CN104672472A - Preparation method of thermally reversible crosslinked bromide polyisobutene-p-methylstyrene copolymer rubber - Google Patents
Preparation method of thermally reversible crosslinked bromide polyisobutene-p-methylstyrene copolymer rubber Download PDFInfo
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- CN104672472A CN104672472A CN201410259853.7A CN201410259853A CN104672472A CN 104672472 A CN104672472 A CN 104672472A CN 201410259853 A CN201410259853 A CN 201410259853A CN 104672472 A CN104672472 A CN 104672472A
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Abstract
The invention relates to a preparation method of thermally reversible crosslinked rubber. A bromide polyisobutene-p-methylstyrene copolymer is selected as thermally reversible crosslinked rubber matrix; tetramethylethylenediamine is adopted as a crosslinking agent; and the crosslinked three-dimensional mesh polymer is formed under blending and hot-pressing conditions. The crosslinked three-dimensional mesh polymer has the characteristics of vulcanized rubber. The thermally reversible crosslinked rubber can have an inverse crosslinking reaction at a relatively high temperature; the polymer three-dimensional structure is depolymerized to form a two-dimensional structure; and the material has hot-plastic processability.
Description
Technical field
What Novel hot reversible crosslink rubber matrix was selected is brominated polyisobutylene and p-methylstyrene multipolymer, and it has bromotoluene functional group, can with Tetramethyl Ethylene Diamine generation quaternary ammonium reaction, obtain the polyisobutenyl rubber be cross-linked.Under higher temperature conditions, can there is hofmann elimination in this thermal reversion cross-linked rubber, three-dimensional polymer again depolymerization forms two-dirnentional structure, has thermoplastic processibility.
Background technology
Tire, sebific duct and sealing member etc. to be absolutely necessary rubber item for the life of our schedule.These rubber items add the mixing sulfidization molding of other systems such as vulcanizing agent and strengthening agent in rubber.The three-dimensional sulfuration that rubber carries out, improves polymer thermostable, modulus and other use propertieies.But rubber is once form cross-linked structure through over cure, and rubber Middle molecule chain is just difficult to become linear condition again, greatly limit its recycle.Day by day exhausted along with Nonrenewable resources such as oil, preparation secondary or the rubber elastomer goods repeatedly processed can more and more seem important.
Polyisobutene and p-methylstyrene multipolymer are a kind of rubber products with excellent properties, and it had both had good resistance to air loss and the high damping of traditional isoprene-isobutylene rubber, also have the advantages such as the weathering resistance of ethylene-propylene rubber(EPR) and chemical stability simultaneously.Brominated polyisobutylene and p-methylstyrene multipolymer have unique bromotoluene functional group as cross-linking set, avoid traditional isoprene-isobutylene rubber bromine content low, the shortcoming that degree of unsaturation is high, ensure that the sulfuration of rubber item is even, excellent mechanical.
Harumi publication (JP73-36293) reports using polyvinyl chloride or chloroprene rubber as rubber matrix the earliest, adopts dicyclopentadiene sodium as linking agent, prepares thermal reversion cross-linked rubber masses.
Kennedy publication (USP4138441) adopts dimethylcyclo-pentadienyl aluminium (Me
2alCPD) as linking agent, carry out permutoid reaction with chlorine-containing polymer, prepare the chlorinated butyl rubber with CPD side base and chlorination second third glue thermal reversion cross-linked rubber.
Masatoshi reports (Masatoshi Miura*, Soluble cyclopentadienylated polymers, Makromolekulare Chemie, 1985,186(3)) under excessive sodium Metal 99.5 condition, gather p-methylstyrene by chlorination and cyclopentadiene reacts, synthesize the poly-p-methylstyrene with cyclopentadienyl.
(the preparation and property research of Polystyrene Type Resins Bearing Bisquarternary Ammonium Founctions of Fan Yunge report, Ion Exchange and Adsorption, 2006) triethylene diamine and Tetramethyl Ethylene Diamine and Chloromethyl polystyrene is adopted to react, obtain simultaneously containing quaternary ammonium and tertiary amine strong-weak base type resin, use the quaternized tertiary amine of methyl iodide again, prepare the two Quaternary Ammonium Resin of polystyrene.
Li Yan (thermal reversion of brominated butyl rubber is cross-linked, China Synthetic Rubber Industry, 2009) reports and adopts the polymkeric substance of tertiary amine functional group as linking agent, prepares thermal-reversible cross-linking agent using brominated butyl rubber as matrix.What select in article is brominated butyl rubber, and linking agent is that the tertiary amine of synthesis hangs compound of reuniting, and what adopt in this patent is high bromine content brominated polyisobutylene and p-methylstyrene random copolymers, and linking agent is Tetramethyl Ethylene Diamine class tertiary amine linking agent.
