CN107216424B - A kind of polymerization of carboxylic styrene butadiene latex - Google Patents
A kind of polymerization of carboxylic styrene butadiene latex Download PDFInfo
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- CN107216424B CN107216424B CN201710611936.1A CN201710611936A CN107216424B CN 107216424 B CN107216424 B CN 107216424B CN 201710611936 A CN201710611936 A CN 201710611936A CN 107216424 B CN107216424 B CN 107216424B
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- reaction vessel
- polymerization
- styrene butadiene
- carboxylic styrene
- butadiene latex
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 94
- 239000004816 latex Substances 0.000 title claims abstract description 86
- 229920000126 latex Polymers 0.000 title claims abstract description 86
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 63
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 63
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 52
- 239000003999 initiator Substances 0.000 claims description 52
- 239000000178 monomer Substances 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000007373 indentation Methods 0.000 claims description 14
- -1 alkyl phenol Chemical compound 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 239000000344 soap Substances 0.000 claims description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000011276 wood tar Substances 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 125000005313 fatty acid group Chemical group 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 13
- 239000003292 glue Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QVGURAHKOZSVQR-UHFFFAOYSA-N 3-cyanopentanoic acid Chemical compound CCC(C#N)CC(O)=O QVGURAHKOZSVQR-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical group CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003703 image analysis method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C08F236/06—Butadiene
-
- 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
-
- 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
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of polymerizations of carboxylic styrene butadiene latex, its polymerization process carries out respectively in two polymeric kettles, main reaction carries out in the first reaction vessel, particle diameter increases and molecule is stablized growth course and carried out in the second reaction vessel, second reaction vessel can keep temperature more lower than polymerization temperature, on the one hand make branching and be crosslinked the reduction of these rate of side reactions, thereby reduce the probability of glue residue generation, the mobility and stability of latex improve, improve latex quality, increase added value of product, on the other hand the second reaction vessel, which does not have temperature, reduces raised process again, reduce energy consumption, improve production efficiency.In addition, two sections of polymerization techniques of carboxylic styrene butadiene latex of the present invention can reduce emulsifier 30%-40%, production cost can be not only reduced, but also residual emulsifiers content in glue can be reduced, be conducive to improve latex quality and processing performance.
Description
Technical field
The present invention relates to a kind of polymerizations of carboxylic styrene butadiene latex, belong to technical field of emulsion polymerization.
Background technique
Emulsion polymerization is monomer by emulsifier and mechanical stirring, makes monomer be dispersed in water to form lotion, adds and draw
It sends out agent to cause, generates emulsion particle isolated each other by micella mechanism or oligomer mechanism, and it is poly- to carry out free radical addition wherein
It closes or ion addition polymerize to produce a kind of polymerization of high polymer.Recently as the development of emulsion polymerization technology, lotion
Polymerization process has increasing importance to the production of commercial polymer, in many polymer such as synthetic rubber, synthesis modeling
Material, synthetic resin coating, adhesive, flocculant, impact copolymer production in, emulsion polymerization have become main method it
One.
Carboxylic styrene butadiene latex is to add a small amount of carboxylic acid and other auxiliary agents with butadiene, styrene, is generated by emulsion polymerization
Copolymer is a kind of milky aqueous dispersion with bluish violet gloss.Carboxylic styrene butadiene latex has conjunctiva intensity and bonding force
Higher, stability, mobility are all good, and loading is big, and moldability is good, mechanical, chemistry is excellent with freeze-thaw stability, with pigment, fill out
Expect the features such as compatibility is good, purposes includes that papermaking, carpet, weaving, ornaments (charcoal carving and plastic flower), architectural decoration (change
Property cement mortar, timber glue, modified pitch, oil drilling) etc..
