CN108285513A - 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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- CN108285513A CN108285513A CN201810132923.0A CN201810132923A CN108285513A CN 108285513 A CN108285513 A CN 108285513A CN 201810132923 A CN201810132923 A CN 201810132923A CN 108285513 A CN108285513 A CN 108285513A
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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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Abstract
The present invention relates to a kind of styrene-butadiene latex and preparation method thereof, especially a kind of styrene-butadiene latex and preparation method thereof with network blackboard, especially suitable for modified emulsifying asphalt.Its main method is using butadiene and styrene as main monomer, styrene, divinylbenzene, acrylic acid, methacrylate etc. are mix monomer, compound emulsifying agent, initiator, electrolyte, diffusant, molecular weight regulator is added, mix monomer swelling is added after the polymerization of high/low temperature two-stage method to cause, synthesize the styrene-butadiene latex that the solid content with inierpeneirating network structure is 55% or more, the softening point of its modified emulsifying asphalt is higher than 57 DEG C, and ductility is more than 50cm.The present invention's is mainly characterized by, and two-step method polymerization improves the solid content of latex；Prepared styrene-butadiene latex is mainly used for modified emulsifying asphalt, and modified effect is apparent.
Description
Technical field
The present invention relates to a kind of styrene-butadiene latex and preparation method thereof, especially a kind of butadiene-styrene rubber with network blackboard
Breast and preparation method thereof, especially suitable for modified emulsifying asphalt.
Background technology
Modified emulsifying asphalt is widely used in highway construction and maintenance project, and styrene-butadiene latex SBRL is more commonly used at present
Emulsified bitumen modifying agent.SBRL used at present is mainly used for improving the low-temperature ductility of pitch, for high temperature performance of asphalt
Improving influences less.
For many years, countries in the world constantly carry out the research of asphalt modification, have delivered a large amount of related patents.The country drips oil
The synthesis attention rate of green modification styrene-butadiene latex is relatively low, is at most at present styrene-butadiene latex about styrene-butadiene latex and its study on the modification
The problem of the deficiencies of as construction material, the binder of Paper Coating, caking property and water resistance.In relation to the more of modified emulsifying asphalt
For research modified emulsifying asphalt preparation process etc. and styrene-butadiene latex synthesis patent be also mostly applied to binder and carpet
And in terms of process modification etc., relevant patent has " the high softening-point emulsification drip that virtuous and beautiful, horse distances of travel of roc of CN105273420 high etc. are delivered
Blueness and preparation method thereof "；About modified butadiene-styrene latex, patent CN102898584 discloses a kind of styrene-butadiene-isoamyl
Propylene-diene terpolymer integrates latex, and this latex is good by the good cold tolerance of polybutadiene latex, polyisoprene latex
Physical mechanical property and the good rheology processability of styrene-butadiene latex roll into one, be a kind of splendid high property of comprehensive performance
It can latex.
Common two kinds of latex of high temperature and low temperature are all not exclusively suitable for modified emulsifying asphalt, and wherein low temperature latex is than high
Warm latex intensity is high, and modified emulsifying asphalt after-tack point is higher than high temperature latex, and (after-tack o'clock of 70# asphalt modifications can be improved by 47 DEG C
To 53 DEG C), tensile strength also accordingly improves, but solid content is low, and 58-60 DEG C of softening point and external product still has larger gap.
Although high temperature latex high conversion rate, due to degree of branching height, cause intensity low, poor toughness after modified emulsifying asphalt, softening point is low.
Invention content
There is network blackboard, the butadiene-styrene rubber especially suitable for modified emulsifying asphalt the purpose of the present invention is invention is a kind of
The preparation method of breast.
Purpose to realize the present invention, the technology used for：
A kind of styrene-butadiene latex, in parts by weight, raw material group become：50-70 parts of deionized water；20-40 parts of styrene；Fourth
60-80 parts of diene；2-5 parts of mix monomer；1-6 parts of emulsifier；0.1-0.3 parts of electrolyte；0.1-0.5 parts of diffusant；Initiator 1
0.05-0.2 parts；2 0.05-0.2 parts of initiator；0.1-0.5 parts of molecular weight regulator；0.1-0.8 parts of free radical stabilizer；It is anti-
Old agent 0.1-0.15 parts；
The mix monomer is by two kinds and above group in styrene, divinylbenzene, acrylic acid, methacrylate
At.
The initiator 1, to Meng's alkane, di isopropyl benzene hydroperoxide or cyclohexanone peroxide, causes styrene using hydrogen peroxide
With the polymerisation of two kinds of monomers of butadiene.
