CN106699970A - Butadiene styrene vinyl-pyridine latex and preparation method thereof - Google Patents
Butadiene styrene vinyl-pyridine latex and preparation method thereof Download PDFInfo
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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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- 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
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
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Abstract
The invention discloses butadiene styrene vinyl-pyridine latex and a preparation method thereof, and belongs to the technical field of high-molecular compounds. The butadiene styrene vinyl-pyridine latex is characterized by being prepared from the following raw materials in parts by mass: 55-75 parts of butadiene, 10-25 parts of styrene, 5-20 parts of 2-vinylpyridine, 140-150 parts of soft water, 1.3-10 parts of an emulsifier, 2-4 parts of rosin soap, 0.5-1.5 parts of stearate soap, 0.5-1 part of a diffusant, 0-1 part of OP-10, 0.05-0.5 part of an electrolyte, 0.5-1 part of a molecular weight regulator, 0.3-0.5 part of an initiator, 0.05-1 part of a deoxidant, and 0.05-1 part of a terminator; and the emulsifier is prepared from the following raw materials in parts by mass: 360-395 parts of soft water, 60-80 parts of carbamide,2.5-3 parts of phosphoric acid, 3-5 parts of ethylenediamine tetraacetic acid, and 0.5-1 part of caustic alkali. The adhesion property, the mechanical stability, the chemical stability and the foam property of the latex are obviously improved, the usability of the latex during impregnation is also improved correspondingly, rubber sheets and rubber scraps generated by impregnation are reduced, and the impregnation cycle is prolonged.
Description
Technical field
The invention belongs to macromolecular compound technical field, and in particular to a kind of butylbenzene pyrrole latex and preparation method thereof.
Background technology
Butylbenzene pyrrole latex can be reacted due to the polarity nitrogen-atoms on pyridine ring with the organic group on RF resins and fiber,
Form the strong combination with dipole of hydrogen so that the cohesive of butylbenzene pyrrole latex and synthetic fibers be significantly better than Heveatex and other
Synthetic latex, so as to be widely used as the framework material of the rubbers such as tire, sebific duct, adhesive tape, as universal in world wide
The critical material that the rubber of use is bonded with fiber, with irreplaceability.The quality of butylbenzene pyrrole latex determines impregnation
The quality of framework material and rubber binding ability.
With developing rapidly for auto industry and tire industry, the world is to the demand of butylbenzene pyrrole latex in increasing substantially
Gesture.At present, butylbenzene pyrrole latex is substantially hot using batch tank in water phase by butadiene, styrene, 2- vinylpyridines
The aqueous dispersion that polymerizing technology is made.The technology has that gel fraction is low, the of a relatively high shortcoming of cost, and the butylbenzene pyrrole breast for producing
Glue has the deficiency of not strong enough cohesive force, easy decomposition and mechanical stability difference.
For above-mentioned present situation, how to improve butylbenzene pyrrole breast combination property is still that those skilled in the art need to face and overcome
Technical barrier.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of butylbenzene pyrrole latex and preparation method thereof, it is possible to increase its is comprehensive
Close performance.
In order to solve the above technical problems, the technical scheme is that：Design a kind of butylbenzene pyrrole latex, it is characterised in that：
Raw material and its mass fraction are as follows：
The emulsifying agent is made into by the following raw material by mass fraction：
Preferably, the emulsifying agent is made into by the following raw material by mass fraction：
Preferably, the terminator be isopropylhydroxyla or, aromatic hydrocarbons base dithiocarboxylic acid or its salt.
Preferably, the diffusant be naphthalene sulfonic acids and formaldehyde condensation sodium salt or, alkyl naphthalene sulfonic acid and formaldehyde condensation
Sodium salt.
Preferably, the molecular weight regulator is processed by pre-emulsification, and solution used by pre-emulsification is that mass percentage concentration is
10~15% soap water.