The emulsion polymerization process of carboxylic styrene butadiene latex carries out in same kettle in prior art, when reaction reaches holding stage
When, monomer droplet disappears substantially, and residual monomer largely swells in emulsion particle or soluble in water, the branching of macromolecular chain at this time and
Crosslinking aggravation, easily generates gel in this stage, and bulk gels are precipitated as glue residue and from lotion, and yield is brought to reduce,
Emulsifier increases, and product glue residue content is high, and environmental treatment burden increases, and the particle diameter distribution of emulsion particle broadens, system colloid
Mobility and stability decline etc. a series of adverse effects；In addition, in existing technique, one kettle latex of every production has anti-
Kettle temperature degree is answered to reduce raised process again, the energy consumption of generation is high.
Currently, research of the countries in the world all in terms of carrying out carboxylic styrene butadiene latex polymerization technique, in the hope of improving existing product
Some shortcomings, realize the multifunction of carboxylic styrene butadiene latex.
Summary of the invention
The technical problem to be solved by the present invention is to overcome emulsifier existing in the prior art high, product glue residue
Content is high, the non-uniform technical problem of molecular weight, provides that a kind of emulsifier is low, and product impurity content is few, and molecular weight is more equal
The polymerization of even carboxylic styrene butadiene latex.
The technical solution adopted by the present invention to solve the technical problems is:
The present invention provides a kind of polymerization of carboxylic styrene butadiene latex, and the polymerization process of this method is distinguished in two polymeric kettles
It carries out, main reaction carries out in the first reaction vessel, and particle diameter increases and molecule stablizes growth course in the second reaction
It is carried out in container, the specific process is as follows:
Prepare raw material: in terms of mass fraction, comprising: 100 parts of polymerized monomers, 0.9-1.05 parts of emulsifiers, 50-180 parts go
Ionized water, 0.3-0.9 part molecular weight regulator, 0.3-1.5 parts of initiators；
Polymerization process:
After (1) first reaction vessel vacuumizes, by the deionized water of 70-80%, 20- in the composition of raw materials stirred evenly
The mixed material of the molecular weight regulator of 40% polymerized monomer in addition to butadiene, the emulsifier of 20-40% and 20-40% is thrown
Enter the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, and the butadiene of 15-25% is pressed into first with nitrogen
In reaction vessel；
(3) material in the first reaction vessel is heated, 65-70 DEG C is increased to temperature, the initiator of 25-30% is added,
Stop heating；
(4) remaining deionized water, polymerized monomer, emulsification are added by several times or in a manner of being added dropwise into the first reaction vessel
Agent, initiator and molecular weight regulator make the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the gas pressure of the material in the first reaction vessel
Enter the second reaction vessel；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined value, be added eventually
Only agent adjusts pH value, completes polymerization.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the step (3) is middle to heat in the first reaction vessel
The method of material is to be passed through steam into the first reaction vessel.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the intake of water vapour described in the step (3)
For 2000-3000kg/h, the initiator is added in 0.2-0.3h and finishes, and keeps water vapour to be passed through during the addition process.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the gas in the step (5) are water vapour and nitrogen
The mixed gas of gas, wherein water vapour and nitrogen volume ratio are 0.1-0.2:1.
Further, the polymerization of carboxylic styrene butadiene latex of the invention, the temperature of the water vapour are 145-175 DEG C.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, it is remaining deionized water in the step (4), poly-
Close monomer, emulsifier, initiator and the molecular weight regulator investment in 2-4 hours.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the emulsifier are fatty acid soaps, disproportionated rosin acid
One of soap, alkyl sulfate, alkyl phenol polyoxyethylene ether and sorbitan fatty acid ester are a variety of.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the initiator are ammonium persulfate, benzoyl peroxide first
One of acyl, peracetic acid, azodiisobutyronitrile, azo dicyano valeric acid and azo dicyclohexyl formonitrile HCN are more
Kind.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the molecular weight regulator are tertiary dodecyl sulphur
Alcohol.
Preferably, the polymerization of carboxylic styrene butadiene latex of the invention, the terminator are hydroquinone, to tert-butyl o
One kind of benzenediol, wood tar.