The initiator 2 uses isopropyl benzene hydroperoxide-tetraethylenepentamine or tetra- ethylene five of tert-butyl hydroperoxide-
The redox initiation systems such as amine, wherein oxidant are isopropyl benzene hydroperoxide or tert-butyl hydroperoxide, and reducing agent is tetrem
Five amine of alkene, the wherein molar ratio of oxidant and reducing agent are more than 1, and free radical is avoided to react and inactivate with excessive reductant, cause
Mix monomer forms cross-linked structure.
The emulsifier is oleate, linoleate, rosinate, laruate, one kind in fatty acid salt or more
The aqueous solution of the compounding of kind, mass concentration 25%-35%, and the pH value of emulsifier solution are 8~11, ensure that modified milk
Change the de-emulsification speed of pitch.
The diffusant is alkyl polyoxyethylene ether class, lignin sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, oleoyl
The aqueous solution of one or more compoundings in polyamine group hydroxy acid salt, mass concentration 25%-35% ensure that latex has
Good mobility.
The electrolyte is one or more compoundings in sodium bicarbonate, potassium chloride, dibastic sodium phosphate, sodium acetate.
The molecular weight regulator is one or more, the guarantee high temperature fourth in alkyl hydrosulfide or polythiols compound
The molecular size of benzene rubber.
The anti-aging agent is SP or MB, prevents latex aging and reduced performance in de- single and swelling.
The method for preparing the styrene-butadiene latex, is as follows：
1) two-stage method polymerize：
Taken according to metering part and prepare each component of styrene-butadiene latex, be added into polymeric kettle emulsifier, electrolyte, reducing agent,
After starting stirring whole butadiene, styrene is added, when temperature of reaction kettle reaches 5- in molecular weight regulator and deionized water
At 15 DEG C, 1 initiation reaction of initiator is added, after reacting 2-5h, is warming up to 30-50 DEG C, stops reaction after the reaction was continued 2-4h；
Degassing kettle vacuum degree is that -0.10Mpa is added the anti-aging agent of metering part, is de-gassed residual to remove under conditions of kettle temperature is 40 DEG C
Remaining monomer；
2) the poly- inierpeneirating network structure of breast is formed：
The each component for preparing styrene-butadiene latex is taken according to metering part, and mix monomer is added in the latex prepared to step 1), draws
The mixed liquor of oxidant in agent 2 is sent out, 0.5-1.5h is swollen, reducing agent in initiator 2 is added dropwise, insulation reaction 1-3h is added and terminates
Agent stops reaction.
In the poly- inierpeneirating network structure formation of breast, degree of swelling will directly affect the form of heterophasic copolymer latex particle,
Therefore it must assure that the swelling time of mix monomer and lotion is not less than 0.5h.
After mix monomer swelling is added, emulsifier is not added, the generation of new latex particle is inhibited, effectively control mixing is single
The production quantity of body homopolymer.This is because the addition of mixing hard monomer is not very big, the emulsifier guarantee enough of latex is new single
Body enters in micelle, still can maintain near latex particle saturation adsorption concentration；On the other hand mixing hard monomer and butadiene-styrene rubber
Breast has much like structure, and according to the principle of similar compatibility, this kind of monomer can be very good to be swollen in styrene-butadiene latex micelle, because
This does not add new emulsifier.The process mix monomer is swollen to form latex particle.
Initiator 2 uses the oxygen such as one tetraethylenepentamine of isopropyl benzene hydroperoxide or one tetraethylenepentamine of tert-butyl hydroperoxide
Change reduction initiating system, this is because be added mix monomer it is mainly lipophilic, initiation reaction occur mainly in oil phase with
Aqueous phase interface, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide have moderate hydrophilic and oleophilic in the redox initiation system
Property, and under low temperature polymerization, its decomposition rate is by being controlled by redox reaction with the tetraethylenepentamine in water phase
, efficiency of initiation is high.Initiator 2 causes mix monomer and forms cross-linked structure.
Interpenetrating net polymer has the cross-linked phase of co-continuous, and two kinds of cross-linked networks mutually tangle, interweave so that two kinds of originals
This incompatible polymers is provided with higher mixability, and phases were separated is seriously obstructed, to realize forced mutual tolerance.It is newborn
At cross-linked structure endlessly bother another person, interweave with latex particle, form network blackboard.
The present invention has the advantage that compared with prior art：High/low temperature two-stage method polymerisation ensures styrene-butadiene latex
Conversion ratio is up to 92% or more, solid content >=55%；The forced mutual tolerance of network blackboard, interface interpenetrating increase latex particle with
The compatibility of pitch, the addition for mixing hard monomer are remarkably improved the softening point of modified emulsifying asphalt, modified emulsifying asphalt it is soft
Change point and be higher than 57 DEG C, ductility is more than 50cm.
