CN106478883A - A kind of styrene-butadiene latex and preparation method thereof - Google Patents
A kind of styrene-butadiene latex and preparation method thereof Download PDFInfo
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- CN106478883A CN106478883A CN201611079586.0A CN201611079586A CN106478883A CN 106478883 A CN106478883 A CN 106478883A CN 201611079586 A CN201611079586 A CN 201611079586A CN 106478883 A CN106478883 A CN 106478883A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- Chemical Kinetics & Catalysis (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to styrene-butadiene latex preparation method is used in a kind of emulsified asphalt modification, its main method is with butadiene and styrene as main monomer, add compound emulsifying agent, redox initiator, electrolyte, diffusant, molecular weight regulator, the styrene-butadiene latex that solid content is more than 55% is synthesized using ultrasonic wave added seeded emulsion polymerization technique.Being mainly characterized by of the present invention is assisted by ultrasonic device, reduces initiator amount, reduces reaction temperature, improves the molecular weight of latex；Prepared styrene-butadiene latex process is simple, is easily controlled, and is mainly used in modified emulsifying asphalt, and modified effect is obvious.
Description
Technical field
The present invention relates to a kind of low temperature synthesis high molecular, the preparation method of the styrene-butadiene latex of high conversion, particularly suitable
In modified emulsifying asphalt.
Background technology
High Solid Content SBR Latex viscosity is big, and stability is poor, and because butadiene boiling point is -4.4 DEG C, is gas under room temperature
Body, styrene-butadiene latex polymerization is substantially the reaction of gas-liquid mixed phase, and the therefore response time is long, and conversion ratio is low to react it is desirable to improve
Conversion ratio must extend the response time, common law synthesis styrene-butadiene latex conversion ratio reach 90% the reaction time be up to 30～
60h.Patent CN1254490 discloses a kind of latex preparation method of high conversion, the secondary monomer of the present invention (aliphatic conjugation two
Alkene and aromatic ethenyl compound) disposable addition, more than three times addition molecular weight regulators, more than four times addition emulsifying
Agent, initiator carry out batch (-type) emulsion polymerization, and polymerization temperature is 10～55 DEG C, obtain the rubber-like glue that conversion ratio is more than 90%
Breast, preparation method complex process, need repeatedly to feed, repeatedly heat up, and the response time is longer.Patent CN1341667A is using often
Pressure reaction is unsatisfactory for styrene-butadiene latex synthesis condition, and the higher cryogenic property being unfavorable for modified emulsifying asphalt of reaction temperature.
Content of the invention
The purpose of the present invention is invention a kind of low temperature synthesis high molecular, high conversion, is applied to modified emulsifying asphalt
The preparation method of styrene-butadiene latex.
For realizing the object of the invention, the technology of employing is：
A kind of styrene-butadiene latex, is to be prepared from by following each component in parts by weight：
Seed breast 5-40 part；Deionized water 40-60 part；Styrene 20-40 part；Butadiene 60-80 part；Emulsifying agent 0-5 part；
Electrolyte 0.1-0.3 part；Diffusant 0.1-0.5 part；Initiator 0.05-0.2 part；Molecular weight regulator 0.1-0.5 part；Free radical
Stabilizer 0.1-0.8 part；Terminator 0.05-0.1 part, age resistor 0.1-0.15 part；
Described seed breast is to be prepared from by following each component in parts by weight：
Deionized water 233-900 part；Styrene 20-40 part；Butadiene 60-80 part；Emulsifying agent 10-36 part；Electrolyte
0.1-0.3 part；Initiator 0.05-0.2 part；Reducing agent 0.01-0.05 part；Molecular weight regulator 0.1-0.5 part.
Described emulsifier solution is one of oleate, linoleate, rosinate, laruate, soap
Or multiple compounding aqueous solutions, its mass concentration is 25%-35%.
Described diffusant is alkyl polyoxyethylene ether class, lignin sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, oleoyl
The compounding aqueous solution of one or more of polyamine group hydroxy acid salt, its mass concentration is 25%-35%.
Described electrolyte is the compounding of one or more of sodium bicarbonate, potassium chloride, dibastic sodium phosphate, Sodium Acetate Trihydrate.
