrabromo cyclic ketones, benzene
Base trimethyl tribromide ammonium, benzyl trimethyl tribromide ammonium, dibromo isocyanurate, N-bromoacetamide, N- bromo-succinimide,
N- bromo O-phthalic base amide, N, one of bromo- 5,5 ' dimethyl hydantoin of N '-two or a variety of；
In the bromating agent in bromo element and isobutene-p-methylstyrene copolymer to methyl mole for (0.7~
2):1。
Preferably, the acid binding agent is selected from one of sodium hydroxide, sodium hydrogensulfite, sodium carbonate, sodium bicarbonate or more
Kind；The molar ratio of bromo element is (0.5~2.5) in the acid binding agent and bromating agent: 1；
It is described to tie up sour promotor selected from fatty alcohol, polyethers, alkali or alkaline earth metal carboxylate, epoxides, metal oxygen
One of inorganic salts of compound or hydroxide, highly basic and weak acid are a variety of；The sour promotor and isobutene-tied up is to methyl
The mass ratio of styrol copolymer is (0.001~10): 100.
Preferably, the stabilizer is selected from one of calcium stearate, zinc stearate, epoxidized soybean oil or a variety of；It is described
Stabilizer and isobutene-p-methylstyrene mass ratio are (1~2.5): 100.
Preferably, step B) in, the temperature of the reaction is 20~55 DEG C, and the time is 1~60min.
The present invention also provides a kind of brominated isobutylene that above-mentioned preparation method is prepared-p-methylstyrene copolymerization
Object.
Compared with prior art, the present invention provides a kind of brominated isobutylene-p-methylstyrene copolymer preparation sides
Method, comprising the following steps: A) isobutene-p-methylstyrene copolymer is mixed with low pole aliphatic hydrocarbon, obtain glue；B) will
After oxidant, radical initiator, bromating agent and the glue are mixed, reacted, the glue after being reacted；C)
Acid binding agent is sequentially added into the glue after the reaction and ties up sour promotor and is reacted, and reaction solution is obtained；It D) will be described
After reaction solution washing, stabilizer mixing is added, then flash removing solvent, obtains sizing material；E) by the sizing material extrusion dehydration, drying
Afterwards, brominated isobutylene-p-methylstyrene copolymer is obtained.The present invention is using low pole aliphatic hydrocarbon as bromination solvent to isobutyl
Alkene-p-methylstyrene copolymer has good dissolubility, and can improve the mass transfer and heat-transfer capability of system, improves bromination
Reaction rate；Meanwhile the present invention improves the conversion ratio and utilization rate of bromating agent bromo element using oxidant, reduces bromating agent and uses
Amount reduces the discharge of Br element；Finally, the present invention improves neutralization efficiency using sour promotor is tied up, byproduct residue is reduced, is guaranteed
Product quality.
Specific embodiment
The present invention provides a kind of brominated isobutylene-p-methylstyrene copolymer preparation methods, comprising the following steps:
A isobutene-p-methylstyrene copolymer is mixed with low pole aliphatic hydrocarbon), obtains glue；
B it after) oxidant, radical initiator, bromating agent and the glue are mixed, is reacted, is obtained anti-
Glue after answering；
C acid binding agent) is sequentially added into the glue after the reaction and ties up sour promotor and is reacted, and is reacted
Liquid；
D) by after reaction solution washing, stabilizer mixing is added, then flash removing solvent, obtains sizing material；
E) by after the sizing material extrusion dehydration, drying, brominated isobutylene-p-methylstyrene copolymer is obtained.
The present invention first mixes isobutene-p-methylstyrene copolymer with low pole aliphatic hydrocarbon, obtains glue.
Specifically, graininess isobutene-p-methylstyrene copolymer is swollen in aliphatic hydrocarbon, stirring is sufficiently molten to it
Solution, obtains glue.
Wherein, the isobutene-p-methylstyrene molecular weight of copolymer is 100000~450000g/mol, molecular weight
Distribution 1.0~4.5, p-methylstyrene content are 3%mol, and 125 DEG C of Mooney viscosity ML (1+8) are 46 ± 5.