Specific implementation mode
Embodiment 1
1) two-stage method polymerize：
Using 2L polymeric kettles, inventory amounts to 1200g, vacuumizes first, then is replaced with nitrogen, disposable into polymeric kettle
Aqueous solution 3.5 parts (mass concentrations 27%), the tertiary cetyl of molecular weight regulator of whole emulsifier sodium abietates is added
Aqueous solution 0.3 part (mass concentration 30%), the free radical stabilizer 16 of 0.4 part of mercaptan, diffusant naphthal sodium sulfonate
66 parts of 0.6 part of ethoxylated fatty amines oxide, 0.1 part of electrolyte sodium bicarbonate and deionized water start stirring, work as reaction
When kettle temperature degree reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pair0.15 part of alkane is continuous to be added dropwise
Enter in reaction kettle, reaction is warming up to 40 DEG C after 4 hours, and the reaction was continued, and when conversion ratio reaches 92.0% or more, latex is shifted
To degassing kettle, it is that 0.13 part of antioxidant SP is added under conditions of kettle temperature is 50 DEG C in -0.10Mpa in degassing kettle vacuum degree, carries out
To remove residual monomer, degassing time is 2 hours for degassing；
2) the poly- inierpeneirating network structure of breast is formed：
3 parts of 0.15 part of initiator (oxidant) tert-butyl hydroperoxide, mix monomer (styrene are added：Divinylbenzene：
Acrylic acid=1：1：1) it is swollen 1 hour, adds the 0.05 part of initiation reaction of initiator (reducing agent) tetraethylenepentamine, 50 DEG C of reactions
0.1 part of terminator sodium dimethyl dithiocarbamate is added after 2 hours and stops reaction.Finished product is finally obtained after filtering.
The performance indicator of latex is：Conversion ratio 92.23%；Solid content 56.96%；Modified emulsifying asphalt softening point 58.0
DEG C, ductility 55cm.
Embodiment 2
1) two-stage method polymerize：
Using 2L polymeric kettles, inventory amounts to 1200g, vacuumizes first, then is replaced with nitrogen, disposable into polymeric kettle
Aqueous solution 3.45 parts (mass concentrations 25%), the tertiary dodecyl of molecular weight regulator of whole emulsifier sodium abietates is added
Aqueous solution 0.3 part (mass concentration 25%), the free radical stabilizer octadecane of 0.3 part of mercaptan, diffusant sodium lignin sulfonate
63 parts of 0.4 part of base amine polyoxyethylene ether oxide, 0.1 part of electrolyte potassium chloride and deionized water start stirring, when reaction kettle temperature
When degree reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pair0.1 part of alkane is continuous to be added dropwise to instead
It answers in kettle, reaction is warming up to 40 DEG C after 3 hours, and the reaction was continued, when conversion ratio reaches 92.0% or more, latex is transferred to de-
Gas kettle is that -0.10Mpa is added 0.15 part of antioxidant MB, is de-gassed under conditions of kettle temperature is 40 DEG C in degassing kettle vacuum degree
To remove residual monomer, degassing time is 2 hours；
2) the poly- inierpeneirating network structure of breast is formed：
2 parts of 0.12 part of initiator (oxidant) isopropyl benzene hydroperoxide, mix monomer (styrene are added：Divinylbenzene
=1：1) it is swollen 1 hour, the 0.06 part of initiation reaction of initiator (reducing agent) tetraethylenepentamine is added, after 50 DEG C are reacted 2 hours
Terminator is added, terminator N -0.08 part of isopropylhydroxyla stopping reaction being added.Finished product is finally obtained after filtering.
The performance indicator of latex is：Conversion ratio 93.17%；Solid content 58.26%；Modified emulsifying asphalt softening point 58.7
DEG C, ductility 50cm.
