CN104448060A - Preparation method of epoxidized solution polymerized styrene-butadiene rubber - Google Patents
Preparation method of epoxidized solution polymerized styrene-butadiene rubber Download PDFInfo
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- CN104448060A CN104448060A CN201410806562.5A CN201410806562A CN104448060A CN 104448060 A CN104448060 A CN 104448060A CN 201410806562 A CN201410806562 A CN 201410806562A CN 104448060 A CN104448060 A CN 104448060A
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- butadiene styrene
- styrene rubber
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Abstract
The invention discloses a preparation method of epoxidized solution polymerized styrene-butadiene rubber. According to the preparation method, performic acid is generated in situ by H2O2 and HCOOH peracid system under a mild reaction condition, and the performic acid and double bonds on a solution polymerized styrene-butadiene rubber (SSBR) molecular chain undergo epoxidation reaction in an organic phase to obtain the epoxidized solution polymerized styrene-butadiene rubber. Epoxy groups introduced into SSBR have relatively strong reaction activity and can improve the polarity of the SSBR molecular chain, enhance the interaction between the SSBR molecular chain and the packing and improve the compatibility between an SSBR rubber matrix and a reinforcing agent.
Description
Technical field
The preparation method of this solution polymerized butadiene styrene rubber in-situ oxidation epoxy styrene-butadiene rubber(SBR) is that the approach reacted by polymer chemistry is realized, and this invention belongs to the preparation field of macromolecular material.
Background technology
In solution polymerized butadiene styrene rubber (SSBR), introduce epoxide group, can increase SSBR polarity of chain, strengthen the interaction force between filler, improving the consistency of SSBR rubber matrix and strengthening agent, is one of Main Means preparing high-performance tire.Epoxide group has stronger reactive behavior simultaneously, and the further modification for SSBR provides conveniently, therefore studies SSBR epoxidation reaction tool and is of great significance.Process for epoxidation mainly contains: cross acid system, superoxide method and ketone peroxide method, these methods respectively have its relative merits.With H
2o
2with the acid system excessively that HCOOH is representative, reaction conditions is gentle, and by product is water, and environmental pollution is little, is one of epoxidised prefered method.
Invention CN201410023422 discloses a kind of styrene butadiene rubber modified asphalt water-proof material, and its composition with mass fraction representation is: pitch 100 parts; Toluene 20-40 part; Petroleum hydrocarbon 15-25 part; Stearyl trimethyl ammonium chloride 2-3 part; Styrene-butadiene rubber(SBR) 8-12 part; Rosin sodium oleate soap 8-10 part; Sulphur 0.2-0.5 part; Sodium alkyl benzene sulfonate is 1-2 part; Hydrochloric acid is 5-8 part; Sodium hydroxide 0.1-0.3 part; Polyvinyl alcohol 2-5 part; Tetracol phenixin 40-50 part; Cats product 20-30 part; Product solid content 65-75%, surface drying 3-4h, does solid work 22-24h; Resistance to solar radiation, resistance to 90-110 DEG C high temperature, at 100 DEG C, 5h is non-foaming does not trickle; 0.1-0.2MPa, 30min are waterproof, viscosity 175Pas.
Solution polymerized butadiene styrene rubber (SSBR) good combination property, use properties are superior, are widely used in tire, shoemaking and other industry.Along with the generation of " green tire " concept, require that tire has low-rolling-resistance, high wet-sliding resistant and excellent wear resisting property, at present, the SSBR matrix material of white carbon black reinforcement can improve wear resisting property by low-rolling-resistance significantly, but white carbon black is easily reunited in SSBR matrix, cause its dispersiveness poor, become a principal element of the SSBR matrix material application of restriction white carbon black reinforcement.
Summary of the invention
The object of this invention is to provide a kind of preparation method of epoxidation solution polymerized butadiene styrene rubber.
The present invention is the preparation method of epoxidation solution polymerized butadiene styrene rubber, and concrete preparation process is as follows:
In the container that agitator, reflux exchanger, thermometer and constant pressure funnel are housed, add the solution polymerized butadiene styrene rubber of formula ratio, pentamethylene or toluene, stirred at ambient temperature, treats that solution polymerized butadiene styrene rubber dissolves post-heating completely to temperature of reaction, adds the formic acid of formula ratio, the hydrogen peroxide of formula ratio is dripped by the speed of 1ml/min, control temperature of reaction, after question response terminates, with distilled water, epoxidation solution polymerized butadiene styrene rubber is washed till neutrality, when pentamethylene is solvent, at 70 DEG C, boil off pentamethylene; When toluene is solvent, go out epoxidation solution polymerized butadiene styrene rubber with alcohol settling, be placed in vacuum drying oven under room temperature and be dried to constant weight, epoxidation solution polymerized butadiene styrene rubber can be obtained.
