CN1425701A - Process for preparing lacto styrene butadiene rubber of different bound styrene content - Google Patents
Process for preparing lacto styrene butadiene rubber of different bound styrene content Download PDFInfo
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- CN1425701A CN1425701A CN 01135285 CN01135285A CN1425701A CN 1425701 A CN1425701 A CN 1425701A CN 01135285 CN01135285 CN 01135285 CN 01135285 A CN01135285 A CN 01135285A CN 1425701 A CN1425701 A CN 1425701A
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Abstract
The emulsion polymerized styrene-butadiene rubber is prepared through the emulsion polymerization of styrene and butadiene and features that the mass percentage of styrene 20-60% and butadiene 40-80% and the amount of molecular weight regulator of 0.18-0.35 wt% for no-oil rubber and 0.12-0.25 wt% for oil-extended rubber. The present invention makes it possible to produce various oil-extended and no-oil styrene-butadiene rubber in common styrene-butadiene rubber producing apparatus for different requirement.
Description
Technical field
The invention belongs to China Synthetic Rubber Industry, relate to divinyl and the letex polymerization of vinylbenzene low temperature.
Background technology
General styrene-butadiene rubber(SBR) is meant that combined styrene content that divinyl (account for amount of monomer 71%) and vinylbenzene (account for amount of monomer 29%) make through emulsion polymerization at low temperatures is 23.5% butadienestyrene copolymer.The used oxygenant of emulsion polymerization be di-isopropylbenzene hydroperoxide, hydrogen peroxide pinane or hydrogen peroxide to alkane in the Meng, its consumption is generally 0.025～0.08% of monomer total amount.Reductive agent is sodium formaldehyde sulphoxylate and iron edta sodium salt, and its consumption is generally 0.04～0.1% of monomer total amount.Use RA rosin acid and fatty acid soaps blending emulsifiers, its consumption is generally 4～6% of monomer total amount.Molecular weight regulator can adopt tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan.Its consumption is 0.18%～0.3% of a monomer total amount for non-oil-filled glue, is 0.1～0.2% of monomer total amount for oil-filled glue.Temperature of reaction is 5～8 ℃.
According to different service requirementss, styrene-butadiene rubber(SBR) can be used to produce rubber items such as doughnut, cycle tyre, hand cart tyre, wire belt, travelling belt, sealing-ring, sebific duct, rubber overshoes, especially doughnut, cycle tyre, travelling belt and rubberized fabrics etc.
After improving the combined styrene content of styrene-butadiene rubber(SBR), some properties of rubber such as hardness, stress at definite elongation etc. all have raising in various degree, and distortion reduces, and is particularly suitable for preparing higher, the wear-resisting rubber products of hardness.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation technology of emulsion polymerized styrene butadiene rubber of different combined styrene content, can improve the combined styrene content of styrene-butadiene rubber(SBR).
The preparation technology of the emulsion polymerized styrene butadiene rubber of different combined styrene content of the present invention, it is the emulsion polymerization that carries out at low temperatures by divinyl and vinylbenzene, it is characterized in that adjusting vinylbenzene and quality of butadiene percentage ratio is respectively: vinylbenzene is 20～60% (are 100% in the monomer total amount), divinyl is 40～80% (are 100% in the monomer total amount), the consumption of the molecular weight regulator that adds, for non-oil-filled glue is 0.18～0.35% of monomer total amount, is 0.12～0.25% of monomer total amount for oil-filled glue.
The present invention still is an emulsion polymerization as prior art, the oxygenant that adopts in the reaction process, reductive agent, emulsifying agent, molecular weight regulator, temperature of reaction can be constant, is that the amount of the molecular weight regulator of ratio by regulating vinylbenzene and divinyl and adding realizes.Cinnamic binding capacity is 15～55% in the styrene-butadiene rubber(SBR), and the amount of styrene monomer is low, and the amount of combined styrene is just few in the styrene-butadiene rubber(SBR) relatively.