Embodiment 3
1) two-stage method polymerize：
Using 2L polymeric kettles, inventory amounts to 1200g, vacuumizes first, then is replaced with nitrogen, disposable into polymeric kettle
Aqueous solution 5 parts (mass concentrations 28%), the tertiary hexadecyl mercaptan of molecular weight regulator of whole emulsifier potassium oleates is added
0.4 part, aqueous solution 0.4 part (mass concentration 32%), the free radical stabilizer hexadecane of diffusant sodium metnylene bis-naphthalene sulfonate
59 parts of 0.2 part of base amine polyoxyethylene ether oxide, 0.2 part of electrolyte sodium bicarbonate and deionized water start stirring, work as reaction kettle
When temperature reaches 5-15 DEG C, 70 parts of butadiene, 30 parts of styrene, 0.15 part of initiator cumyl hydroperoxide are continuously added dropwise to
In reaction kettle, reaction is warming up to 40 DEG C after 3 hours, and the reaction was continued, and when conversion ratio reaches 92.0% or more, latex is transferred to
Deaerate kettle, is that -0.10Mpa is added 0.1 part of antioxidant MB, is de-gassed under conditions of kettle temperature is 40 DEG C in degassing kettle vacuum degree
To remove residual monomer, degassing time is 1.5 hours；
2) the poly- inierpeneirating network structure of breast is formed：
4 parts of 0.09 part of initiator (oxidant) tert-butyl hydroperoxide, mix monomer (styrene are added：Divinylbenzene：
Acrylic acid=1：2：1) it is swollen 1 hour, adds the 0.04 part of initiation reaction of initiator (reducing agent) tetraethylenepentamine, 50 DEG C of reactions
0.07 part of terminator sodium dimethyl dithiocarbamate is added after 2 hours and stops reaction.Finished product is finally obtained after filtering.
The performance indicator of latex is：Conversion ratio 92.05%；Solid content 59.77%；Modified emulsifying asphalt softening point 59.0
DEG C, ductility 52cm.
Embodiment 4
1) two-stage method polymerize：
Using 2L polymeric kettles, inventory amounts to 1200g, vacuumizes first, then is replaced with nitrogen, disposable into polymeric kettle
Aqueous solution 5.6 parts (mass concentrations 28%), the molecular weight regulator dodecyl sulphur of whole emulsifier potassium oleates is added
Aqueous solution 0.5 part (mass concentration 32%), the free radical stabilizer 18 of 0.2 part of alcohol, diffusant sodium metnylene bis-naphthalene sulfonate
68 parts of 0.3 part of ethoxylated fatty amines oxide, 0.2 part of electrolyte potassium chloride and deionized water start stirring, work as reaction kettle
When temperature reaches 5-15 DEG C, by 70 parts of butadiene, 30 parts of styrene, initiator hydrogen peroxide pair0.2 part of alkane is continuously added dropwise to
Being warming up to 40 DEG C in reaction kettle, after reaction 2, the reaction was continued, and when conversion ratio reaches 92.0% or more, latex is transferred to degassing
Kettle, degassing kettle vacuum degree be -0.10Mpa, kettle temperature be 40 DEG C under conditions of, be added 0.15 part of antioxidant MB, be de-gassed with
Residual monomer is removed, degassing time is 3 hours；
2) the poly- inierpeneirating network structure of breast is formed：
3 parts of 0.08 part of initiator (oxidant) tert-butyl hydroperoxide, mix monomer (styrene are added：Divinylbenzene：
Methacrylate=1：1：1) it is swollen 1 hour, adds the 0.04 part of initiation reaction of initiator (reducing agent) tetraethylenepentamine, 50
DEG C reaction is added 0.1 part of terminator sodium dimethyl dithiocarbamate after 2 hours and stops reaction.Finally after filtering at
Product.
The performance indicator of latex is：Conversion ratio 93.92%；Solid content 57.45%；Modified emulsifying asphalt softening point 57.5
DEG C, ductility 59cm.
Embodiment 5
1) two-stage method polymerize：
Using 2L polymeric kettles, inventory amounts to 1200g, vacuumizes first, then is replaced with nitrogen, disposable into polymeric kettle
Aqueous solution 5.2 parts of (mass concentration 35%), molecular weight regulators of whole emulsifier neopelexes are added just
0.5 part of lauryl mercaptan, the aqueous solution 0.2 part (mass concentration 33%) of diffusant dodecyl polyoxyethylene ether, freedom
70 parts of 0.7 part of based stabilizer octadecylamine polyoxyethylene ether oxide, 0.3 part of electrolyte potassium phosphate and 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
0.08 part is continuously added dropwise in reaction kettle, and reaction is warming up to 40 DEG C of continuation after 4 hours, when conversion ratio reaches 92.0% or more,
Latex is transferred to degassing kettle, is that anti-aging agent is added under conditions of kettle temperature is 40 DEG C in -0.10Mpa in degassing kettle vacuum degree
It SP0.14 parts, is de-gassed to remove residual monomer, degassing time is 3 hours；
2) the poly- inierpeneirating network structure of breast is formed：
4 parts of 0.13 part of initiator (oxidant) isopropyl benzene hydroperoxide, mix monomer (divinylbenzenes are added：Methyl-prop
Olefin(e) acid ester=1：3) it is swollen 1 hour, adds the 0.07 part of initiation reaction of initiator (reducing agent) tetraethylenepentamine, 50 DEG C of reactions 2
Terminator N -0.06 part of isopropylhydroxyla is added after hour and stops reaction.Finished product is finally obtained after filtering.