The low pole aliphatic hydrocarbon be selected from C5~C8 low pole aliphatic hydrocarbon, preferably n-hexane, pentane, isohexane,
Isopentane or normal heptane.
The viscosity of the glue is 250~650cp, preferably 350~550cp, the content of butyl rubber in the glue
For 5wt%~25wt%, preferably 10wt%~20wt%.
After obtaining glue, after oxidant, radical initiator, bromating agent and the glue are mixed, carry out anti-
It answers, the glue after being reacted.
Wherein, the oxidant is one of hydrogen peroxide, hypochlorite, bromate or a variety of, preferably hypochlorous acid
Sodium or hydrogen peroxide；It is (0.7 to the molar ratio of methyl group in the oxidant and isobutene-p-methylstyrene copolymer
~2): 1, preferably (1.0~1.5): 1.
The radical initiator is selected from azobisisoheptonitrile, azodiisobutyronitrile, azo two (2- methyl fourth) nitrile, 2,2-
One of azo two (trimethylpentane nitrile) and azo two (2,4- dimethyl-penten) nitrile are a variety of, preferably two isobutyl of azo
Nitrile；The radical initiator and isobutene-p-methylstyrene copolymer mass ratio are (0.2~5): 100, preferably
(0.5~4.5): 100, further preferably (1.5~3.5): 100.
The bromating agent is selected from Br2, HBr, cross pyridinium bromide hydrobromide, C5H6Br2N2O2, tetrabromo cyclic ketones, phenyl trimethicone
Tribromide ammonium, benzyl trimethyl tribromide ammonium, dibromo isocyanurate, N-bromoacetamide, N- bromo-succinimide, N- bromo are adjacent
Xyxylene amide, N, N '-two bromo- 5, one of 5 ' dimethyl hydantoins or a variety of, preferably Br2, HBr or NBS；
In the bromating agent in bromo element and isobutene-p-methylstyrene copolymer to methyl mole for (0.7~
2): 1, preferably (1.0~1.5): 1.
After oxidant, radical initiator, bromating agent and the glue are mixed, reacted, the reaction
Temperature be 20~55 DEG C, preferably 30~50 DEG C；Time is 1~60min, preferably 10~50min.
Then, acid binding agent is sequentially added into the glue after the reaction and ties up sour promotor and is reacted, and is obtained anti-
Answer liquid
The acid binding agent is selected from one of sodium hydroxide, sodium hydrogensulfite, sodium carbonate, sodium bicarbonate or a variety of, preferably
For the mixed solution or sodium hydrate aqueous solution of sodium hydroxide and sodium hydrogensulfite；Bromine member in the acid binding agent and bromating agent
The molar ratio of element is (0.5~2.5): 1, preferably (1.0~2.0): 1；
It is described to tie up sour promotor selected from fatty alcohol, polyethers, alkali or alkaline earth metal carboxylate, epoxides, metal oxygen
One of inorganic salts of compound or hydroxide, highly basic and weak acid are a variety of, preferably methanol, ethyl alcohol, the tert-butyl alcohol, epoxidation
Esters, C8~C24 unsaturated fatty acid glyceride, Ca (OH)2、CaO、Mg(OH)2, MgO, sodium carbonate, sodium bicarbonate,
One of epoxidized soybean oil, epoxidized linseed oil, calcium stearate, stearic acid are a variety of；It is described to tie up sour promotor and isobutyl
Alkene-p-methylstyrene copolymer mass ratio is (0.001~10): 100, preferably (0.01~5): 100, further preferably
For (0.1~1): 100.
Then, by after reaction solution washing, stabilizer mixing is added, then flash removing solvent, obtains sizing material
Specifically, sufficiently washed with deionized water to reaction solution pH be 6.5~8.0 after be added stabilizer be uniformly mixed.
The stabilizer is selected from one of calcium stearate, zinc stearate, epoxidized soybean oil or a variety of, preferably stearic acid
Calcium and epoxidized soybean oil；The stabilizer and isobutene-p-methylstyrene mass ratio are (1~2.5): 100, preferably
(1.0~2.0): 100.