The styrene-butadiene rubber(SBR) of the present invention preparation also should be controlled the molecular weight of product, and for non-oil-filled glue: number-average molecular weight is 11～150,000, and weight-average molecular weight is 30～380,000; For oil-filled glue: number-average molecular weight is 20～270,000, and weight-average molecular weight is 55～700,000.
Advantage of the present invention: can utilize common styrene-butadiene rubber(SBR) production equipment, produce and prepare the oil-filled and non-oil-extended styrene-butadiene rubber of various combined styrene content, satisfy the needs of the different purposes of rubber.The content of combined styrene can be controlled in 15～55% in the styrene-butadiene rubber(SBR).After particularly improving the content of combined styrene in the styrene-butadiene rubber(SBR), can prepare higher, the wear-resisting rubber products of hardness.The method of closing of the low temperature emulsion that the present invention adopts, energy consumption is low, and polymeric kettle and pipeline kiss-coating are light, easy to operate, stable production process, running period is long.
Embodiment
Embodiment 1
In the 10L polymeric kettle, add 200 parts of water, 1.5 parts of RA rosin acids, 3.5 parts of fatty acid soaps, 30 parts of vinylbenzene feed the nitrogen pressure testing, confirm that polymeric kettle does not have the back of leakage with nitrogen replacement for several times, adds 70 parts of divinyl then.Starting polymeric kettle stirs, and logical cold water cooling in polymeric kettle, treat to add when the polymeric kettle temperature is reduced to 5 ℃ 0.04 part of di-isopropylbenzene hydroperoxide, formaldehyde closes bisulphite and receives (SFS) 0.05 part, 0.05 part of iron edta sodium salt (EDTAFeNa), 0.34 part of tert-dodecyl mercaptan, reacted 12 hours down at 5 ℃, monomer conversion is controlled at 70%, and rubber condenses after outgasing, and obtains product of the present invention after the hot air dries.
Reaction conditions and product test the results are shown in Table 1.
Embodiment 2
Add hydrogen peroxide to 0.045 part in alkane in the Meng (PMHP), EDTAFeNa0.008 part was reacted 8 hours, and all the other are with embodiment 1.
Embodiment 3
Add hydrogen peroxide pinane (PHP) 0.03 part, SFS0.05, EDTAFeNa0.012 reacted 8 hours. and all the other are with embodiment 1.
Embodiment 4
Add di-isopropylbenzene hydroperoxide (DIP) 0.08 part, SFS0.10 part, 0.009 part of EDTAFeNa reacted 7 hours.All the other are with embodiment 1.
Embodiment 5
The vinylbenzene consumption is brought up to 50 parts in the prescription, and all the other are with embodiment 4.
Embodiment 6
The vinylbenzene consumption is brought up to 55 parts in the prescription, 0.2 part of tert-dodecyl mercaptan, and all the other are with embodiment 4.The product Mooney is 120, fills that the Mooney of oil-filled glue is 51 after 37.5 parts of high aromatic oils or the naphthenic oil.
Embodiment 7
Styrene monomer content is 20%, and the divinylic monomer amount is 80%.The molecular weight regulator tert-dodecyl mercaptan is 0.20% of a monomer total amount, other technology such as embodiment 1.The combined styrene content that makes in the non-oil-filled glue is 15%.
Embodiment 8
Styrene monomer content is 35%, and the divinylic monomer amount is 65%.The molecular weight regulator tert-dodecyl mercaptan is 0.25% of a monomer total amount, other technology such as embodiment 1.The combined styrene content that makes in the non-oil-filled glue is 29%.
Embodiment 9
Styrene monomer content is 50%, and the divinylic monomer amount is 50%.The molecular weight regulator tert-dodecyl mercaptan is 0.27% of a monomer total amount, other technology such as embodiment 1.The combined styrene content that makes in the non-oil-filled glue is 44%.