Described molecular weight regulator is one or more of alkyl hydrosulfide or polythiol class compound.
The method of the described styrene-butadiene latex of preparation, using ultrasonic wave added reaction, it comprises the following steps that：
1) preparation of seed breast：
Take, according to metering part, each component preparing seed breast, add emulsifier solution, electrolyte, reduction in polymeric kettle
Agent, molecular weight regulator and deionized water, after starting stirring, add whole butadiene, styrene, when temperature of reaction kettle reaches
When 5-15 DEG C, add whole initiator initiation reactions, when conversion ratio reaches 100%, stopped reaction；
2) preparation of High Solid Content SBR Latex
Take each component of the emulsified asphalt modification styrene-butadiene latex preparing high-solid lower-viscosity according to metering part, to step 1) preparation
Seed latex in add emulsifier solution, electrolyte, reducing agent, molecular weight regulator, diffusant, free radical stabilizer and go
Ionized water, when temperature of reaction kettle reaches 5-15 DEG C, continuous Deca styrene and butadiene and initiator in reactor, simultaneously
By in the ultrasonic amplitude transformer insertion reaction kettle on Vltrasonic device HC-SG-202000, and start Vltrasonic device, using ultrasonic wave added
Reaction, continues reaction 6-8h, when conversion ratio reaches more than 95.0%, adds terminator stopped reaction, in degassing kettle vacuum
For -0.10Mpa, under conditions of kettle temperature is 50 DEG C, add the age resistor of metering part, be de-gassed to remove residual monomer, finally
Obtain finished product after filtering.
Step 2) described in Vltrasonic device power be 60～100W.
Using (5-15 DEG C) reaction of whole low temperature, response time 6-8h, low-temp reaction can ensure that the molecular structure of latex
Regularity, improves the performance of modified emulsifying asphalt.
Monomer is added by the way of continuous Deca, and the joining day is 2-4h, there is not monomer droplet due in system, gathers
Fit system is under " hungry " state, and the continuous monomer instilling is diffused in seed latex grain and is polymerized, it is possible to increase particle diameter, carries
High monomer conversion ratio.
The present invention compared with prior art has the advantage that：Reaction temperature is 5-15 DEG C, and low-temp reaction can ensure that
The molecular structure regularity of latex, improves the performance of modified emulsifying asphalt, and ultrasonic assistant reaction shortens the response time, reaches
More than 95% required response time was 6-8h, and by using continuity method seeded emulsion polymerization, can be obtained that particle diameter is big, molecular weight
It is distributed wide High Solid Content SBR Latex.
Specific embodiment
Embodiment 1
1) preparation of seed breast：
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 13 parts of whole emulsifying agents (mass concentration is 30%, wherein 4 parts of fatty acid soaps, 9 parts of disproportionated rosin acid soap), electrolyte chlorination
0.3 part of potassium, 0.03 part of reducing agent ferrous salt, 0.3 part of molecular weight regulator tert-dodecylmercaotan and 345 parts of deionized water, open
After dynamic stirring, add 70 parts of butadiene, 30 parts of styrene, when temperature of reaction kettle reaches 5-15 DEG C, add whole initiators
Hydrogen peroxide pair0.15 part of initiation reaction of alkane.Reaction 2-4h, when conversion ratio reaches 100%, stopped reaction.
2) preparation of High Solid Content SBR Latex
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 5 parts whole of seed breasts, 3.3 parts of the aqueous solution (mass concentration is 25%) of emulsifying agent sodium abietate, molecular weight regulator
0.3 part of tert-dodecylmercaotan, 0.3 part of the aqueous solution (mass concentration is 25%) of diffusant sodium lignin sulfonate, free radical are steady
Determine 0.4 part of agent octadecylamine polyoxyethylene ether oxide, 0.1 part of electrolyte potassium chloride and 60 parts of deionized water, start stirring,
When temperature of reaction kettle reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pair0.1 part of company of alkane
Continue and be added dropwise in reactor, and open supersonic generator, power is 70W, monomer and initiator completion of dropping in 2-4h.Deca
After the completion of, continue reaction 2h, when conversion ratio reaches more than 95.0%, add terminator SDD
0.06 part of stopped reaction.It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, add antioxidant SP 0.12
Part, it is de-gassed to remove residual monomer, degassing time is 3 hours.Finished product is become after eventually passing filter.