The beneficial effects of the present invention are:
(1) polymerization of carboxylic styrene butadiene latex of the present invention, polymerization process carries out respectively in two polymeric kettles, main
Reaction carries out in the first reaction vessel, and particle diameter increases and molecule is stablized growth course and carried out in the second reaction vessel,
Second reaction vessel can keep temperature more lower than polymerization temperature, so that branching and crosslinking these rate of side reactions reduction, into
And the probability of glue residue generation is reduced, so that the mobility of latex and stability improve, latex quality is improved, it is attached to increase product
It is value added.
(2) two sections of polymerization techniques of carboxylic styrene butadiene latex of the present invention can reduce emulsifier 30%-40%, can both reduce
Production cost, and residual emulsifiers content in glue can be reduced, be conducive to improve latex quality and processing performance.
(3) in existing technique, one kettle latex of every production has temperature of reaction kettle to reduce raised process again, and this hair
The second reaction vessel can remain same temperature in the polymerization of bright carboxylic styrene butadiene latex, just further reduced in this way
Energy consumption improves production efficiency.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, now illustrate of the invention specific
Embodiment.
Embodiment 1
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 0.95 part of emulsifier, 50 parts of deionized waters, 0.3 part of molecular weight regulator,
0.3 part of initiator；
The polymerized monomer composition are as follows: 40wt% butadiene, 55wt% styrene, 5wt% acrylic acid；The emulsifier is
Fatty acid soaps；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is ammonium persulfate；
Polymerization the following steps are included:
(1) polymerized monomer by 80% deionized water, 20% in composition of raw materials in addition to butadiene, 40% emulsifier
Molecular weight regulator with 40% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N215% the first reaction of butadiene indentation is held
In device；
(3) it is 145 DEG C of water vapours that the intake into the first reaction vessel with 3000kg/h, which is passed through temperature, by temperature of charge
After being increased to 69 DEG C, 25% initiator is added, stops being passed through for steam；
(4) remaining deionized water, polymerized monomer, emulsifier, initiator is added by several times into the first reaction vessel and divides
Son amount regulator, makes the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, be added to benzene
Diphenol completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.1, and the temperature of the water vapour is 175 DEG C, gas can be made to be maintained at suitable temperature in this way
Degree, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation, have
It is carried out conducive to stablizing for polymerization, is conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator is added in 0.25h
Finish, and during the addition process keep water vapour be passed through, the remaining deionized water, polymerized monomer, emulsifier, initiator and
Molecular weight regulator is put into 3 hours, rate of polymerization can be made to slow down in this way, prevents the even cruelly poly- danger of blunt temperature
Danger guarantees production safety.
Embodiment 2
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 1 part of emulsifier, 180 parts of deionized waters, 0.9 part of molecular weight regulator, 1.5
Part initiator；
The polymerized monomer composition are as follows: 45wt% butadiene, 40wt% styrene, 15wt% acrylic acid；The emulsifier
For disproportionated rosin acid soap；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is benzoyl peroxide；
Polymerization the following steps are included:
(1) polymerized monomer by 70% deionized water, 40% in composition of raw materials in addition to butadiene, 20% emulsifier
Molecular weight regulator with 20% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N225% the first reaction of butadiene indentation is held
In device；
(3) it after the temperature of charge in the first reaction vessel being increased to 67 DEG C by the way of collet heating, adds
30% initiator；
(4) remaining deionized water, polymerized monomer, emulsifier, initiation is added in a manner of being added dropwise into the first reaction vessel
Agent and molecular weight regulator make the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, be added to uncle
Butyl-catechol completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.15:1, and the temperature of the water vapour is 165 DEG C, gas can be made to be maintained at suitable in this way
Temperature, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation,
Be conducive to stablizing for polymerization to carry out, be conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator has been added in 0.2h
To finish, the remaining deionized water, polymerized monomer, emulsifier, initiator and molecular weight regulator are put into 2.5 hours, this
Sample can be such that rate of polymerization slows down, and prevent the even cruelly poly- danger of blunt temperature, guarantee production safety.