Embodiment 10
Styrene monomer content is 60%, and the divinylic monomer amount is 40%.The molecular weight regulator tert-dodecyl mercaptan is 0.25% of a monomer total amount, other technology such as embodiment 6.The combined styrene content that makes in the oil-filled glue is 55%.
Table 1 reaction conditions and product test result
| Sequence number | Oxygenant | ?SFS | ?EDTAFeNa | Temperature (℃) | Styrene content in the monomer (%) | Time (h) | Mooney |
| Embodiment 1 | ?DIP0.04 | ?0.05 | ?0.05 | ?5 | ?30 | ?12 | ?53 |
| Embodiment 2 | ?PMHP ?0.045 | ?0.05 | ?0.008 | ?5 | ?30 | ?8 | ?58 |
| Embodiment 3 | ?PHP ?0.03 | ?0.05 | ?0.008 | ?5 | ?30 | ?10 | ?57 |
| Embodiment 4 | ?DIP0.08 | ?0.10 | ?0.009 | ?5 | ?30 | ?7 | ?57 |
| Embodiment 5 | ?DIP0.08 | ?0.10 | ?0.009 | ?5 | ?50 | ?7 | ?50 |
| Embodiment 6 | ?DIP0.08 | ?0.10 | ?0.009 | ?5 | ?55 | ?7 | ?120 |
With embodiment 5 is that the performance index of the styrene-butadiene rubber(SBR) goods that make of example are as follows:
| Preface | Project | The conventional rubber goods | High combined styrene goods |
| ?1 | Mooney | ??50 | ??50 |
| ?2 | Stress at definite elongation (Mpa) 35 ' | ??6.9 | ??9.0 |
| ?3 | Tensile strength (Mpa) 35 ' | ??18.0 | ??17.5 |
| ?4 | Elongation (%) | ??620 | ??520 |
| ?5 | Tension set (%) | ??32 | ??28 |
| ?6 | Hardness (Shao A) | ??60 | ??62 |
Claims (3)
1, the preparation technology of the emulsion polymerized styrene butadiene rubber of different combined styrene content, it is the emulsion polymerization that carries out at low temperatures by divinyl and vinylbenzene, it is characterized in that adjusting vinylbenzene and quality of butadiene percentage ratio is respectively: vinylbenzene is 20～60%, divinyl is 40～80%, the consumption of the molecular weight regulator that adds, for non-oil-filled glue is 0.18～0.35% of monomer total amount, is 0.12～0.25% of monomer total amount for oil-filled glue.
2, technology according to claim 1 is characterized in that the styrene-butadiene rubber(SBR) for preparing, and for non-oil-filled glue: number-average molecular weight is 11～150,000, and weight-average molecular weight is 30～380,000; For oil-filled glue: number-average molecular weight is 20～270,000, and weight-average molecular weight is 55～700,000.