The physical index of latex is：Conversion ratio 96.51%；Solid content 60.35%.
Embodiment 2
1) preparation of seed breast：
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 16 parts of whole emulsifying agents (mass concentration is 30%, wherein 5 parts of fatty acid soaps, 11 parts of disproportionated rosin acid soap), electrolyte carbon
0.2 part of sour hydrogen sodium, 0.02 part of reducing agent ferrous salt, 0.2 part of molecular weight regulator tert-dodecylmercaotan and deionized water 425
Part, after starting stirring, add 70 parts of butadiene, 30 parts of styrene, when temperature of reaction kettle reaches 5-15 DEG C, add whole drawing
Send out agent hydrogen peroxide pair0.15 part of initiation reaction of alkane.Reaction 2-4h, when conversion ratio reaches 100%, stopped reaction.
2) preparation of High Solid Content SBR Latex
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 25 parts of whole seeds breast, 4.3 parts of the aqueous solution (mass concentration I 28%) of emulsifying agent potassium oleate, molecular weight regulator uncle
0.4 part of hexadecyl mercaptan, 0.4 part of the aqueous solution (mass concentration is 32%) of diffusant sodium metnylene bis-naphthalene sulfonate, free radical
0.2 part of stabilizer hexadecylamine polyoxyethylene ether oxide, 0.2 part of electrolyte sodium bicarbonate and 40 parts of deionized water, start
Stirring, when temperature of reaction kettle reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator cumyl hydroperoxide
0.15 part is continuously added dropwise in reactor, and opens supersonic generator, and power is 60W, monomer and initiator Deca in 2-4h
Finish.After being added dropwise to complete, continue reaction 2h, when conversion ratio reaches more than 95.0%, add terminator diethyl hydroxylamine 0.08
Part stopped reaction.It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, adds 0.1 part of antioxidant MB, carry out
To remove residual monomer, degassing time is 3 hours for degassing.Finished product is become after eventually passing filter.
The physical index of latex is：Conversion ratio 97.45%；Solid content 63.28%.
Embodiment 3
1) preparation of seed breast：
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 23 parts of whole emulsifier solutions (concentration is 30%, wherein 8 parts of fatty acid soaps, 15 parts of disproportionated rosin acid soap), electrolyte phosphorus
0.3 part of sour potassium, 0.4 part of molecular weight regulator n-dodecyl mercaptan and 395 parts of deionized water, after starting stirring, add fourth two
70 parts of alkene, 30 parts of styrene, when temperature of reaction kettle reaches 5-15 DEG C, add whole initiator cumyl hydroperoxides 0.1
Part initiation reaction.When conversion ratio reaches 100%, stopped reaction.
2) preparation of High Solid Content SBR Latex
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 40 parts whole of seed breasts, 4.5 parts of the aqueous solution (mass concentration is 35%) of emulsifying agent dodecylbenzene sodium sulfonate, molecule
0.5 part of regulator n-dodecyl mercaptan of amount, (mass concentration is 0.2 part of the aqueous solution of diffusant alkylpolyoxyethylene
33%), 0.7 part of free radical stabilizer octadecylamine polyoxyethylene ether oxide, 0.3 part of electrolyte potassium phosphate and deionized water
40 parts, start stirring, when temperature of reaction kettle reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide
0.08 part of isopropylbenzene is continuously added dropwise in reactor, and opens supersonic generator, and power is 85W, monomer and initiation in 2-4h
Agent completion of dropping.After being added dropwise to complete, continue reaction 2h, when conversion ratio reaches more than 95.0%, add terminator N isopropyl
0.06 part of stopped reaction of azanol.It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, add age resistor
SP0.14 part, is de-gassed to remove residual monomer, and degassing time is 3 hours.Finished product is become after eventually passing filter.
The physical index of latex is：Conversion ratio 95.61%；Solid content 59.45%.