Preferably, the molecular weight regulator is processed by microemulsified, and raw materials used in microemulsified and its mass fraction is such as
Under：
Present invention also offers a kind of method for preparing above-mentioned butylbenzene pyrrole latex, it is characterised in that：Comprise the following steps：
(1) to the phosphorus of the phosphoamide of 60~80 mass parts of addition, 2.5~3 mass parts in the soft water of 360~395 mass parts
The caustic alkali of acid, the ethylenediamine tetra-acetic acid of 3~5 mass parts and 0.5~1 mass parts, stirs in the environment that temperature is 65 DEG C
60min, is obtained emulsifying agent；
(2) in 140~150 mass parts soft water add 2~4 mass parts rosin soaps, 0.5~1.5 mass parts stearate soap,
0.5~1 mass parts diffusant, 0.05~1 mass parts oxygen scavenger, 0~1 mass parts OP-10,0.05~0.5 mass parts electrolyte
With emulsifying agent obtained in 1.3~10 mass parts steps (1), the first mixed liquor is obtained；
(3) the first mixed liquor obtained in whipping step (2), to 10~25 mass parts benzene of addition in the first mixed liquor of stirring
Ethene, 45~55 mass parts butadiene and 3~15 mass parts 2- vinylpyridines, are obtained the second mixed liquor；
(4) when the second mixed liquor of heating is to 50 DEG C, 0.3~0.5 mass parts initiator is added to start reaction, reaction temperature is
50~55 DEG C, 0.3~0.5MPa of reaction pressure；When solid content reaches 16%, side border ring adds remaining butadiene, residue 2-
Vinylpyridine, continues to react；
In step (2) and step (4), butadiene amounts to 55~75 mass parts, and 2- vinylpyridines amount to 5~20 mass
Part；
(5) when solid content reaches 38% in step (4), 0.5~1 mass parts molecular weight regulator is added, continues to react；
(6) when solid content reaches 42% in step (4), 0.05~1 mass parts terminator, finished product are added.
Preferably, the terminator be isopropylhydroxyla or, aromatic hydrocarbons base dithiocarboxylic acid or its salt.
Preferably, the diffusant be naphthalene sulfonic acids and formaldehyde condensation sodium salt or, alkyl naphthalene sulfonic acid and formaldehyde condensation
Sodium salt.
Preferably, the molecular weight regulator is processed by pre-emulsification or microemulsified, and solution used by pre-emulsification is quality
Percentage concentration is 10~15% soap water；Raw materials used and its mass fraction is as follows in microemulsified：
Compared with prior art, the beneficial effects of the invention are as follows：
1st, due to having used the emulsifying agent of especial manufacture so that the bond properties of product, mechanical stability, chemically stable
Property, foaming properties substantially improved, also improve performance of the latex in immersing glue process accordingly, reduce impregnation and produce
Rubber and buffings, extend the impregnation cycle.
2nd, due to having used the environment-friendly type molecular weight regulator processed by pre-emulsification or microemulsified, existing skill is overcome
Health hazard and environmental pollution problem of the butadiene styrene vinyl pyridine latex during production and use to workman in art.
3rd, as a result of isopropylhydroxyla or aromatic hydrocarbons base dithiocarboxylic acid or its salt, further improve environmental protection and ask
Topic, overcomes prior art and secondary amine is easily generated during cohesion and willowization, and in secondary amine and nitrating agent and air
The defect of reaction of nitrogen oxides nitroso compound.
4th, the dissolved oxygen in polymerization reaction system being removed by increasing oxygen scavenger so that polymerization process stabilization and
Quickly, the production cycle can be down to 15~19 hours by 23 hours of the prior art or so, improves production efficiency, saved
Production cost.