Chen Xiao agriculture publication (CN101955592A) report using traditional isoprene-isobutylene rubber as rubber matrix, adopt dicyclopentadiene formate and containing the polymkeric substance of pyridine side base as linking agent, prepare thermal reversion cross-linked rubber.Colloid in patent is traditional isoprene-isobutylene rubber, and bromine content is low, and adopt dicyclopentadiene sodium formiate poor as linking agent reaction effect, and traditional isoprene-isobutylene rubber is with unsaturated double-bond, heatproof air aging performance is poor, and thermoplastic processability affects by very large.
Summary of the invention
The object of the invention is to prepare a kind of can thermoplastic processing elastomeric material, adopt special brominated polyisobutylene and p-methylstyrene multipolymer as the matrix of elastomeric material, it has unique bromotoluene functional group, can with Tetramethyl Ethylene Diamine generation quaternary ammonium reaction, form thermal reversion cross-linked rubber.This macromolecular material molecular chain is full saturated structures, there is excellent weathering resistance and heatproof air aging performance, be very beneficial for the thermoplastic processing in later stage, and bromine content can be undertaken rationally accurately controlling by controlling p-methylstyrene content in polymkeric substance, ensures the abundant reaction of bromotoluene and dicyclopentadiene sodium formiate.
The present invention, mainly through synthesis brominated polyisobutylene and p-methylstyrene random copolymers and the blended processing of Tetramethyl Ethylene Diamine, obtains brominated polyisobutylene that thermal reversion is cross-linked and p-methylstyrene copolymer rubber.
1, control polymerization synthesizing polyisobutylene and p-methylstyrene random copolymers by positive ion, then carry out bromination modification and obtain brominated polyisobutylene with bromotoluene functional group and p-methylstyrene multipolymer, as the material of main part of thermal reversion cross-linked rubber.
2, mill is adopted, rubber and Tetramethyl Ethylene Diamine are carried out fully mixing, roll spacing 10mm bottom sheet, after room temperature cooling placement 10 hours, use vulcanizing press, at 100 ~ 160 DEG C, under pressure 10Mpa condition, curing time 40 ~ 60min hot pressing, to cold pressing 60min in pressurize, obtains reversible crosslink rubber.
Base rubber in the present invention is brominated polyisobutylene and p-methylstyrene random copolymers.
Base rubber bromine content in the present invention is at 0.8 ~ 2.3%(mol), preferably 1.1 ~ 2.3%(mol).
In the present invention, the consumption of tetramethyl-diethylamide is 0.3 ~ 3 part (in every 100 parts of rubber).
Hot pressing temperature in the present invention selects 100 DEG C ~ 160 DEG C, and the preferable temperature of linking agent Tetramethyl Ethylene Diamine is 100 ~ 130 DEG C.
After brominated polyisobutylene mixes with carbon black with p-methylstyrene random copolymers in the present invention, add thermal-reversible cross-linking agent, hot-forming, pressurize is solidified, and prepares thermal reversion cross-linked rubber.
Tetramethyl-diethylamide rubber unvulcanizate formula is as follows:
| Composition | Number |
| BIMS | 100 |
| Carbon black | 10～40 |
| Tetramethyl-diethylamide | 0.3～3 |
Embodiment
Enumerate 11 embodiments below, further illustrated the present invention, the present invention is not only limited to these embodiments.
embodiment 1
In nitrogen glove box, under-80 DEG C of conditions, in there-necked flask, add 120ml iso-butylene, 200ml methyl chloride and 10ml p-methylstyrene, abundant mixing, adds 10ml alkyl aluminum chloride initiator (0.04mol/L) synthesizing polyisobutylene and p-methylstyrene random copolymers.
embodiment 2
100g polyisobutene and p-methylstyrene multipolymer are dissolved in 800ml hexane, add a certain amount of bromine solutions (bromine content is 0.6g/ml), react 30 minutes under illumination condition, product flash distillation removing solvent hexane, be dried to constant weight at 30 DEG C of vacuum drying ovens, obtain brominated polyisobutylene and the p-methylstyrene random copolymers of a series of different bromine content.
embodiment 3
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 0.8%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 4
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 1.8%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 5
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.2%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 6
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 0.3g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 7
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 1.0g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 8
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 20g, tetramethyl-diethylamide linking agent 3.0g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 9
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 10g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 10
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 30g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
embodiment 11
Example 2 gained brominated polyisobutylene and p-methylstyrene copolymer 1 00g, bromine content 2.3%(mol), carbon black 40g, tetramethyl-diethylamide linking agent 1.5g.Under room temperature condition, mill mixing is even, and roll spacing 10mm bottom sheet, room temperature cools 24 hours.Vulcanizing press 100 DEG C, under pressure 10Mpa condition, mold pressing 50min, 60min film of colding pressing is shaping.Film is cut into small pieces, and again vulcanizing press 130 DEG C, under pressure 10Mpa condition, mold pressing 60min, film is again shaping.Film is cut into small pieces again, and again vulcanizing press 160 DEG C, under pressure 10Mpa condition, mold pressing 60min, film third time is secondary shaping.