Usefulness of the present invention is: prepare and have high-elastic waterproof corrosion-resistant material, common method is rubber and epoxy resin Mixed Pinyin, and add exhibiting high surface promoting agent, coupling agents to improve rubber, consistency between epoxy resin and inorganic particulate, improve the strength of materials.Solution polymerized butadiene styrene rubber mid-molecule is divided double bond epoxidation by the present invention, the problem of the resin system instability that epoxy resin and rubber compatibility difference cause can be solved, reduce a large amount of coupling agent consumption to the impact of material property, improve the consistency between rubber molecule and inorganic particulate.
Embodiment
The preparation of epoxidation solution polymerized butadiene styrene rubber, is characterized in that syntheti c route is as follows:
（a）
（b）
The present invention realizes by following measure:
In the container with agitator, reflux exchanger, thermometer and constant pressure funnel, add SSBR and the organic solvent (pentamethylene or toluene) of formula ratio, stirred at ambient temperature, treat that SSBR dissolves post-heating completely to temperature of reaction, add the formic acid of formula ratio, the hydrogen peroxide of formula ratio is dripped by the speed of 1ml/min, control temperature of reaction, after question response terminates, with distilled water, epoxidation solution polymerized butadiene styrene rubber (ESSBR) is washed till neutrality, when pentamethylene is solvent, at 70 DEG C, boil off pentamethylene; When toluene is solvent, go out ESSBR with alcohol settling, be placed in vacuum drying oven under room temperature and be dried to constant weight.
Embodiment 1:
6.034gSSBR and 85.0ml toluene is added in the container with the 500ml of agitator, reflux exchanger, thermometer and constant pressure funnel, stirred at ambient temperature, treat that SSBR dissolves post-heating completely to 50 DEG C, add 3.21ml formic acid, drip 7.64ml hydrogen peroxide by the speed of 1ml/min, react 2 hours at 50 DEG C, with distilled water, ESSBR is washed till neutrality, go out ESSBR with alcohol settling, be placed in vacuum drying oven under room temperature and be dried to constant weight.Recording epoxy content after drying is 32.68%.
Embodiment 2:
120.0gSSBR and 1440ml pentamethylene is added in the container with the 2000ml of agitator, reflux exchanger, thermometer and constant pressure funnel, stirred at ambient temperature, treat that SSBR dissolves post-heating completely to 40 DEG C, add 63.8ml formic acid, drip 76.0ml hydrogen peroxide by the speed of 3ml/min, react 2 hours at 40 DEG C, with distilled water, ESSBR is washed till neutrality, boil off pentamethylene at 70 DEG C, be placed in vacuum drying oven under room temperature and be dried to constant weight.Recording epoxy content after drying is 14.73%.
Embodiment 3:
120.3gSSBR and 1443ml pentamethylene is added in the container with the 2000ml of agitator, reflux exchanger, thermometer and constant pressure funnel, stirred at ambient temperature, treat that SSBR dissolves post-heating completely to 40 DEG C, add 32.0ml formic acid, drip 30.5ml hydrogen peroxide by the speed of 3ml/min, react 2 hours at 40 DEG C, with distilled water, ESSBR is washed till neutrality, boil off pentamethylene at 70 DEG C, be placed in vacuum drying oven under room temperature and be dried to constant weight.Recording epoxy content after drying is 6.87%.
Embodiment 4:
120.0gSSBR and 1440ml pentamethylene is added in the container with the 2000ml of agitator, reflux exchanger, thermometer and constant pressure funnel, stirred at ambient temperature, treat that SSBR dissolves post-heating completely to 40 DEG C, add 63.8ml formic acid, drip 76.0ml hydrogen peroxide by the speed of 3ml/min, react 2 hours at 40 DEG C, with distilled water, ESSBR is washed till neutrality, boil off pentamethylene at 70 DEG C, be placed in vacuum drying oven under room temperature and be dried to constant weight.Recording epoxy content after drying is 14.73%.