85 DEG C~98 DEG C hot water flash evaporations are added in above-mentioned system and remove solvent, obtain sizing material；
Sizing material extrusion dehydration on a mill is taken out, brominated isobutylene-p-methylstyrene copolymer is dried to obtain.Its
In, the temperature of the extrusion dehydration is 98~105 DEG C, and the time is 1~3min.
The present invention also provides a kind of brominated isobutylene that above-mentioned preparation method is prepared-p-methylstyrene copolymerization
Object.
Brominated isobutylene provided by the invention-p-methylstyrene copolymer preparation method, it is right to specifically include isobutene-
Methylstyrene copolymer dissolution, initiation, bromination, neutralization, washing, Product recycling, the present invention is using low pole fat
Hydrocarbon carries out bromination to isobutene-p-methylstyrene copolymer as bromination solvent and improves bromination reaction rate, and bromination workshop section adds
Enter conversion ratio and utilization rate that oxidant improves bromating agent bromo element, is added in and in workshop section and ties up in sour promotor raising and imitate
Rate reduces the incomplete possibility of neutralization, and gained brominated isobutylene-p-methylstyrene copolymer indices are excellent, knot
Structure is more stable, and safety is higher.
For a further understanding of the present invention, below with reference to embodiment to brominated isobutylene-provided by the invention to methylbenzene
Ethylene copolymer and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
The present embodiment is using isohexane as bromination solvent, Br2For bromating agent, NaClO is oxidant, to isobutene-to methyl
Styrol copolymer carries out bromination, and 2wt%NaOH is acid binding agent, and ethyl alcohol is to tie up sour promotor, obtains BIMSM.Specific steps are such as
Under:
1) isobutene-p-methylstyrene copolymer 60g is weighed, 340g isohexane is added, is swollen, stirring obtains quality
Score is the glue of 15wt%.Isobutene-p-methylstyrene copolymer p-methylstyrene content 3%mol, Mooney viscosity ML
125 DEG C of (1+8) is 46 ± 5.
2) it under the conditions of 50 DEG C, is added in the 4g 25wt%NaClO aqueous solution addition resulting glue of step 1) and mixes into glue
It closes uniform.
3) 2g 20wt% azodiisobutyronitrile/iso-hexane and 20g10wt%Br are added into step 2) glue2/ different
Hexane solution reacts 40min.
4) 25g 2wt%NaOH and 0.2g ethyl alcohol are successively added in step 3) system and stir 5min.
5) glue obtained by step 4) is washed, then according to isobutene-p-methylstyrene: calcium stearate: epoxy soybean
Oil=100:1.5:1.5 mass ratio stirs evenly after corresponding stabilizer is added.
6) glue obtained by step 5) is flashed into removing solvent, then 100 DEG C of open mill dehydration and drying at 98 DEG C, obtained
BIMSM product.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.45 ± 0.2wt%, and bromine utilization rate is greater than 80% in bromating agent, 125 DEG C of Mooney viscosity ML (1+8)
It is 32 ± 4.
Embodiment 2
For the present embodiment using isopentane as bromination solvent, HBr is bromating agent, H2O2For oxidant, to isobutene-to methylbenzene
Ethylene copolymer carries out bromination, 2wt%NaOH and 0.5wt%NaHSO3Mixed solution is acid binding agent, and calcium stearate is to tie up sour rush
Into agent, BIMSM is obtained.Specific step is as follows:
1) isobutene-p-methylstyrene copolymer 30g is weighed, 270g isopentane is added, is swollen, stirring obtains quality
Score is the glue of 10wt%.Isobutene-p-methylstyrene copolymer p-methylstyrene content is 3%mol, Mooney viscosity
125 DEG C of ML (1+8) are 46 ± 5.
2) under the conditions of 25 DEG C, 3g 30wt%H is added into glue2O2Aqueous solution is added in the resulting glue of step 1) and mixes
Uniformly.
3) 2g 10wt% azodiisobutyronitrile/iso-hexane and 20g10wt%HBr water are added into step 2) glue
Solution reaction 60min.
4) 30g 2wt%NaOH and 0.5g calcium stearate are successively added in step 3) system and stir 5min.
