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CN105017483A - Preparation method of emulsion polymerized butadiene styrene rubber special-purpose emulsifier - Google Patents

Preparation method of emulsion polymerized butadiene styrene rubber special-purpose emulsifier Download PDF

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Publication number
CN105017483A
CN105017483A CN201510354261.8A CN201510354261A CN105017483A CN 105017483 A CN105017483 A CN 105017483A CN 201510354261 A CN201510354261 A CN 201510354261A CN 105017483 A CN105017483 A CN 105017483A
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China
Prior art keywords
emulsion polymerized
preparation
butadiene rubber
acid
styrene butadiene
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CN201510354261.8A
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Chinese (zh)
Inventor
王新东
孙楠
谢淑婷
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Zibo Tenghui Oil Chemical Co Ltd
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Zibo Tenghui Oil Chemical Co Ltd
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Priority to CN201510354261.8A priority Critical patent/CN105017483A/en
Publication of CN105017483A publication Critical patent/CN105017483A/en
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Abstract

The invention belongs to the field of emulsion polymerized butadiene styrene rubber and relates to a preparation method of an emulsion polymerized butadiene styrene rubber special-purpose emulsifier. The preparation method comprises adding a dispersant into deoxidized softened water, carrying out stirring to obtain a dispersant solution with a mass fraction of 0.01-0.05%, adding aliphatic acid into the dispersant solution, carrying out stirring dissolution, keeping a temperature of 50 DEG C, adding sodium hydroxide into the mixed solution, carrying out stirring, and adjusting the solution pH in a range of 10.0-11.0 to obtain a solution which is the emulsion polymerized butadiene styrene rubber special-purpose emulsifier. The emulsion polymerized butadiene styrene rubber special-purpose emulsifier is used for polymerization monomer polymerization for emulsion polymerized butadiene styrene rubber preparation. The preparation method has clean processes, has no pollution, does not discharge waste water and refuse, substantially improves emulsion polymerized butadiene styrene rubber solution reaction stability, effectively improves a butadiene conversion rate and improves emulsion polymerized butadiene styrene rubber market competitiveness.

