CN104672472B - The preparation method of thermal reversion crosslinking brominated polyisobutylene and p-methylstyrene copolymer rubber - Google Patents
The preparation method of thermal reversion crosslinking brominated polyisobutylene and p-methylstyrene copolymer rubber Download PDFInfo
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- CN104672472B CN104672472B CN201410259853.7A CN201410259853A CN104672472B CN 104672472 B CN104672472 B CN 104672472B CN 201410259853 A CN201410259853 A CN 201410259853A CN 104672472 B CN104672472 B CN 104672472B
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Abstract
The present invention relates to a kind of thermal reversions to be crosslinked method for preparing rubber.What thermal reversion was crosslinked rubber matrix selection is brominated polyisobutylene and p-methylstyrene copolymer, using tetramethylethylenediamine as crosslinking agent, it is blended, cross-linked three D reticular polymer is formed under hot pressing condition, has the characteristics that vulcanized rubber, under the conditions of higher temperature inverse cross-linking reaction can occur for this thermal reversion crosslinking rubber, again depolymerization forms two-dimensional structure to polymer three-dimensional structure, and material has thermoplastic processability.
Description
Technical field
What novel thermal reversion crosslinking rubber matrix was selected is brominated polyisobutylene and p-methylstyrene copolymer, it has
With tetramethylethylenediamine quaternary ammonium reaction, the polyisobutenyl rubber being crosslinked can occur for benzyl bromo functional groups.This heat
Hofmann elimination can occur for reversible crosslink rubber, depolymerization forms two to three-dimensional polymer again under higher temperature conditions
Structure is tieed up, there is thermoplastic processing.
Background technique
Tire, sebific duct and sealing element etc. are essential rubber products for our schedule lives.These rubber products
It is that other systems such as vulcanizing agent and reinforcing agent are added in raw rubber to be kneaded sulfidization molding.The three-dimensional vulcanization that rubber carries out, is improved
Polymer thermostable, modulus and other service performances.But rubber once forms cross-linked structure, rubber through over cure
Middle strand is difficult to become linear condition again, greatly limits it and recycles.Increasingly with non-renewable resources such as petroleum
Exhaustion, preparation can be secondary or the rubber elastomer product repeatedly processed increasingly seem important.
Polyisobutene and p-methylstyrene copolymer are a kind of rubber products with excellent properties, it both has tradition
The good air-tightness and high damping of butyl rubber, while also the weatherability with EP rubbers and chemical stability etc. are excellent
Point.Brominated polyisobutylene and p-methylstyrene copolymer have unique benzyl bromo functional groups as crosslinking points, avoid biography
Uniting, butyl rubber bromine content is low, and the high disadvantage of degree of unsaturation ensure that the vulcanization of rubber product is uniform, excellent mechanical.
Earliest Harumi publication (JP73-36293) is reported using polyvinyl chloride or neoprene as rubber-based
Body prepares thermal reversion cross-linked rubber masses using dicyclopentadiene sodium as crosslinking agent.
Kennedy publication (USP4138441) uses dimethylcyclo-pentadienyl aluminium (Me2AlCPD) as crosslinking
Agent is swapped with chlorine-containing polymer and is reacted, and is prepared for chlorinated butyl rubber and chlorination second the third glue thermal reversion with CPD side group and is handed over
Join rubber.
Masatoshi reports (Masatoshi Miura*, Soluble cyclopentadienylated
Polymers, Makromolekulare Chemie, 1985,186(3)) under the conditions of excessive metallic sodium, pass through poly- pair of chlorination
Methyl styrene is reacted with cyclopentadiene, and synthesis has the poly- p-methylstyrene of cyclopentadienyl group.
Fan Yunge reports (preparation of Polystyrene Type Resins Bearing Bisquarternary Ammonium Founctions and performance study, Ion Exchange and
Adsorption, 2006) it is reacted using triethylene diamine and tetramethylethylenediamine with Chloromethyl polystyrene, contained simultaneously
Strong-weak base type resin of quaternary ammonium and tertiary amine, then with the quaternized tertiary amine of iodomethane, prepare the double Quaternary Ammonium Resins of polystyrene.
Li Yan (thermal reversion of brombutyl is crosslinked, China Synthetic Rubber Industry, 2009) is reported using tertiary amine functional group
Polymer as crosslinking agent, prepare thermal-reversible cross-linking agent using brombutyl as matrix.What is selected in article is bromination
Butyl rubber, crosslinking agent is that the tertiary amine extension of synthesis can roll into a ball polymer, using high bromine content brominated polyisobutylene in this patent
With p-methylstyrene random copolymer, crosslinking agent is tetramethylethylenediamine class tertiary amine crosslinking agent.