Embodiment 3
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 1.05 parts of emulsifiers, 90 parts of deionized waters, 0.5 part of molecular weight regulator,
0.5 part of initiator；
The polymerized monomer composition are as follows: 40wt% butadiene, 45wt% styrene, 15wt% acrylic acid；The emulsifier
For weight ratio be 1:1 alkyl sulfate and alkyl phenol polyoxyethylene ether；The molecular weight regulator is tert-dodecylmercaotan,
The initiator is peracetic acid；
Polymerization the following steps are included:
(1) polymerized monomer by 75% deionized water, 30% in composition of raw materials in addition to butadiene, 30% emulsifier
Molecular weight regulator with 30% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N220% the first reaction of butadiene indentation is held
In device；
(3) it is 160 DEG C of water vapours that the intake into the first reaction vessel with 2400kg/h, which is passed through temperature, by temperature of charge
After being increased to 66 DEG C, 26% initiator is added, stops being passed through for steam；
(4) remaining deionized water, polymerized monomer, emulsifier, initiator is added by several times into the first reaction vessel and divides
Son amount regulator, makes the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, be added to uncle
Butyl-catechol completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.2:1, and the temperature of the water vapour is 155 DEG C, gas can be made to be maintained at suitable in this way
Temperature, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation,
Be conducive to stablizing for polymerization to carry out, be conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator has been added in 0.3h
Finish, and during the addition process keep water vapour be passed through, the remaining deionized water, polymerized monomer, emulsifier, initiator and point
Son amount regulator is put into 4 hours, rate of polymerization can be made to slow down in this way, prevents the even cruelly poly- danger of blunt temperature,
Guarantee production safety.
Embodiment 4
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 0.9 part of emulsifier, 160 parts of deionized waters, 0.6 part of molecular weight regulator,
0.8 part of initiator；
The polymerized monomer composition are as follows: 50wt% butadiene, 35wt% styrene, 15wt% acrylic acid；The emulsifier
For sorbitan fatty acid ester；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is two isobutyl of azo
Nitrile；
Polymerization the following steps are included:
(1) polymerized monomer by 72% deionized water, 25% in composition of raw materials in addition to butadiene, 25% emulsifier
Molecular weight regulator with 30% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N220% the first reaction of butadiene indentation is held
In device；
(3) it after the temperature of charge in the first reaction vessel being increased to 70 DEG C by the way of collet heating, adds
30% initiator adds 27% initiator；
(4) remaining deionized water, polymerized monomer, emulsifier, initiation is added in a manner of being added dropwise into the first reaction vessel
Agent and molecular weight regulator make the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, it is burnt that wood is added
Oil completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.18:1, and the temperature of the water vapour is 165 DEG C, gas can be made to be maintained at suitable in this way
Temperature, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation,
Be conducive to stablizing for polymerization to carry out, be conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator is added in 0.28h
It finishing, the remaining deionized water, polymerized monomer, emulsifier, initiator and molecular weight regulator are put into 2 hours, this
Sample can be such that rate of polymerization slows down, and prevent the even cruelly poly- danger of blunt temperature, guarantee production safety.
Embodiment 5
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 1 part of emulsifier, 110 parts of deionized waters, 0.7 part of molecular weight regulator, 1 part
Initiator；
The polymerized monomer composition are as follows: 30wt% butadiene, 35wt% styrene, 35wt% acrylic acid；The emulsifier
For fatty acid soaps；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is the azo two that mass fraction is 2:3
Cyanopentanoic acid and azo dicyclohexyl formonitrile HCN；
Polymerization the following steps are included:
(1) polymerized monomer by 73% deionized water, 30% in composition of raw materials in addition to butadiene, 30% emulsifier
Molecular weight regulator with 30% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N220% the first reaction of butadiene indentation is held
In device；
(3) it is 175 DEG C of water vapours that the intake into the first reaction vessel with 2000kg/h, which is passed through temperature, by temperature of charge
After being increased to 65 DEG C, 28% initiator is added, stops being passed through for steam；
(4) remaining deionized water, polymerized monomer, emulsifier, initiator is added by several times into the first reaction vessel and divides
Son amount regulator, makes the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, be added to benzene
Diphenol completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.15:1, and the temperature of the water vapour is 170 DEG C, gas can be made to be maintained at suitable in this way
Temperature, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation,
Be conducive to stablizing for polymerization to carry out, be conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator is added in 0.25h
Finish, and during the addition process keep water vapour be passed through, the remaining deionized water, polymerized monomer, emulsifier, initiator and
Molecular weight regulator is put into 3 hours, rate of polymerization can be made to slow down in this way, prevents the even cruelly poly- danger of blunt temperature
Danger guarantees production safety.