Claims (6)
1. the preparation method of epoxidation solution polymerized butadiene styrene rubber, is characterized in that, concrete preparation process is as follows:
In the container that agitator, reflux exchanger, thermometer and constant pressure funnel are housed, add the solution polymerized butadiene styrene rubber of formula ratio, pentamethylene or toluene, stirred at ambient temperature, treats that solution polymerized butadiene styrene rubber dissolves post-heating completely to temperature of reaction, adds the formic acid of formula ratio, the hydrogen peroxide of formula ratio is dripped by the speed of 1ml/min, control temperature of reaction, after question response terminates, with distilled water, epoxidation solution polymerized butadiene styrene rubber is washed till neutrality, when pentamethylene is solvent, at 70 DEG C, boil off pentamethylene; When toluene is solvent, go out epoxidation solution polymerized butadiene styrene rubber with alcohol settling, be placed in vacuum drying oven under room temperature and be dried to constant weight, epoxidation solution polymerized butadiene styrene rubber can be obtained.
2. the preparation method of epoxidation solution polymerized butadiene styrene rubber according to claim 1, the consumption that it is characterized by solvent for use pentamethylene or toluene is 6 ~ 12 times of solution polymerized butadiene styrene rubber quality.
3. the preparation method of epoxidation solution polymerized butadiene styrene rubber according to claim 1, is characterized by: the consumption of formic acid is 0.5 ~ 1.5 times of the amount of substance of carbon-carbon double bond.
4. the preparation method of epoxidation solution polymerized butadiene styrene rubber according to claim 1, is characterized by: the consumption of hydrogen peroxide is 0.5 ~ 1.5 times of the amount of substance of carbon-carbon double bond.
5. the preparation method of epoxidation solution polymerized butadiene styrene rubber according to claim 1, is characterized by: temperature of reaction is 40 ~ 70 DEG C.
6. the preparation method of epoxidation solution polymerized butadiene styrene rubber according to claim 1, is characterized by: the reaction times controls at 2 ~ 5h.
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| CN201410806562.5A CN104448060A (en) | 2014-12-23 | 2014-12-23 | Preparation method of epoxidized solution polymerized styrene-butadiene rubber |
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| CN201410806562.5A CN104448060A (en) | 2014-12-23 | 2014-12-23 | Preparation method of epoxidized solution polymerized styrene-butadiene rubber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200820A (en) * | 2017-06-27 | 2017-09-26 | 江门盈骅光电科技有限公司 | Epoxidation vinyl benzene butadiene double-heptene block copolymer and its production and use |
| CN114507300A (en) * | 2022-01-28 | 2022-05-17 | 河北科技大学 | Epoxy resin toughening agent and preparation method and application thereof |
| CN115477795A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Wear-resistant and anti-slippery rubber composite material for tire and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103528985A (en) * | 2012-07-04 | 2014-01-22 | 中国石油天然气股份有限公司 | Infrared spectroscopy measurement method for bound styrene content of emulsion styrene-butadiene rubber |
| CN103848939A (en) * | 2012-12-05 | 2014-06-11 | 北方爆破工程有限责任公司 | Synthetic method of solution-polymerized styrene-butadiene rubber |
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2014
- 2014-12-23 CN CN201410806562.5A patent/CN104448060A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103528985A (en) * | 2012-07-04 | 2014-01-22 | 中国石油天然气股份有限公司 | Infrared spectroscopy measurement method for bound styrene content of emulsion styrene-butadiene rubber |
| CN103848939A (en) * | 2012-12-05 | 2014-06-11 | 北方爆破工程有限责任公司 | Synthetic method of solution-polymerized styrene-butadiene rubber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200820A (en) * | 2017-06-27 | 2017-09-26 | 江门盈骅光电科技有限公司 | Epoxidation vinyl benzene butadiene double-heptene block copolymer and its production and use |
| CN115477795A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Wear-resistant and anti-slippery rubber composite material for tire and preparation method thereof |
| CN115477795B (en) * | 2021-06-16 | 2023-12-05 | 中国石油化工股份有限公司 | Rubber composite material for wear-resistant and moisture-resistant tyre and preparation method thereof |
| CN114507300A (en) * | 2022-01-28 | 2022-05-17 | 河北科技大学 | Epoxy resin toughening agent and preparation method and application thereof |
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Application publication date: 20150325 |