5th, the present invention can greatly improve the combination property of butylbenzene pyrrole latex and produce and the environmental pollution during use
Problem, is easy to popularization and application in industry.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment one
(1) to the second that the phosphoamide of 80 mass parts, the phosphoric acid of 3 mass parts, 5 mass parts are added in the soft water of 360 mass parts
The caustic alkali of ethylenediamine tetraacetic acid (EDTA) and 1 mass parts, 60min is stirred in the environment that temperature is 65 DEG C, and emulsifying agent is obtained；
(2) to adding 2.8 mass parts rosin soaps, 0.8 mass parts stearate soap, 0.5 mass parts sub- in 145 mass parts soft water
Methyl sodium dinaphthalenesulfonate, 0.08 mass parts oxygen scavenger, 0.5 mass parts OP-10,0.2 mass parts electrolyte K3PO4Walked with 2 mass parts
Suddenly emulsifying agent obtained in (1), is obtained the first mixed liquor；
(3) the first mixed liquor obtained in whipping step (2), 20 mass parts benzene second are added in the first mixed liquor to stirring
Alkene, 55 mass parts butadiene and 3 mass parts 2- vinylpyridines, are obtained the second mixed liquor；
(4) when the second mixed liquor of heating is to 50 DEG C, 0.4 mass parts K is added2S2O3Start reaction, reaction temperature is 55 DEG C,
Reaction pressure 0.5MPa；When solid content reaches 16%, side border ring adds 20 mass parts butadiene, 2 mass parts 2- vinyl
Pyridine, continues to react；
In step (2) and step (4), butadiene amounts to 75 mass parts, and 2- vinylpyridines amount to 5 mass parts；
(5) when solid content reaches 38% in step (4), 0.8 mass parts molecular weight regulator is added, continues to react；
(6) when solid content reaches 42% in step (4), 0.05 mass parts isopropylhydroxyla, finished product are added.
Molecular weight regulator used is the molecular weight regulator processed by pre-emulsification, pre-emulsification institute in above-mentioned steps (5)
It is the soap water that mass percentage concentration is 10% with solution, also soap water concentration can be adjusted to 13% and 15%.
Embodiment two
The present embodiment is with the difference of embodiment one：
In step (2), to adding 3.5 mass parts rosin soaps, 1.5 mass parts stearate soaps, 0.73 in 140 mass parts soft water
Mass parts sodium metnylene bis-naphthalene sulfonate, 0.05 mass parts oxygen scavenger, 1 mass parts OP-10,0.38 mass parts electrolyte K3PO4With 8
Emulsifying agent obtained in mass parts step (1), is obtained the first mixed liquor；
In step (3), the first mixed liquor obtained in whipping step (2) adds 25 mass in the first mixed liquor to stirring
Part styrene, 50 mass parts butadiene and 15 mass parts 2- vinylpyridines, are obtained the second mixed liquor；
In step (4), 0.45 mass parts K is added2S2O3Start reaction, reaction temperature is 53 DEG C, reaction pressure 0.4MPa；
When solid content reaches 16%, side border ring adds 5 mass parts butadiene, 5 mass parts 2- vinylpyridines, continues to react；
In step (2) and step (4), butadiene amounts to 55 mass parts, and 2- vinylpyridines amount to 20 mass parts；
In step (5), when solid content reaches 38% in step (4), 0.4 mass parts molecular weight regulator is added, continued
Reaction；
In step (6), when solid content reaches 42% in step (4), 0.08 mass parts isopropylhydroxyla is added, be obtained into
Product.
Embodiment three
This implementation is with the difference of embodiment one：
In step (2), to adding 2 mass parts rosin soaps, 1.2 mass parts stearate soaps, 0.62 matter in 150 mass parts soft water
Amount part methylene dinaphthalene disodium sulfonate, 1 mass parts oxygen scavenger, 0.8 mass parts OP-10,0.5 mass parts electrolyte K3PO4With 10 matter
Emulsifying agent obtained in amount part step (1), is obtained the first mixed liquor；
In step (3), the first mixed liquor obtained in whipping step (2) adds 18 mass in the first mixed liquor to stirring
Part styrene, 45 mass parts butadiene and 10 mass parts 2- vinylpyridines, are obtained the second mixed liquor；
In step (4), 0.45 mass parts K is added2S2O3Start reaction, reaction temperature is 53 DEG C, reaction pressure 0.4MPa；
When solid content reaches 16%, side border ring adds 20 mass parts butadiene, 2.5 mass parts 2- vinylpyridines, continues to react；
In step (2) and step (4), butadiene amounts to 65 mass parts, and 2- vinylpyridines amount to 12.5 mass parts；
In step (5), when solid content reaches 38% in step (4), 0.6 mass parts molecular weight regulator is added, continued
Reaction；
In step (6), when solid content reaches 42% in step (4), 1 mass parts sodium p styrene sulfonate is added, be obtained
Finished product.