Embodiment 6
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 1 part of emulsifier, 70 parts of deionized waters, 0.8 part of molecular weight regulator, 1.2 parts
Initiator；
The polymerized monomer composition are as follows: 40wt% butadiene, 40wt% styrene, 20wt% acrylic acid；The emulsifier
For fatty acid soaps；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is ammonium persulfate；
Polymerization the following steps are included:
(1) polymerized monomer by 80% deionized water, 35% in composition of raw materials in addition to butadiene, 35% emulsifier
Molecular weight regulator with 35% is first mixed and stirred in mixing kettle uniform mixed material, vacuumizes to the first reaction vessel
Afterwards, mixed material is put into the first reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, uses N220% the first reaction of butadiene indentation is held
In device；
(3) it is 170 DEG C of water vapours that the intake into the first reaction vessel with 2700kg/h, which is passed through temperature, by temperature of charge
After being increased to 68 DEG C, 30% initiator is added, stops being passed through for steam；
(4) it is passed through cooling water to the inner coil pipe of the first reaction vessel, remaining go is added by several times into the first reaction vessel
Ionized water, polymerized monomer, emulsifier, initiator and molecular weight regulator make the temperature in the first reaction vessel be maintained at 80-90
℃；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, by the material water vapour in the first reaction vessel
The second reaction vessel is pressed into the mixed gas of nitrogen；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined, it is burnt that wood is added
Oil completes polymerization.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, the mixed gas of water vapour and nitrogen described in step (5)
Middle water vapour and nitrogen ratios are 0.12, and the temperature of the water vapour is 160 DEG C, gas can be made to be maintained at suitable temperature in this way
Degree, so that it is smaller containing low molecular small grain size latex temperature fluctuation from the first reaction vessel the second reaction vessel of indentation, have
It is carried out conducive to stablizing for polymerization, is conducive to improve latex quality.
The polymerization of the carboxylic styrene butadiene latex of the present embodiment, in step (3), the initiator is added in 0.25h
Finish, and during the addition process keep water vapour be passed through, the remaining deionized water, polymerized monomer, emulsifier, initiator and
Molecular weight regulator is put into 3 hours, rate of polymerization can be made to slow down in this way, prevents the even cruelly poly- danger of blunt temperature
Danger guarantees production safety.
Comparative example 1
The present embodiment provides a kind of polymerizations of carboxylic styrene butadiene latex, the specific process is as follows:
Prepare raw material: 100 parts of polymerized monomers, 1.5 parts of emulsifiers, 70 parts of deionized waters, 0.8 part of molecular weight regulator, 1.2
Part initiator；
The polymerized monomer composition are as follows: 40wt% butadiene, 40wt% styrene, 20wt% acrylic acid；The emulsifier
For fatty acid soaps；The molecular weight regulator is tert-dodecylmercaotan, and the initiator is ammonium persulfate；
Polymerization the following steps are included:
(1) polymerized monomer by 80% deionized water, 35% in composition of raw materials in addition to butadiene, 35% emulsifier
Molecular weight regulator with 35% is first mixed and stirred in mixing kettle uniform mixed material, after reaction vessel vacuumizes,
Mixed material is put into reaction vessel；
(2) air is displaced with nitrogen in the reaction vessel, uses N2It will be in 20% butadiene indentation polymeric kettle；
(3) it is 170 DEG C of water vapours that the intake into reaction vessel with 2700kg/h, which is passed through temperature, and temperature of charge is increased
To after 68 DEG C, 30% initiator is added, initiator is added in 0.25h and finishes, and stops being passed through for steam；
(4) remaining deionized water, polymerized monomer, emulsifier, initiator and molecular-weight adjusting is added by several times in 3 hours
Agent makes the temperature in reaction vessel be maintained at 80-90 DEG C in reaction vessel, and pressure is maintained at 0.8Mpa hereinafter, rate to be transformed
After reaching predetermined, wood tar is added, completes polymerization.