Chen Xiaonong publication (CN101955592A) is reported using traditional butyl rubber as rubber matrix, using bicyclic penta
Diene formates and the polymer of the side group containing pyridine prepare thermal reversion crosslinking rubber as crosslinking agent.Colloid in patent is to pass
The butyl rubber of system, bromine content is low, poor as crosslinking agent reaction effect using dicyclopentadiene sodium formate, and traditional butyl
Rubber has unsaturated double-bond, and heatproof air aging performance is poor, and thermoplastic processability is influenced by very big.
Summary of the invention
It can be with the rubber material of thermoplastic processing, using special brominated polyisobutylene it is an object of the invention to prepare one kind
Matrix with p-methylstyrene copolymer as rubber material, it has unique benzyl bromo functional groups, can be with tetramethyl
Quaternary ammonium reaction occurs for ethylenediamine, forms thermal reversion and is crosslinked rubber.This high molecular material strand is full saturated structures, is had
Excellent weatherability and heatproof air aging performance is very beneficial for the thermoplastic processing in later period, and bromine content can pass through control
P-methylstyrene content progress rationally accurate control in polymer, guarantee benzyl bromide are abundant anti-with dicyclopentadiene sodium formate
It answers.
The present invention mainly passes through synthesis brominated polyisobutylene and p-methylstyrene random copolymer and tetramethylethylenediamine
Processing is blended, obtains the brominated polyisobutylene and p-methylstyrene copolymer rubber of thermal reversion crosslinking.
1, polymerization synthesizing polyisobutylene and p-methylstyrene random copolymer are controlled by cation, then carries out bromination
The modified brominated polyisobutylene and p-methylstyrene copolymer obtained with benzyl bromo functional groups, is crosslinked rubber as thermal reversion
Material of main part.
2, using open mill, rubber is sufficiently kneaded with tetramethylethylenediamine, roll spacing 10mm bottom sheet, room temperature cooling is put
After setting 10 hours, using vulcanizing press, under the conditions of 100~160 DEG C, pressure 10Mpa, vulcanization time 40~60min heat
Pressure is cold-pressed 60min in pressure maintaining, obtains reversible crosslink rubber.
Base rubber in the present invention is brominated polyisobutylene and p-methylstyrene random copolymer.
Base rubber bromine content in the present invention is in 0.8~2.3%(mol), preferably 1.1~2.3%(mol).
The dosage of tetramethyl diethylamide is 0.3~3 part (in every 100 parts of rubber) in the present invention.
Hot pressing temperature in the present invention selects 100 DEG C~160 DEG C, and the preferable temperature of crosslinking agent tetramethylethylenediamine is 100
~130 DEG C.
After brominated polyisobutylene is mixed with p-methylstyrene random copolymer with carbon black in the present invention, thermal reversion is added and hands over
Join agent, hot-forming, pressure maintaining solidification prepares thermal reversion crosslinking rubber.
It is as follows that tetramethyl diethylamide is kneaded glue formula:
| Ingredient | Number |
| BIMS | 100 |
| Carbon black | 10~40 |
| Tetramethyl diethylamide | 0.3~3 |
Specific embodiment
11 embodiments are set forth below, the present invention is further illustrated, the present invention is not limited solely to these embodiments.
Embodiment 1
In nitrogen glove box, under the conditions of -80 DEG C, in three-necked flask be added 120ml isobutene, 200ml chloromethanes and
10ml p-methylstyrene, is sufficiently mixed, be added 10ml alkyl aluminum chloride initiator (0.04mol/L) synthesizing polyisobutylene with it is right
Methyl styrene random copolymer.
Embodiment 2
100g polyisobutene and p-methylstyrene copolymer are dissolved in 800ml hexane, it is molten that a certain amount of bromine is added
Liquid (bromine content is 0.6g/ml) reacts 30 minutes under illumination condition, and product flash distillation removes solvent hexane, in 30 DEG C of vacuum drying ovens
Drying obtains the brominated polyisobutylene and p-methylstyrene random copolymer of a series of different bromine contents to constant weight.
Embodiment 3
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 0.8%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 4
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 1.8%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 5
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.2%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 6
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 0.3g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 7
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 1.0g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 8
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 20g, tetramethyl diethylamide crosslinking agent 3.0g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 9
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 10g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 10
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 30g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
Embodiment 11
2 gained brominated polyisobutylene of Example and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), charcoal
Black 40g, tetramethyl diethylamide crosslinking agent 1.5g.Under room temperature, mill mixing is uniform, roll spacing 10mm bottom sheet, and room temperature is cold
But 24 hours.100 DEG C of vulcanizing press, under the conditions of pressure 10Mpa, it is molded 50min, cold pressing 60min film molding.Film is cut into
Small pieces are molded 60min again under the conditions of 130 DEG C of vulcanizing press, pressure 10Mpa, and film forms again.Film is cut out again
At small pieces, again under the conditions of 160 DEG C of vulcanizing press, pressure 10Mpa, it is molded 60min, film third time time molding.