3, technology according to claim 1 is characterized in that molecular weight regulator is selected from tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135285 CN1425701A (en) | 2001-12-14 | 2001-12-14 | Process for preparing lacto styrene butadiene rubber of different bound styrene content |
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| CN 01135285 CN1425701A (en) | 2001-12-14 | 2001-12-14 | Process for preparing lacto styrene butadiene rubber of different bound styrene content |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724542A (en) * | 2013-12-17 | 2014-04-16 | 杭州浙晨橡胶有限公司 | Method for preparing dark-colored styrene butadiene rubber |
| CN103739781A (en) * | 2013-12-17 | 2014-04-23 | 杭州浙晨橡胶有限公司 | Non-contamination-type non-oil-charge type styrene-butadiene rubber preparation method |
| CN103739782A (en) * | 2013-12-17 | 2014-04-23 | 杭州浙晨橡胶有限公司 | Environmental-friendly type styrene-butadiene rubber preparation method |
| CN103755871A (en) * | 2013-12-17 | 2014-04-30 | 杭州浙晨橡胶有限公司 | Preparation method for highly stable styrene-butadiene rubber |
| CN101715462B (en) * | 2007-04-05 | 2015-08-05 | 朗盛艾拉托麦罗斯巴西有限公司 | Styrene-butadiene copolymer, its preparation method and high cohesion binder composition |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | The preparation method and butadiene-styrene rubber of butadiene-styrene rubber |
| CN110527020A (en) * | 2018-05-24 | 2019-12-03 | 中国石油天然气股份有限公司 | Butadiene-styrene rubber and preparation method thereof |
| CN110708637A (en) * | 2019-10-31 | 2020-01-17 | 歌尔股份有限公司 | Vibrating diaphragm for miniature sound generating device and miniature sound generating device |
| JP2020508361A (en) * | 2017-01-26 | 2020-03-19 | アランセオ・ドイチュランド・ゲーエムベーハー | Filler-filled sealing gel, method for producing it and its use in sealing compounds for self-sealing tires |
| CN111548449A (en) * | 2020-05-22 | 2020-08-18 | 浙江维泰橡胶有限公司 | Method for preparing deep-color high-strength styrene-butadiene rubber |
-
2001
- 2001-12-14 CN CN 01135285 patent/CN1425701A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101715462B (en) * | 2007-04-05 | 2015-08-05 | 朗盛艾拉托麦罗斯巴西有限公司 | Styrene-butadiene copolymer, its preparation method and high cohesion binder composition |
| CN103724542B (en) * | 2013-12-17 | 2016-09-21 | 杭州浙晨橡胶有限公司 | A kind of preparation method of dark SBR styrene butadiene rubbers |
| CN103755871A (en) * | 2013-12-17 | 2014-04-30 | 杭州浙晨橡胶有限公司 | Preparation method for highly stable styrene-butadiene rubber |
| CN103739781A (en) * | 2013-12-17 | 2014-04-23 | 杭州浙晨橡胶有限公司 | Non-contamination-type non-oil-charge type styrene-butadiene rubber preparation method |
| CN103755871B (en) * | 2013-12-17 | 2016-05-18 | 杭州浙晨橡胶有限公司 | A kind of preparation method of high stability SBR styrene butadiene rubbers |
| CN103739781B (en) * | 2013-12-17 | 2016-09-21 | 杭州浙晨橡胶有限公司 | A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber |
| CN103739782A (en) * | 2013-12-17 | 2014-04-23 | 杭州浙晨橡胶有限公司 | Environmental-friendly type styrene-butadiene rubber preparation method |
| CN103724542A (en) * | 2013-12-17 | 2014-04-16 | 杭州浙晨橡胶有限公司 | Method for preparing dark-colored styrene butadiene rubber |
| CN103739782B (en) * | 2013-12-17 | 2016-09-21 | 杭州浙晨橡胶有限公司 | A kind of environmental-friendtype type styrene-butadiene rubber preparation method |
| JP2020508361A (en) * | 2017-01-26 | 2020-03-19 | アランセオ・ドイチュランド・ゲーエムベーハー | Filler-filled sealing gel, method for producing it and its use in sealing compounds for self-sealing tires |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | The preparation method and butadiene-styrene rubber of butadiene-styrene rubber |
| CN109776726B (en) * | 2017-11-15 | 2021-11-02 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber and styrene butadiene rubber |
| CN110527020A (en) * | 2018-05-24 | 2019-12-03 | 中国石油天然气股份有限公司 | Butadiene-styrene rubber and preparation method thereof |
| CN110527020B (en) * | 2018-05-24 | 2022-02-01 | 中国石油天然气股份有限公司 | Styrene butadiene rubber and preparation method thereof |
| CN110708637A (en) * | 2019-10-31 | 2020-01-17 | 歌尔股份有限公司 | Vibrating diaphragm for miniature sound generating device and miniature sound generating device |
| CN111548449A (en) * | 2020-05-22 | 2020-08-18 | 浙江维泰橡胶有限公司 | Method for preparing deep-color high-strength styrene-butadiene rubber |
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