Description

The preparation method of emulsion polymerized styrene butadiene rubber emulsifier special
Technical field
The invention belongs to emulsion polymerized styrene butadiene rubber field, be specifically related to a kind of preparation method of emulsion polymerized styrene butadiene rubber emulsifier special.
Background technology
According to the difference of polymerization technique, styrene-butadiene rubber(SBR) is divided into emulsion polymerized styrene butadiene rubber and solution polymerized butadiene styrene rubber.Compared with solution polymerized butadiene styrene rubber technique, emulsion polymerized styrene butadiene rubber technique is more preponderated in cost-saving, and global styrene-butadiene rubber(SBR) device about has the production capacity of 75% based on emulsion polymerized styrene butadiene rubber technique.Emulsion polymerized styrene butadiene rubber is with divinyl, vinylbenzene for principal monomer, prepares through emulsion method polymerization.Emulsion polymerized styrene butadiene rubber has good over-all properties, and technical maturity is widely used, and production capacity, output and consumption all account for first place in styrene-butadiene rubber(SBR).Traditional styrene-butadiene rubber(SBR) production technique, production process has the shortcomings such as letex polymerization is thorough, feed stock conversion is low, and product easily lumps, toughness is low, and quality reduces greatly.
Summary of the invention
The object of this invention is to provide a kind of preparation method of emulsion polymerized styrene butadiene rubber emulsifier special, this emulsifying agent can increase the stability of emulsion polymerized styrene butadiene rubber solution reaction, effectively improves the transformation efficiency of divinyl.
The preparation method of emulsion polymerized styrene butadiene rubber emulsifier special of the present invention, comprises the following steps:
(1) be added to the water by dispersion agent, stirring obtained massfraction is the dispersant solution of 0.01 ~ 0.05%;
(2) lipid acid is joined in the obtained solution of step (1), stirring and dissolving;
(3) in the obtained mixing solutions of step (2), add sodium hydroxide, stir, make solution ph 10.0 ~ 11.0, be emulsion polymerized styrene butadiene rubber emulsifier special.
Wherein: dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is that 1:1 ~ 2 mix according to weight ratio.
In step (1), water is preferably deoxidation softening water.
The temperature stirred in step (1) is 50 DEG C.Stirring obtained massfraction in step (1) is the dispersant solution of 0.01 ~ 0.05%, and preferably obtained massfraction is the dispersant solution of 0.02%.
The massfraction of the lipid acid in the mixing solutions obtained after adding lipid acid in step (2) is 7% ~ 8%.
In step (2), lipid acid is one or more in saturated fatty acid, monounsaturated fatty acid or polybasic unsaturated fatty acid.Be preferably in semi-harden tallow fatty acids, stearic acid, palmitinic acid, tetradecanoic acid, oleic acid, lauric acid, Zoomeric acid or linolenic acid one or more.
The massfraction of the sodium hydroxide after preferably adding sodium hydroxide in step (3) in solution is 1% ~ 1.2%.
The temperature keeping mixing solutions when adding sodium hydroxide in step (3) is 45 ~ 55 DEG C.
In step (3), solution final ph is 10.0 ~ 11.0, is preferably 10.6 ~ 11.0.
In step (3), churning time is 15 ~ 20min, preferred 15min.
The emulsifying agent that the present invention prepares is a kind of fatty acid sodium soap.The application of emulsion polymerized styrene butadiene rubber emulsifier special of the present invention, is used for, in the polyreaction of polymerization single polymerization monomer, preparing emulsion polymerized styrene butadiene rubber by this kind of emulsifying agent.Adopt the preparation method of existing emulsion polymerized styrene butadiene rubber, in reaction process, add the emulsifying agent that the present invention is made.As: this kind of emulsifying agent is mixed by existing formula with polymerization single polymerization monomer, ionogen, initiator, molecular weight regulator, carries out polyreaction, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber; Polymerization single polymerization monomer is preferably divinyl and vinylbenzene.
Emulsifying agent stable in properties prepared by the present invention, the airtight rear long-term preservation of solution is not stratified.When this emulsifying agent is applied to emulsion polymerized styrene butadiene rubber production, significantly can increase the stability of emulsion polymerized styrene butadiene rubber solution reaction, effectively improve the transformation efficiency of divinyl, improve the market competitiveness of emulsion polymerized styrene butadiene rubber.
The present invention compared with prior art, has following beneficial effect:
(1) the present invention is simple, and exploitativeness is strong, and production process cleanliness without any pollution, does not have waste water and waste discharge, nontoxic pollution-free again, can significantly improve the transformation efficiency of raw material divinyl, reduces the cost of product styrene-butadiene rubber(SBR).
(2) feed stock conversion of the present invention is high, and product working substance purity is high, stable performance.
(3) the present invention changes the character of conventional emulsifier, and the emulsifying agent obtained is creamy white or light yellow transparent liquid.This emulsifying agent stable in properties, the airtight rear long-term preservation of solution is not stratified.
(4) when emulsifying agent prepared by the present invention being applied to emulsion polymerized styrene butadiene rubber production, significantly can increase the stability of emulsion polymerized styrene butadiene rubber solution reaction, effectively improve more than the transformation efficiency to 84% of divinyl, improve the market competitiveness of emulsion polymerized styrene butadiene rubber.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment
In embodiment, dispersion agent is purchased from Zhejiang development of evil in febrile disease limited energy company; Semi-harden tallow fatty acids, stearic acid are commercially available prod; Lauric acid, tetradecanoic acid are purchased from Guangzhou Sheng Yue foreign trade company limited; Palmitinic acid, oleic acid, Zoomeric acid, linolenic acid are purchased from Fujian Zhong Min Chemical Co., Ltd.; Sodium hydroxide is purchased from Shandong Xin Shan Trade Co., Ltd.; Divinyl and vinylbenzene are purchased from Beijing Yanshan Petrochemical Co., Ltd., Sinopec Corp..
In embodiment 1-5, electrolyte solution adopts disodium edta, initiator to adopt sodium sulfoxylate formaldehyde, molecular weight regulator to adopt tert-dodecyl mercaptan, terminator to adopt Sodium Dimethyldithiocarbamate, is commercially available prod.
Embodiment 1
Prepare a kind of emulsion polymerized styrene butadiene rubber emulsifier special: take dispersion agent and be dissolved in 1000g deoxidation softening water, make the dispersant solution (dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is 1:1 mixing according to weight ratio) that mass percentage concentration is 0.02%, add 81.4g lipid acid (stearic acid) again, be warming up to 50 DEG C, stirring and dissolving lipid acid, sodium hydroxide 12.3g is added in above-mentioned mixing solutions, 50 DEG C are kept to stir 15 minutes, obtain light yellow transparent liquid, be emulsifying agent, the pH value of testing this emulsifying agent is 10.8.
Then emulsifying agent is mixed with polymerization single polymerization monomer, electrolyte solution, initiator, molecular weight regulator, carry out emulsion polymerization, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber.Polyreaction tracing detection, monomer polymerization rate reaches 95%.
Embodiment 2
Prepare a kind of emulsion polymerized styrene butadiene rubber emulsifier special: take dispersion agent and be dissolved in 1000g deoxidation softening water, make the dispersant solution (dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is 1:2 mixing according to weight ratio) that mass percentage concentration is 0.01%, add 74g lipid acid (palmitinic acid) again, be warming up to 50 DEG C, stirring and dissolving lipid acid, sodium hydroxide 12.0g is added in above-mentioned mixing solutions, 50 DEG C are kept to stir 15 minutes, obtain light yellow transparent liquid, be emulsifying agent, the pH value of testing this emulsifying agent is 9.7.
Then emulsifying agent being mixed according to necessarily filling a prescription with polymerization single polymerization monomer, ionogen, initiator, molecular weight regulator, carrying out emulsion polymerization, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber.Polyreaction tracing detection, monomer polymerization rate reaches 84%.
Embodiment 3
Prepare a kind of emulsion polymerized styrene butadiene rubber emulsifier special: take dispersion agent and be dissolved in 1000g deoxidation softening water, make the dispersant solution (dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is 1:1.5 mixing according to weight ratio) that mass percentage concentration is 0.05%, add 58g lipid acid (lauric acid) again, be warming up to 50 DEG C, stirring and dissolving lipid acid, sodium hydroxide 12.1g is added in above-mentioned mixing solutions, 50 DEG C are kept to stir 15 minutes, obtain light yellow transparent liquid, be emulsifying agent, the pH value of testing this emulsifying agent is 10.1.
Then emulsifying agent being mixed according to necessarily filling a prescription with polymerization single polymerization monomer, ionogen, initiator, molecular weight regulator, carrying out emulsion polymerization, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber.Polyreaction tracing detection, monomer polymerization rate reaches 88%.
Embodiment 4
Prepare a kind of emulsion polymerized styrene butadiene rubber emulsifier special: take dispersion agent and be dissolved in 1000g deoxidation softening water, make the dispersant solution (dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is 1:1 mixing according to weight ratio) that mass percentage concentration is 0.02%, add 78g lipid acid (linolenic acid) again, be warming up to 50 DEG C, stirring and dissolving lipid acid, sodium hydroxide 13.0g is added in above-mentioned mixing solutions, 50 DEG C are kept to stir 15 minutes, obtain light yellow transparent liquid, be emulsifying agent, the pH value of testing this emulsifying agent is 11.2.
Then emulsifying agent being mixed according to necessarily filling a prescription with polymerization single polymerization monomer, ionogen, initiator, molecular weight regulator, carrying out emulsion polymerization, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber.Polyreaction tracing detection, monomer polymerization rate reaches 85%.
Embodiment 5
Prepare a kind of emulsion polymerized styrene butadiene rubber emulsifier special: take dispersion agent and be dissolved in 1000g water, make the dispersant solution (dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is 1:2 mixing according to weight ratio) that mass percentage concentration is 0.02%, add 81g lipid acid (oleic acid) again, be warming up to 50 DEG C, stirring and dissolving lipid acid, sodium hydroxide 13.5g is added in above-mentioned mixing solutions, 50 DEG C are kept to stir 15 minutes, obtain light yellow transparent liquid, be emulsifying agent, the pH value of testing this emulsifying agent is 12.
Then emulsifying agent being mixed according to necessarily filling a prescription with polymerization single polymerization monomer, ionogen, initiator, molecular weight regulator, carrying out emulsion polymerization, after reaction terminates, add terminator termination reaction, finally obtained emulsion polymerized styrene butadiene rubber.Polyreaction tracing detection, monomer polymerization rate reaches 85%.