Example IV
This implementation is with the difference of embodiment one：The specific preparation of emulsifying agent in step (1).To 384 mass parts
Soft water in add the phosphoamide of 73.5 mass parts, the phosphoric acid of 2.846 mass parts, the ethylenediamine tetra-acetic acid of 3.969 mass parts and
The caustic alkali of 0.763 mass parts, is obtained emulsifying agent.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 40 matter that microemulsified is raw materials used
Amount part soft water, 20 mass of surface activating agents, 0.5 mass parts KCl and 3 mass parts cosurfactants.
Embodiment five
The present embodiment is with the difference of embodiment two：The specific preparation of emulsifying agent in step (1).To 384 mass
Phosphoamide, the phosphoric acid of 2.846 mass parts, the ethylenediamine tetra-acetic acid of 3.969 mass parts of 73.5 mass parts are added in the soft water of part
With the caustic alkali of 0.763 mass parts, emulsifying agent is obtained.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 40 matter that microemulsified is raw materials used
Amount part soft water, 20 mass of surface activating agents, 0.5 mass parts KCl and 3 mass parts cosurfactants.
Embodiment six
The present embodiment is with the difference of embodiment three：The specific preparation of emulsifying agent in step (1).To 384 mass
Phosphoamide, the phosphoric acid of 2.846 mass parts, the ethylenediamine tetra-acetic acid of 3.969 mass parts of 73.5 mass parts are added in the soft water of part
With the caustic alkali of 0.763 mass parts, emulsifying agent is obtained.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 40 matter that microemulsified is raw materials used
Amount part soft water, 20 mass of surface activating agents, 0.5 mass parts KCl and 3 mass parts cosurfactants.
Embodiment seven
The present embodiment is with the difference of embodiment one：The specific preparation of emulsifying agent in step (1).To 395 mass
Phosphoamide, the phosphoric acid of 2.5 mass parts, the ethylenediamine tetra-acetic acid of 3 mass parts and 0.5 mass of 60 mass parts are added in the soft water of part
The caustic alkali of part, is obtained emulsifying agent.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 55 matter that microemulsified is raw materials used
Amount part soft water, 5 mass of surface activating agents, 0.4 mass parts KCl and 0.5 mass parts cosurfactant.
Embodiment eight
The present embodiment is with the difference of embodiment two：The specific preparation of emulsifying agent in step (1).To 395 mass
Phosphoamide, the phosphoric acid of 2.5 mass parts, the ethylenediamine tetra-acetic acid of 3 mass parts and 0.5 mass of 60 mass parts are added in the soft water of part
The caustic alkali of part, is obtained emulsifying agent.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 55 matter that microemulsified is raw materials used
Amount part soft water, 5 mass of surface activating agents, 0.4 mass parts KCl and 0.5 mass parts cosurfactant.
Embodiment nine
The present embodiment is with the difference of embodiment three：The specific preparation of emulsifying agent in step (1).To 395 mass
Phosphoamide, the phosphoric acid of 2.5 mass parts, the ethylenediamine tetra-acetic acid of 3 mass parts and 0.5 mass of 60 mass parts are added in the soft water of part
The caustic alkali of part, is obtained emulsifying agent.
Step (5) middle-molecular-weihydroxyethyl conditioning agent is processed through microemulsified, and it is 40 mass parts conditioning agents, 55 matter that microemulsified is raw materials used
Amount part soft water, 5 mass of surface activating agents, 0.4 mass parts KCl and 0.5 mass parts cosurfactant.
Electrolyte in above-described embodiment is not limited in K3PO4, other the general electrolysis that can also be selected in the industry
, from general raw material in industry, the concrete technology of microemulsified is also for matter, surfactant, cosurfactant and oxygen scavenger etc.
Common process, therefore in this not go into detail.