Table 1 Tetramethyl Ethylene Diamine linking agent sulfurizing formula
Claims (11)
1. thermal reversion cross-linked rubber preparation method: what thermal reversion cross-linked rubber matrix was selected is brominated polyisobutylene and a p-methylstyrene multipolymer, adopts Tetramethyl Ethylene Diamine as linking agent, blended, hot-forming.
2. thermal reversion cross-linked rubber preparation method according to claim 1, it is characterized in that: rubber selects brominated polyisobutylene and p-methylstyrene multipolymer, whole macromolecular chain is full saturated structures, and process based prediction model is stablized, and containing unique bromotoluene functional group.
3. thermal reversion cross-linked rubber preparation method according to claim 1, is characterized in that: the bromine content in the brominated polyisobutylene of rubber matrix and p-methylstyrene multipolymer is higher, and sulfuration processing is active good, and rubber bromine content is in 0.8 ~ 2.3% molar content.
4. thermal reversion cross-linked rubber preparation method according to claim 1, is characterized in that: the bromine content in the brominated polyisobutylene of rubber matrix and p-methylstyrene multipolymer is higher, and sulfuration processing is active good, and rubber bromine content is in 1.1 ~ 2.3% molar content.
5. thermal reversion cross-linked rubber preparation method according to claim 1, is characterized in that: thermal reversion is crosslinked selects Tetramethyl Ethylene Diamine.
6. thermal reversion cross-linked rubber preparation method according to claim 1, is characterized in that: the thermal reversion cross-linked rubber of preparation has suitability for secondary processing, has better tensile strength and elongation at break after secondary processing.
7. thermal reversion cross-linked rubber preparation method according to claim 1, sulfurizing formula: rubber 100 parts, carbon black 10 ~ 40 parts, Tetramethyl Ethylene Diamine 0.3 ~ 3 part.
8. thermal reversion cross-linked rubber preparation method according to claim 1, hot pressing temperature selects 100 DEG C ~ 160 DEG C.
9. thermal reversion cross-linked rubber preparation method according to claim 1, hot pressing temperature selects 100 ~ 130 DEG C.
10. thermal reversion cross-linked rubber preparation method according to claim 1, prepares reversible crosslink rubber and can be applicable to pump valve seal material, the sealing material such as tyre airtight layer or the inner tube of a tyre.
11. thermal reversion cross-linked rubber preparation methods according to claim 1, concrete operations are: adopt mill, rubber and Tetramethyl Ethylene Diamine are carried out fully mixing, roll spacing 10mm bottom sheet, after room temperature cooling placement 10 hours, use vulcanizing press, at 100 ~ 160 DEG C, under pressure 10Mpa condition, curing time 40 ~ 60min hot pressing, to cold pressing 60min in pressurize, obtain reversible crosslink rubber.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733110A (en) * | 2016-02-25 | 2016-07-06 | 北京石油化工学院 | Method for preparing thermal-reversible cross-linking polyisobutene rubber capable of being processed repeatedly |
| CN106046578A (en) * | 2016-05-27 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Tire tread rubber composition easy to recycle and preparation method thereof |
| CN110234704A (en) * | 2017-02-01 | 2019-09-13 | 横滨橡胶株式会社 | Thermoplastic resin composition, liner layer and pneumatic tire |
| CN111770960A (en) * | 2018-07-27 | 2020-10-13 | 住友橡胶工业株式会社 | Rubber composition and tire |
| CN111808377A (en) * | 2020-07-22 | 2020-10-23 | 四川远星橡胶有限责任公司 | Self-repairing tire inner liner rubber material and preparation method thereof |
Citations (4)
| 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 |
| CN1751086A (en) * | 2003-03-06 | 2006-03-22 | 埃克森美孚化学专利公司 | Thermoplastic elastomer composition having viscosity-enhanced and vulcanized elastomer dispersions |
| 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 |
-
2014
- 2014-06-12 CN CN201410259853.7A patent/CN104672472B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| CN1751086A (en) * | 2003-03-06 | 2006-03-22 | 埃克森美孚化学专利公司 | Thermoplastic elastomer composition having viscosity-enhanced and vulcanized elastomer dispersions |
| 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 |
|---|
| 李岩等: "溴化丁基橡胶的热可逆共价交联", 《合成橡胶工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733110A (en) * | 2016-02-25 | 2016-07-06 | 北京石油化工学院 | Method for preparing thermal-reversible cross-linking polyisobutene rubber capable of being processed repeatedly |
| 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 |
| CN106046578A (en) * | 2016-05-27 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Tire tread rubber composition easy to recycle and preparation method thereof |
| 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 |
| CN110234704A (en) * | 2017-02-01 | 2019-09-13 | 横滨橡胶株式会社 | Thermoplastic resin composition, liner layer and pneumatic tire |
| CN111770960A (en) * | 2018-07-27 | 2020-10-13 | 住友橡胶工业株式会社 | Rubber composition and tire |
| CN111808377A (en) * | 2020-07-22 | 2020-10-23 | 四川远星橡胶有限责任公司 | Self-repairing tire inner liner rubber material and preparation method thereof |
| 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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