Effect example
In order to more clearly represent the raw material dosage and properties of product obtained of 6 embodiments and 1 comparative example, under
It lists in a tabular form in face.
Table 1 is the composition of raw materials of carboxylic styrene butadiene latex
Table 2 is measurement after the obtained latex of the carboxylic styrene butadiene latex polymerization of embodiment 1-6 and comparative example 1 is sampled
Average grain diameter, particle diameter distribution
Note: average grain diameter and particle diameter distribution are measured using transmission electron microscopy image analysis method；
Viscosity is measured using NDJ-1 type rotational viscometer.
It can be seen from Table 1 that producing same amount of carboxylic styrene butadiene latex, embodiment 1-6 is used compared with comparative example
The amount of emulsifier reduces 30-40%, and especially embodiment 6 is compared with comparative example 1, in addition to the amount of emulsifier used reduces 33%,
Other composition of raw materials are identical, it is seen that the polymerization of carboxylic styrene butadiene latex of the invention can substantially reduce the use of emulsifier
Amount reduces production cost.
It can be seen from Table 2 that the preparation-obtained carboxylic styrene butadiene latex of embodiment 1-6, compared with comparative example 1, partial size divides
Cloth is more concentrated, and the percentage that the carboxylic styrene butadiene latex amounts of particles that particle size is 120-140nm accounts for total particle quantity is big
In 79%, embodiment 6 is that particle size is distributed the most preferred embodiment most concentrated, and can also be seen that the present invention by Electronic Speculum result
The residual impurity content of preparation-obtained carboxylic styrene butadiene latex is few, and mobility and stability are high, and latex quality is good.
In addition, the second reaction vessel can be protected always in the polymerization of carboxylic styrene butadiene latex in 1-6 of the embodiment of the present invention
Hold same temperature, and the temperature is lower than polymerization temperature, and the every production kettle latex of comparative example 1, there is temperature of reaction kettle reduction again
Raised process, it is seen then that the polymerization of carboxylic styrene butadiene latex of the present invention can further decrease energy consumption, improve production effect
Rate.
It should be pointed out that polymerization of the invention is equally applicable to the polymerization of styrene-butadiene latex.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of polymerization of carboxylic styrene butadiene latex, which is characterized in that the composition of raw materials and polymerization process of the method are as follows:
Composition of raw materials: in terms of mass fraction, comprising: 100 parts of polymerized monomers, 0.9-1.05 parts of emulsifiers, 50-180 parts of deionizations
Water, 0.3-0.9 part molecular weight regulator, 0.3-1.5 parts of initiators；
Polymerization process:
After (1) first reaction vessel vacuumizes, the deionized water of 70-80%, 20-40% in the composition of raw materials stirred evenly are removed
The mixed material investment first of the molecular weight regulator of the emulsifier and 20-40% of polymerized monomer, 20-40% other than butadiene
Reaction vessel；
(2) air is displaced with nitrogen in the first reaction vessel, and is reacted the butadiene indentation first of 15-25% with nitrogen
In container；
(3) material in the first reaction vessel is heated, 65-70 DEG C is increased to temperature, the initiator of 25-30% is added, is stopped
Heating；
(4) into the first reaction vessel by several times or be added in a manner of being added dropwise remaining deionized water, polymerized monomer, emulsifier,
Initiator and molecular weight regulator make the temperature in the first reaction vessel be maintained at 80-90 DEG C；
(5) to pressure reduction in the first reaction vessel to 1atm hereinafter, the gas of the material in the first reaction vessel is pressed into the
Two reaction vessels；
(6) temperature in the second reaction vessel is maintained at 70-80 DEG C, after rate to be transformed reaches predetermined value, terminator is added,
PH value is adjusted, polymerization is completed.