Butylbenzene pyrrole latex and prior art obtained in above-described embodiment, after testing, performance parameter contrast is as shown in the table：
The above, is only presently preferred embodiments of the present invention, is not the limitation for making other forms to the present invention, is appointed
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to technical spirit of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of butylbenzene pyrrole latex, it is characterised in that：Raw material and its mass fraction are as follows：
The emulsifying agent is made into by the following raw material by mass fraction：
2. according to the butylbenzene pyrrole latex described in claim 1, it is characterised in that：The emulsifying agent presses mass fraction by the following raw material
It is made into：
3. according to the butylbenzene pyrrole latex described in claim 1 or 2, it is characterised in that：The terminator be isopropylhydroxyla or,
Aromatic hydrocarbons base dithiocarboxylic acid or its salt.
4. according to the butylbenzene pyrrole latex described in claim 1 or 2, it is characterised in that：The diffusant is that naphthalene sulfonic acids contracts with formaldehyde
The sodium salt of conjunction or, the sodium salt of alkyl naphthalene sulfonic acid and formaldehyde condensation.
5. according to the butylbenzene pyrrole latex described in claim 1 or 2, it is characterised in that：The molecular weight regulator is by pre-emulsification
Treatment, solution used by pre-emulsification is the soap water that mass percentage concentration is 10~15%.
6. according to the butylbenzene pyrrole latex described in claim 1 or 2, it is characterised in that：The molecular weight regulator is by microemulsified
Treatment, raw materials used in microemulsified and its mass fraction is as follows：
7. a kind of preparation method of butylbenzene pyrrole latex, it is characterised in that：Comprise the following steps：
(1) to phosphoamide, the phosphoric acid of 2.5~3 mass parts, 3 that 60~80 mass parts are added in the soft water of 360~395 mass parts
The caustic alkali of the ethylenediamine tetra-acetic acid of~5 mass parts and 0.5~1 mass parts, 60min is stirred in the environment that temperature is 65 DEG C,
Emulsifying agent is obtained；
(2) to 2~4 mass parts rosin soaps of addition, 0.5~1.5 mass parts stearate soap, 0.5 in 140~150 mass parts soft water
~1 mass parts diffusant, 0.05~1 mass parts oxygen scavenger, 0~1 mass parts OP-10,0.05~0.5 mass parts electrolyte and
Emulsifying agent obtained in 1.3~10 mass parts steps (1), is obtained the first mixed liquor；
(3) the first mixed liquor obtained in whipping step (2), to 10~25 mass parts benzene second of addition in the first mixed liquor of stirring
Alkene, 45~55 mass parts butadiene and 3~15 mass parts 2- vinylpyridines, are obtained the second mixed liquor；
(4) heating the second mixed liquor to 50 DEG C when, add 0.3~0.5 mass parts initiator start reaction, reaction temperature be 50~
55 DEG C, 0.3~0.5MPa of reaction pressure；When solid content reaches 16%, side border ring adds remaining butadiene, residue 2- ethene
Yl pyridines, continue to react；
In step (2) and step (4), butadiene amounts to 55~75 mass parts, and 2- vinylpyridines amount to 5~20 mass parts；
(5) when solid content reaches 38% in step (4), 0.5~1 mass parts molecular weight regulator is added, continues to react；
(6) when solid content reaches 42% in step (4), 0.05~1 mass parts terminator, finished product are added.
8. according to the preparation method of the butylbenzene pyrrole latex described in claim 7, it is characterised in that：The terminator is isopropyl hydroxyl
Amine or, aromatic hydrocarbons base dithiocarboxylic acid or its salt.
9. according to the butylbenzene pyrrole latex described in claim 7, it is characterised in that：The diffusant is naphthalene sulfonic acids and formaldehyde condensation
Sodium salt or, the sodium salt of alkyl naphthalene sulfonic acid and formaldehyde condensation.
10. according to the butylbenzene pyrrole latex described in claim 7, it is characterised in that：The molecular weight regulator by pre-emulsification or
The treatment of person's microemulsified, solution used by pre-emulsification is the soap water that mass percentage concentration is 10~15%；In microemulsified it is raw materials used and
Its mass fraction is as follows：
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922529A (en) * | 2019-11-21 | 2020-03-27 | 淄博奥固特科技有限公司 | Pyridine styrene butadiene rubber latex and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922529A (en) * | 2019-11-21 | 2020-03-27 | 淄博奥固特科技有限公司 | Pyridine styrene butadiene rubber latex and preparation method thereof |
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