1 tetramethylethylenediamine crosslinking agent sulfurizing formula of table
Claims (4)
1. a kind of preparation method of thermal reversion crosslinking rubber, the thermal reversion crosslinking rubber is used for pump valve seal material, tire
The sealing material of inner liner or the inner tube of a tyre, which is characterized in that polymerization synthesizing polyisobutylene is controlled by cation and to methylbenzene second
Then olefinic random copolymer carries out the modified brominated polyisobutylene and p-methylstyrene for obtaining having benzyl bromo functional groups of bromination
Copolymer；
What thermal reversion was crosslinked rubber matrix selection is the brominated polyisobutylene and p-methylstyrene copolymer, using tetramethyl
Ethylenediamine is blended as crosslinking agent, hot-forming；
Wherein, the entire macromolecular chain of rubber matrix is full saturated structures, and contains benzyl bromo functional groups；Bromine in rubber matrix
Content is in 0.8~2.3% molar content；Hot pressing temperature selects 100 DEG C~160 DEG C；Sulfurizing formula: 100 parts of rubber matrix, carbon black
10~40 parts, 0.3~3 part of tetramethylethylenediamine.
2. the preparation method of thermal reversion crosslinking rubber according to claim 1, it is characterised in that: bromine content in rubber matrix
In 1.1~2.3% molar contents.
3. the preparation method of thermal reversion crosslinking rubber according to claim 1 or 2, which is characterized in that hot pressing temperature is selected
100~130 DEG C.
4. the preparation method of thermal reversion crosslinking rubber according to claim 1 or 2, concrete operations are as follows: open mill is used, it will
Rubber matrix is sufficiently kneaded with tetramethylethylenediamine, roll spacing 10mm bottom sheet, after the cooling placement of room temperature 10 hours, using flat
Plate vulcanizer, under the conditions of 100~160 DEG C, pressure 10Mpa, vulcanization time 40~60min hot pressing is cold-pressed 60min in pressure maintaining,
Obtain thermal reversion crosslinking rubber.
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| CN201410259853.7A CN104672472B (en) | 2014-06-12 | 2014-06-12 | The preparation method of thermal reversion crosslinking brominated polyisobutylene and p-methylstyrene copolymer rubber |
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| CN201410259853.7A CN104672472B (en) | 2014-06-12 | 2014-06-12 | The preparation method of thermal reversion crosslinking brominated polyisobutylene and p-methylstyrene copolymer rubber |
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| CN104672472B true CN104672472B (en) | 2019-03-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105733110B (en) * | 2016-02-25 | 2018-11-27 | 北京石油化工学院 | One kind can repeatedly process thermal reversion crosslinking polyisobutene class method for preparing rubber |
| CN106046578B (en) * | 2016-05-27 | 2018-07-24 | 佛山市南海区平洲振裕金属回收有限公司 | A kind of rubber composition of tire tread and preparation method thereof of easy recycling |
| JP6926495B2 (en) * | 2017-02-01 | 2021-08-25 | 横浜ゴム株式会社 | Thermoplastic composition, inner liner and pneumatic tire |
| EP3730548B1 (en) * | 2018-07-27 | 2023-06-28 | Sumitomo Rubber Industries, Ltd. | Rubber composition and tire |
| CN111808377B (en) * | 2020-07-22 | 2023-06-16 | 四川远星橡胶有限责任公司 | Self-repairing tire inner liner rubber material and preparation method thereof |
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|---|---|---|---|---|
| CN1524109A (en) * | 2001-06-07 | 2004-08-25 | ����ɭ���ڻ�ѧר����˾ | Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof |
| CN101896365A (en) * | 2007-12-18 | 2010-11-24 | 米其林技术公司 | Be used in particular for the rubber composition that tire is made |
| CN101991501A (en) * | 2009-08-27 | 2011-03-30 | 郑州市翱翔医药包装有限公司 | Ultraclean medicinal bottle plug and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538158B2 (en) * | 2003-03-06 | 2009-05-26 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer composition having viscosity-enhanced and vulcanized elastomer dispersions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524109A (en) * | 2001-06-07 | 2004-08-25 | ����ɭ���ڻ�ѧר����˾ | Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof |
| CN101896365A (en) * | 2007-12-18 | 2010-11-24 | 米其林技术公司 | Be used in particular for the rubber composition that tire is made |
| CN101991501A (en) * | 2009-08-27 | 2011-03-30 | 郑州市翱翔医药包装有限公司 | Ultraclean medicinal bottle plug and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
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| 溴化丁基橡胶的热可逆共价交联;李岩等;《合成橡胶工业》;20090715;第32卷(第4期);第302-305页 |
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