5) glue obtained by step 4) is washed, then according to isobutene-p-methylstyrene: calcium stearate: epoxy soybean
Oil=100:0.5:1.6 mass ratio stirs evenly after corresponding stabilizer is added.
6) glue obtained by step 5) is flashed into removing solvent, then 100 DEG C of open mill dehydration and drying at 98 DEG C, obtained
BIMSM product.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.60 ± 0.2wt%, and bromine utilization rate > 85% in bromating agent, 125 DEG C of Mooney viscosity ML (1+8) are
32±4。
Embodiment 3
The present embodiment is using isohexane as bromination solvent, Br2For bromating agent, H2O2For oxidant, to isobutene-to methylbenzene
Ethylene copolymer carries out bromination, 2wt%NaOH and 0.5wt%NaHSO3Mixed solution is acid binding agent, and epoxidized soybean oil is to tie up acid
Promotor obtains BIMSM.Specific step is as follows:
1) isobutene-p-methylstyrene copolymer 60g is weighed, 270g isohexane is added, is swollen, stirring obtains quality
Score is the glue of 20wt%.Isobutene-p-methylstyrene copolymer p-methylstyrene content is 3%mol, Mooney viscosity
125 DEG C of ML (1+8) are 46 ± 5.
2) under the conditions of 45 DEG C, 2g30wt%H is added into glue2O2Aqueous solution is added in the resulting glue of step 1) and mixes
Uniformly.
3) 4g 20wt% azodiisobutyronitrile/iso-hexane and 25g20wt%Br are added into step 2) glue2/ different
Hexane solution.
4) 40g4wt%NaOH and 0.5g epoxidized soybean oil is successively added in step 3) system and stirs 5min.
5) glue obtained by step 4) is washed, then according to isobutene-p-methylstyrene: calcium stearate: epoxy soybean
Oil=100:2:1 mass ratio stirs evenly after corresponding stabilizer is added.
6) glue obtained by step 5) is flashed into removing solvent, then 100 DEG C of open mill dehydration and drying at 98 DEG C, obtained
BIMSM product.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.80 ± 0.2wt%, and bromine utilization rate is greater than 75% in bromating agent, 125 DEG C of Mooney viscosity ML (1+8)
It is 32 ± 4.
Embodiment 4
The present embodiment is using isohexane as bromination solvent, Br2For bromating agent, H2O2For oxidant, to isobutene-to methylbenzene
Ethylene copolymer carries out bromination, 2wt%NaOH and 0.5wt%NaHSO3Mixed solution is acid binding agent, and sodium bicarbonate is to tie up sour rush
Into agent, BIMSM is obtained.Specific step is as follows:
1) isobutene-p-methylstyrene copolymer 30g is weighed, 170g isohexane is added, is swollen, stirring obtains quality
Score is the glue of 15wt%.Isobutene-p-methylstyrene copolymer p-methylstyrene content is 3%mol, Mooney viscosity
125 DEG C of ML (1+8) are 46 ± 5.
2) under the conditions of 35 DEG C, 1g 30wt%H is added into glue2O2Aqueous solution is added in the resulting glue of step 1) and mixes
Uniformly.
3) 3g 10wt% azodiisobutyronitrile/iso-hexane and 10g10wt%Br are added into step 2) glue2/ different
Hexane solution.
4) 40g 2wt%NaOH and 0.5g sodium bicarbonate are successively added in step 3) system and stir 5min.
5) glue obtained by step 4) is washed, then according to isobutene-p-methylstyrene: calcium stearate: epoxy soybean
Oil=100:2:1 mass ratio stirs evenly after corresponding stabilizer is added.
6) glue obtained by step 5) is flashed into removing solvent, then 100 DEG C of open mill dehydration and drying at 98 DEG C, obtained
BIMSM product.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.40 ± 0.2wt%, and bromine utilization rate is greater than 88% in bromating agent, 125 DEG C of Mooney viscosity ML (1+8)
It is 32 ± 4.