The performance indicator of latex is：Conversion ratio 92.61%；Solid content 57.58%；Modified emulsifying asphalt softening point 57.8
DEG C, ductility 65cm.
Claims (8)
1. a kind of styrene-butadiene latex, which is characterized in that in parts by weight, raw material group becomes：50-70 parts of deionized water；Styrene
20-40 parts；60-80 parts of butadiene；2-5 parts of mix monomer；1-6 parts of emulsifier；0.1-0.3 parts of electrolyte；Diffusant 0.1-0.5
Part；1 0.05-0.2 parts of initiator；2 0.05-0.2 parts of initiator；0.1-0.5 parts of molecular weight regulator；Free radical stabilizer
0.1-0.8 parts；0.1-0.15 parts of anti-aging agent.
2. styrene-butadiene latex as described in claim 1, which is characterized in that the mix monomer by styrene, divinylbenzene,
Two kinds in acrylic acid, methacrylate and composition described above.
3. styrene-butadiene latex as described in claim 1, which is characterized in that the initiator 2 uses isopropyl benzene hydroperoxide-
Tetraethylenepentamine or tert-butyl hydroperoxide-tetraethylenepentamine redox initiation system.
4. styrene-butadiene latex as described in claim 1, which is characterized in that the emulsifier is oleate, linoleate, rosin
The aqueous solution of one or more compoundings in hydrochlorate, laruate, fatty acid salt, mass concentration 25%-35%.
5. styrene-butadiene latex as described in claim 1, which is characterized in that the diffusant is alkyl polyoxyethylene ether class, wood
The aqueous solution of mahogany sulfonate class, naphthalene sulfonic acid-formaldehyde condensation product, one or more compoundings in oleoyl polyamine group hydroxy acid salt,
Its mass concentration is 25%-35%.
6. styrene-butadiene latex as described in claim 1, which is characterized in that the electrolyte is sodium bicarbonate, potassium chloride, phosphoric acid
One or more compoundings in hydrogen sodium, sodium acetate.
7. styrene-butadiene latex as described in claim 1, which is characterized in that the molecular weight regulator is alkyl hydrosulfide or more sulphur
It is one or more in alcohol compound.
8. the method for preparing styrene-butadiene latex as described in claim 1, which is characterized in that it is as follows：
1) two-stage method polymerize：
The each component for preparing styrene-butadiene latex is taken according to metering part, and emulsifier, electrolyte, reducing agent, molecule are added into polymeric kettle
Conditioning agent and deionized water are measured, after starting stirring, whole butadiene, styrene is added, when temperature of reaction kettle reaches 5-15 DEG C
When, 1 initiation reaction of initiator is added, after reacting 3-5h, is warming up to 30-50 DEG C, stops reaction after the reaction was continued 2-4h；It is deaerating
Kettle vacuum degree is that the anti-aging agent of metering part is added under conditions of kettle temperature is 50 DEG C in -0.10Mpa, is de-gassed remaining single to remove
Body；
2) the poly- inierpeneirating network structure of breast is formed：
The each component for preparing styrene-butadiene latex is taken according to metering part, and mix monomer, initiator 2 is added in the latex prepared to step 1)
The mixed liquor of middle oxidant is swollen 0.5-1.5h, and reducing agent in initiator 2 is added dropwise, and insulation reaction 1-3h is added terminator and stops
Reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041855A (en) * | 2019-04-22 | 2019-07-23 | 成都新柯力化工科技有限公司 | A kind of environment-friendly building materials special bonding glue and preparation method |
| CN111154040A (en) * | 2020-01-03 | 2020-05-15 | 大连理工大学 | Method for preparing MBS alloy compatilizer based on controllable double-particle-size-distribution latex |
| CN111876105A (en) * | 2020-08-17 | 2020-11-03 | 山东京博中聚新材料有限公司 | Modified styrene-butadiene pressure-sensitive adhesive and preparation method thereof |
| CN113502126A (en) * | 2021-07-06 | 2021-10-15 | 科顺防水科技股份有限公司 | Aqueous base layer treating agent composition, aqueous base layer treating agent, preparation method and application thereof |
| 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 |
| CN114773528A (en) * | 2022-04-29 | 2022-07-22 | 山东京博中聚新材料有限公司 | Vinyl styrene-butadiene latex and preparation method and application thereof |
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