Embodiment 4
1) preparation of seed breast：
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 31 parts of whole emulsifier solutions (concentration is 30%, wherein 9 parts of fatty acid soaps, 22 parts of disproportionated rosin acid soap), electrolyte phosphorus
0.2 part of sour hydrogen sodium, 0.3 part of molecular weight regulator tert-dodecylmercaotan and 480 parts of deionized water, after starting stirring, add fourth
70 parts of diene, 30 parts of styrene, when temperature of reaction kettle reaches 5-15 DEG C, add whole initiator di isopropyl benzene hydroperoxide 0.1
Part initiation reaction.When conversion ratio reaches 100%, stopped reaction.
2) preparation of High Solid Content SBR Latex
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 15 parts whole of seed breasts, 2.8 parts of the aqueous solution (mass concentration is 27%) of emulsifying agent sodium abietate, molecular weight regulator
0.4 part of tertiary hexadecyl mercaptan, 0.3 part of the aqueous solution (mass concentration is 30%) of diffusant naphthal sodium sulfonate, free radical
0.6 part of stabilizer hexadecylamine polyoxyethylene ether oxide, 0.1 part of electrolyte sodium bicarbonate and 55 parts of deionized water, start
Stirring, when temperature of reaction kettle reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pairAlkane
0.15 part is continuously added dropwise in reactor, and opens supersonic generator, and power is 95W, monomer and initiator Deca in 2-4h
Finish.After being added dropwise to complete, continue reaction 2h, when conversion ratio reaches more than 95.0%, add terminator Methyl disulfide for ammonia
0.07 part of stopped reaction of base sodium formate.It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, add age resistor
SP0.13 part, is de-gassed to remove residual monomer, and degassing time is 3 hours.Finished product is become after eventually passing filter.
The physical index of latex is：Conversion ratio 97.73%；Solid content 60.36%.
Embodiment 5
1) preparation of seed breast：
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Add 15 parts of whole emulsifier solutions (mass concentration is 30%, wherein 4 parts of fatty acid soaps, 11 parts of disproportionated rosin acid soap), electrolysis
0.3 part of matter sodium bicarbonate, 0.3 part of the tertiary hexadecyl mercaptan of molecular weight regulator and 410 parts of deionized water, after starting stirring, plus
Enter 70 parts of butadiene, 30 parts of styrene, when temperature of reaction kettle reaches 5-15 DEG C, add whole initiator hydrogen peroxide isopropyls
0.1 part of initiation reaction of benzene.When conversion ratio reaches 100%, stopped reaction.
2) preparation of High Solid Content SBR Latex
Using 2L polymeric kettle, inventory amounts to 1200g, first evacuation, then with nitrogen displacement, disposable in polymeric kettle
Just add 30 parts whole of seed breasts, 4.8 parts of the aqueous solution (mass concentration is 28%) of emulsifying agent potassium oleate, molecular weight regulator
0.2 part of lauryl mercaptan, 0.5 part of the aqueous solution (mass concentration is 32%) of diffusant sodium metnylene bis-naphthalene sulfonate, free radical
0.3 part of stabilizer octadecylamine polyoxyethylene ether oxide, 0.2 part of electrolyte potassium chloride and 45 parts of deionized water, startup is stirred
Mix, when temperature of reaction kettle reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pair0.2 part of alkane
Continuously it is added dropwise in reactor, and opens supersonic generator, power is 90W, monomer and initiator completion of dropping in 2-4h.Drip
Plus after the completion of, continue reaction 2h, when conversion ratio reaches more than 95.0%, add terminator SDD
0.1 part of stopped reaction.It is -0.10Mpa in degassing kettle vacuum, under conditions of kettle temperature is 50 DEG C, add 0.15 part of antioxidant MB,
It is de-gassed to remove residual monomer, degassing time is 3 hours.Finished product is become after eventually passing filter.
The physical index of latex is：Conversion ratio 98.23%；Solid content 60.09%.
Claims (7)
1. a kind of styrene-butadiene latex is it is characterised in that be to be prepared from by following each component in parts by weight：
Seed breast 5-40 part；Deionized water 40-60 part；Styrene 20-40 part；Butadiene 60-80 part；Emulsifying agent 0-5 part；Electrolysis
Matter 0.1-0.3 part；Diffusant 0.1-0.5 part；Initiator 0.05-0.2 part；Molecular weight regulator 0.1-0.5 part；Free radical is stable
Agent 0.1-0.8 part；Terminator 0.05-0.1 part, age resistor 0.1-0.15 part；
Described seed breast is to be prepared from by following each component in parts by weight：
Deionized water 233-900 part；Styrene 20-40 part；Butadiene 60-80 part；Emulsifying agent 10-36 part；Electrolyte 0.1-0.3
Part；Initiator 0.05-0.2 part；Reducing agent 0.01-0.05 part；Molecular weight regulator 0.1-0.5 part.