Embodiment 5
For the present embodiment using isohexane as bromination solvent, NBS is bromating agent, H2O2For oxidant, to isobutene-to methylbenzene
Ethylene copolymer carries out bromination, 2wt%NaOH and 0.5wt%NaHSO3Mixed solution is acid binding agent, and zinc stearate is to tie up sour rush
Into agent, BIMSM is obtained.Specific step is as follows:
1) isobutene-p-methylstyrene copolymer 30g is weighed, 170g isohexane is added, is swollen, stirring obtains quality
Score is the glue of 15wt%.Isobutene-p-methylstyrene copolymer p-methylstyrene content is 3%mol, Mooney viscosity
125 DEG C of ML (1+8) are 46 ± 5.
2) under the conditions of 35 DEG C, 1g30wt%H is added into glue2O2Aqueous solution is added in the resulting glue of step 1) and mixes
Uniformly.
3) 1g 20wt% azodiisobutyronitrile/iso-hexane and 30g10wt%NBS/ third are added into step 2) glue
Ketone solution.
4) 40g3wt%NaOH and 0.5g zinc stearate is successively added in step 3) system and stirs 5min.
5) glue obtained by step 4) is washed, then according to isobutene-p-methylstyrene: calcium stearate: epoxy soybean
Oil=100:2:1 mass ratio stirs evenly after corresponding stabilizer is added.
6) glue obtained by step 4) is flashed into removing solvent, then 100 DEG C of open mill dehydration and drying at 98 DEG C, obtained
BIMSM product.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.8 ± 0.2wt%, and bromine utilization rate is 80% in bromating agent, and 125 DEG C of Mooney viscosity ML (1+8) are 32
±4。
Comparative example 1
Process flow and step are with embodiment 1, and rest materials proportion is also identical, and difference is oxidant, ties up sour promotor
It is replaced with equal amount isohexane.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.2 ± 0.1wt%, and bromine utilization rate is 20% in bromating agent, and 125 DEG C of Mooney viscosity ML (1+8) are 26
±4。
Comparative example 2
Process flow and step are with embodiment 1, and rest materials proportion is also identical, and difference is oxidant equal amount dissident
Alkane replaces.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.4 ± 0.1wt%, and bromine utilization rate is 20% in bromating agent, and 125 DEG C of Mooney viscosity ML (1+8) are 20
±4。
Comparative example 3
Process flow and step are with embodiment 1, and rest materials proportion is also identical, and difference is to tie up sour promotor equal amount
Isohexane replaces.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.25 ± 0.1wt%, and bromine utilization rate is greater than 80% in bromating agent, 125 DEG C of Mooney viscosity ML (1+8)
It is 25 ± 4.
Comparative example 4
Process flow and step are with embodiment 3, and rest materials proportion is also identical, and difference is oxidant, ties up sour promotor
It is replaced with equal amount isohexane.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.2 ± 0.1wt%, and bromine utilization rate is 20% in bromating agent, and 125 DEG C of Mooney viscosity ML (1+8) are 26
±4。
Comparative example 5
Process flow and step are with embodiment 3, and rest materials proportion is also identical, and difference is oxidant equal amount dissident
Alkane replaces.
Nmr analysis, Mooney viscosity analysis, GPC test, gained are carried out to the above-mentioned chlorinated scoline product of preparation
BIMSM benzyl bromine content is 0.45 ± 0.1wt%, and bromine utilization rate is 20% in bromating agent, and 125 DEG C of Mooney viscosity ML (1+8) is
28±4。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of brominated isobutylene-p-methylstyrene copolymer preparation method, which comprises the following steps:
A isobutene-p-methylstyrene copolymer is mixed with low pole aliphatic hydrocarbon), obtains glue；
B it after) oxidant, radical initiator, bromating agent and the glue are mixed, is reacted, after obtaining reaction
Glue；
C acid binding agent) is sequentially added into the glue after the reaction and ties up sour promotor and is reacted, and reaction solution is obtained；
D) by after reaction solution washing, stabilizer mixing is added, then flash removing solvent, obtains sizing material；
E) by after the sizing material extrusion dehydration, drying, brominated isobutylene-p-methylstyrene copolymer is obtained.