2. the polymerization of carboxylic styrene butadiene latex according to claim 1, which is characterized in that lead into the first reaction vessel
Enter steam with heated material.
3. the polymerization of carboxylic styrene butadiene latex according to claim 2, which is characterized in that steam described in step (3)
Intake be 2000-3000kg/h, the initiator is added in 0.2-0.3h and finishes, and keeps during the addition process
Steam is passed through.
4. the polymerization of carboxylic styrene butadiene latex according to claim 2 or 3, which is characterized in that the gas in step (5)
For the mixed gas of water vapour and nitrogen, wherein steam and nitrogen volume ratio are 0.1-0.2:1.
5. the polymerization of carboxylic styrene butadiene latex according to claim 2 or 3, which is characterized in that the temperature of the steam
It is 145-175 DEG C.
6. the polymerization of carboxylic styrene butadiene latex according to claim 5, which is characterized in that remaining in step (4) to go
Ionized water, polymerized monomer, emulsifier, initiator and the molecular weight regulator investment in 2-4 hours.
7. the polymerization of carboxylic styrene butadiene latex according to claim 6, which is characterized in that the emulsifier is fatty acid
One of soap, disproportionated rosin acid soap, alkyl sulfate, alkyl phenol polyoxyethylene ether and sorbitan fatty acid ester are more
Kind.
8. the polymerization of carboxylic styrene butadiene latex according to claim 6, which is characterized in that the initiator is persulfuric acid
Ammonium, benzoyl peroxide, peracetic acid, azodiisobutyronitrile, azo dicyano valeric acid and azo dicyclohexyl formonitrile HCN
One of or it is a variety of.
9. the polymerization of carboxylic styrene butadiene latex according to claim 6, which is characterized in that the molecular weight regulator is
Tert-dodecylmercaotan.
10. the polymerization of carboxylic styrene butadiene latex according to claim 6, which is characterized in that the terminator is to benzene
One kind of diphenol, p-tert-Butylcatechol, wood tar.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139413A (en) * | 2006-09-05 | 2008-03-12 | 中国石油天然气集团公司 | Method for synthesizing carboxyl butadiene-styrene latex used for cement group water-proofing material |
| CN102786620A (en) * | 2012-07-18 | 2012-11-21 | 杭州蓝诚实业有限公司 | Small-particle-size carboxylic styrene-butadiene latex and its preparation method |
| CN104592447A (en) * | 2015-01-12 | 2015-05-06 | 浙江天晨胶业股份有限公司 | Preparation method of carboxylic butadiene-styrene latex |
| CN104628953A (en) * | 2015-01-12 | 2015-05-20 | 浙江天晨胶业股份有限公司 | Carboxylated styrene-butadiene latex |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139413A (en) * | 2006-09-05 | 2008-03-12 | 中国石油天然气集团公司 | Method for synthesizing carboxyl butadiene-styrene latex used for cement group water-proofing material |
| CN102786620A (en) * | 2012-07-18 | 2012-11-21 | 杭州蓝诚实业有限公司 | Small-particle-size carboxylic styrene-butadiene latex and its preparation method |
| CN104592447A (en) * | 2015-01-12 | 2015-05-06 | 浙江天晨胶业股份有限公司 | Preparation method of carboxylic butadiene-styrene latex |
| CN104628953A (en) * | 2015-01-12 | 2015-05-20 | 浙江天晨胶业股份有限公司 | Carboxylated styrene-butadiene latex |
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