2. styrene-butadiene latex as claimed in claim 1 it is characterised in that described emulsifier solution be oleate, linoleate,
The compounding aqueous solution of one or more of rosinate, laruate, soap, its mass concentration is 25%-35%.
3. styrene-butadiene latex as claimed in claim 1 is it is characterised in that described diffusant is alkyl polyoxyethylene ether class, wood
The compounding aqueous solution of one or more of mahogany sulfonate class, naphthalene sulfonic acid-formaldehyde condensation product, oleoyl polyamine group hydroxy acid salt,
Its mass concentration is 25%-35%.
4. styrene-butadiene latex as claimed in claim 1 is it is characterised in that described electrolyte is sodium bicarbonate, potassium chloride, phosphoric acid
One or more of hydrogen sodium, Sodium Acetate Trihydrate compounding.
5. styrene-butadiene latex as claimed in claim 1 is it is characterised in that described molecular weight regulator is alkyl hydrosulfide or many sulfur
One or more of alcohol compound.
6. prepare the method for styrene-butadiene latex as claimed in claim 1 it is characterised in that using ultrasonic wave added reaction, it is concrete
Step is as follows：
1) preparation of seed breast：
Take, according to metering part, each component preparing seed breast, add emulsifier solution, electrolyte, reducing agent in polymeric kettle, divide
Son amount regulator and deionized water, after starting stirring, add whole butadiene, styrene, when temperature of reaction kettle reaches 5-15
DEG C when, add whole initiator initiation reactions, when conversion ratio reaches 100%, stopped reaction；
2) preparation of High Solid Content SBR Latex
Take each component of the emulsified asphalt modification styrene-butadiene latex preparing high-solid lower-viscosity according to metering part, to step 1) kind prepared
Emulsifier solution, electrolyte, reducing agent, molecular weight regulator, diffusant, free radical stabilizer and deionization is added in sub- latex
Water, when temperature of reaction kettle reaches 5-15 DEG C, in reactor, continuous Deca styrene and butadiene and initiator, will surpass simultaneously
In ultrasonic amplitude transformer insertion reaction kettle on acoustic device HC-SG-202000, and start Vltrasonic device, using ultrasonic wave added reaction,
Continue reaction 6-8h, when conversion ratio reaches more than 95.0%, add terminator stopped reaction, degassing kettle vacuum be-
0.10Mpa, under conditions of kettle temperature is 50 DEG C, adds the age resistor of metering part, is de-gassed to remove residual monomer, eventually passes
Finished product is obtained after filter.
7. as claimed in claim 6 a kind of preparation method of ultrasonic-assisted synthesis styrene-butadiene latex it is characterised in that step 2)
Described in Vltrasonic device power be 60～100W.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285513A (en) * | 2018-02-09 | 2018-07-17 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
| 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 |
| CN112125986A (en) * | 2020-09-21 | 2020-12-25 | 山东京博中聚新材料有限公司 | Styrene-butadiene latex demonomerization and concentration device and process |
| CN112500526A (en) * | 2020-12-09 | 2021-03-16 | 湖北分聚新材料有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
| CN113512148A (en) * | 2021-08-04 | 2021-10-19 | 福建亮晶晶新材料有限公司 | Preparation method of special styrene-butadiene latex for road asphalt modification |
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| CN108285513A (en) * | 2018-02-09 | 2018-07-17 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
| 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 |
| CN112125986A (en) * | 2020-09-21 | 2020-12-25 | 山东京博中聚新材料有限公司 | Styrene-butadiene latex demonomerization and concentration device and process |
| CN112125986B (en) * | 2020-09-21 | 2022-12-02 | 山东京博中聚新材料有限公司 | Styrene butadiene latex monomer removal and concentration device and process |
| CN112500526A (en) * | 2020-12-09 | 2021-03-16 | 湖北分聚新材料有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
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