2. preparation method according to claim 1, which is characterized in that the low pole aliphatic hydrocarbon is selected from the weak pole of C5~C8
Property aliphatic hydrocarbon.
3. preparation method according to claim 1, which is characterized in that the viscosity of the glue is 250~650cp, described
Isobutene-p-methylstyrene copolymer mass percentage is 5wt%~25wt% in glue.
4. preparation method according to claim 1, which is characterized in that the oxidant is hydrogen peroxide, hypochlorite, bromine
One of hydrochlorate is a variety of；
It is (0.7~2) to the molar ratio of methyl group in the oxidant and isobutene-p-methylstyrene copolymer: 1.
5. preparation method according to claim 1, which is characterized in that the radical initiator be azobisisoheptonitrile,
Azodiisobutyronitrile, azo two (2- methyl fourth) nitrile, 2,2- azo two (trimethylpentane nitrile) and (the 2,4- dimethyl of azo two
Penta) one of nitrile or a variety of；
Radical initiator and isobutene-p-methylstyrene copolymer mass ratio are (0.2~5): 100.
6. preparation method according to claim 1, which is characterized in that the bromating agent is selected from Br2, HBr, cross pyridinium bromide
Hydrobromate, C5H6Br2N2O2, tetrabromo cyclic ketones, phenyltrimethyl-ammonium tribromide, benzyl trimethyl tribromide ammonium, dibromo isocyanide urine
Acid, N-bromoacetamide, N- bromo-succinimide, N- bromo O-phthalic base amide, N, in bromo- 5,5 ' the dimethyl second of N '-two
One of uride is a variety of；
It in bromo element and isobutene-p-methylstyrene copolymer to methyl mole is (0.7~2) in the bromating agent: 1.
7. preparation method according to claim 1, which is characterized in that the acid binding agent is selected from sodium hydroxide, bisulfite
One of sodium, sodium carbonate, sodium bicarbonate are a variety of；In the acid binding agent and bromating agent the molar ratio of bromo element be (0.5~
2.5):1；
It is described to tie up sour promotor selected from fatty alcohol, polyethers, alkali or alkaline earth metal carboxylate, epoxides, metal oxide
Or one of inorganic salts of hydroxide, highly basic and weak acid or a variety of；The sour promotor and isobutene-tied up is to methylbenzene second
The mass ratio of alkene copolymer is (0.001~10): 100.
8. preparation method according to claim 1, which is characterized in that the stabilizer be selected from calcium stearate, zinc stearate,
One of epoxidized soybean oil is a variety of；The stabilizer and isobutene-p-methylstyrene mass ratio are (1~2.5):
100。
9. preparation method according to claim 1, which is characterized in that step B) in, the temperature of the reaction is 20~55
DEG C, the time is 1~60min.
10. a kind of brominated isobutylene-that preparation method as claimed in any one of claims 1 to 9 wherein is prepared is to methylbenzene
Ethylene copolymer.
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| US5077345A (en) * | 1990-03-01 | 1991-12-31 | Exxon Chemical Patents Inc. | Halogenation of polymers with improved neutralization |
| CN1225648A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Process for halogenation of isomonoolefin/para-alkylstyrene copolymers |
| CN105111347A (en) * | 2015-09-15 | 2015-12-02 | 黄河三角洲京博化工研究院有限公司 | Producing method for brominating butyl rubber |
| CN106661144A (en) * | 2014-07-07 | 2017-05-10 | 阿朗新科新加坡私人有限公司 | Ultrafiltration of polyisoolefin copolymers |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077345A (en) * | 1990-03-01 | 1991-12-31 | Exxon Chemical Patents Inc. | Halogenation of polymers with improved neutralization |
| CN1225648A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Process for halogenation of isomonoolefin/para-alkylstyrene copolymers |
| CN106661144A (en) * | 2014-07-07 | 2017-05-10 | 阿朗新科新加坡私人有限公司 | Ultrafiltration of polyisoolefin copolymers |
| CN105111347A (en) * | 2015-09-15 | 2015-12-02 | 黄河三角洲京博化工研究院有限公司 | Producing method for brominating butyl rubber |
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