Claims (9)

1. a preparation method for emulsion polymerized styrene butadiene rubber emulsifier special, is characterized in that: comprise the following steps:
(1) be added to the water by dispersion agent, stirring obtained massfraction is the dispersant solution of 0.01 ~ 0.05%;
(2) lipid acid is joined in the obtained solution of step (1), stirring and dissolving;
(3) in the obtained mixing solutions of step (2), add sodium hydroxide, stir, make solution ph 10.0 ~ 11.0, be emulsion polymerized styrene butadiene rubber emulsifier special.
2. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: dispersion agent is aliphatic amine polyoxyethylene ether and fatty alcohol-polyoxyethylene ether is that 1:1 ~ 2 mix according to weight ratio.
3. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: in step (1), water is deoxidation softening water.
4. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: the temperature stirred in step (1) is 48 ~ 53 DEG C.
5. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: the massfraction of the lipid acid in the mixing solutions obtained after adding lipid acid in step (2) is 7% ~ 8%.
6. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1 or 5, is characterized in that: in step (2), lipid acid is one or more in saturated fatty acid, monounsaturated fatty acid or polybasic unsaturated fatty acid.
7. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 6, is characterized in that: in step (2), lipid acid is one or more in semi-harden tallow fatty acids, stearic acid, palmitinic acid, tetradecanoic acid, oleic acid, lauric acid, Zoomeric acid or linolenic acid.
8. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: the temperature keeping mixing solutions when adding sodium hydroxide in step (3) is 45 ~ 55 DEG C.
9. the preparation method of emulsion polymerized styrene butadiene rubber emulsifier special according to claim 1, is characterized in that: in step (3), churning time is 15 ~ 20min.
CN201510354261.8A 2015-06-24 2015-06-24 Preparation method of emulsion polymerized butadiene styrene rubber special-purpose emulsifier Pending CN105017483A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406528A (en) * 2015-11-30 2017-11-28 Lg化学株式会社 Process for preparing styrene-butadiene rubber with low bound styrene content
CN114456316A (en) * 2020-11-07 2022-05-10 中国石油化工股份有限公司 Method for improving emulsion polymerized styrene butadiene rubber conversion rate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1271740A (en) * 1999-04-22 2000-11-01 山东省蓬莱市化工总厂 Production method of high styrene
CN1663975A (en) * 2004-03-01 2005-09-07 吉林市大宇化工有限公司 Styrene butadiene rubber sodium type polymer and its preparation method
CN101597383A (en) * 2009-07-10 2009-12-09 淄博腾辉油脂化工有限公司 A kind of synthesis technique of emulsifier special for rubber
CN102731874A (en) * 2011-04-07 2012-10-17 中国石油天然气股份有限公司 Modified rubber and preparation method thereof
CN102942658A (en) * 2012-10-31 2013-02-27 大连理工大学 Functional emulsion styrene-butadiene rubber and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1271740A (en) * 1999-04-22 2000-11-01 山东省蓬莱市化工总厂 Production method of high styrene
CN1663975A (en) * 2004-03-01 2005-09-07 吉林市大宇化工有限公司 Styrene butadiene rubber sodium type polymer and its preparation method
CN101597383A (en) * 2009-07-10 2009-12-09 淄博腾辉油脂化工有限公司 A kind of synthesis technique of emulsifier special for rubber
CN102731874A (en) * 2011-04-07 2012-10-17 中国石油天然气股份有限公司 Modified rubber and preparation method thereof
CN102942658A (en) * 2012-10-31 2013-02-27 大连理工大学 Functional emulsion styrene-butadiene rubber and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406528A (en) * 2015-11-30 2017-11-28 Lg化学株式会社 Process for preparing styrene-butadiene rubber with low bound styrene content
CN107406528B (en) * 2015-11-30 2019-06-04 Lg化学株式会社 Process for preparing styrene-butadiene rubber with low bound styrene content
US10407566B2 (en) 2015-11-30 2019-09-10 Lg Chem, Ltd. Method for preparing styrene-butadiene rubber having low combined styrene content
CN114456316A (en) * 2020-11-07 2022-05-10 中国石油化工股份有限公司 Method for improving emulsion polymerized styrene butadiene rubber conversion rate
CN114456316B (en) * 2020-11-07 2024-01-09 中国石油化工股份有限公司 Method for improving emulsion polymerized styrene-butadiene rubber conversion rate

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Application publication date: 20151104

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