CN1272503A - Preparation method of small grainsize polybutadiene latex - Google Patents
Preparation method of small grainsize polybutadiene latex Download PDFInfo
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- CN1272503A CN1272503A CN 00107134 CN00107134A CN1272503A CN 1272503 A CN1272503 A CN 1272503A CN 00107134 CN00107134 CN 00107134 CN 00107134 A CN00107134 A CN 00107134A CN 1272503 A CN1272503 A CN 1272503A
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- sodium
- latex
- polybutadiene
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- butadiene
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- 229920000126 latex Polymers 0.000 title claims abstract description 34
- 239000004816 latex Substances 0.000 title claims abstract description 33
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 26
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- -1 alkane sulfonate Chemical class 0.000 claims abstract description 4
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 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 abstract description 3
- 229940096992 potassium oleate Drugs 0.000 claims abstract description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims abstract description 3
- 239000000344 soap Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 9
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- 208000006558 Dental Calculus Diseases 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- PFMVLFSAAABWQD-UHFFFAOYSA-M potassium;octadecyl sulfate Chemical compound [K+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O PFMVLFSAAABWQD-UHFFFAOYSA-M 0.000 claims description 2
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 2
- 239000011697 sodium iodate Substances 0.000 claims description 2
- 235000015281 sodium iodate Nutrition 0.000 claims description 2
- 229940032753 sodium iodate Drugs 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 150000008051 alkyl sulfates Chemical class 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 230000009466 transformation Effects 0.000 description 11
- 239000004159 Potassium persulphate Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 235000019394 potassium persulphate Nutrition 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DNPFOADIPJWGQH-UHFFFAOYSA-N octan-3-yl prop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C=C DNPFOADIPJWGQH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A preparation method of small graininess polybutadiene latex for ABS is mainly characterized by that under the action of initiating agent, emulsifying agent, alkali, chain transfer agent and electrolyte, the butadiene can be emulsion-polymerized to obtain the invented product. By adopting compounded emulsifying agent formed from disporportionated rosin acid soap or potassium oleate and alkyl sulfate or alkane sulfonate, the said invention can utilize one-step batch to prepare small graininess polybutadiene latex with 80-120 nm within 8-11hr.
Description
The present invention relates to a kind of emulsion polymerisation process of polybutadiene latex.
Restriction acrylonitrile-butadiene-styrene copolymer (the following ABS that all is called for short) produces efficiently that key factor is that grafting is long with the synthesis cycle of big particle diameter polybutadiene latex, so the synthesis cycle that shortens big particle diameter polybutadiene latex just becomes people's research emphasis.Earlier synthetic latex of polybutadiene in small grain size carries out agglomeration with agglomerant then, and obtaining big particle diameter polybutadiene latex within a short period of time is comparatively advanced in the world at present technology.Wherein the synthetic method of latex of polybutadiene in small grain size mainly contains: (A) add comonomer in polymerization process, as vinyl cyanide, react under 70 ℃ reinforced back, continue to make it after 12 hours cooling, reach the reaction termination, can obtain transformation efficiency more than 98%, be 41% admittedly contain, and median size is the polymkeric substance (CA 123290A) of 120nm; (B) in polymerization process, add comonomer,, once feed intake, reacted 50 hours down, can obtain the polybutadiene latex that median size is 90nm (EP346853) at 60 ℃ as vinylbenzene; (C) in polymerization process, add comonomer, as acrylate, i.e. acrylate C preferably in the butadiene-acrylic acid ester monomer mixture
1-8Alcohol is derived and next acrylate, for example ethyl propenoate, butyl acrylate or vinylformic acid (ethyl hexyl) ester, 30-90 ℃ of following polymerization, just can obtain median size about 20 hours is about 100nm, and monomer conversion reaches 96% polymer latex (EP 062901); (D) add linking agent in polymerization process, as ethylene glycol dimethacrylate, 65 ℃ of down reactions 12 hours, can obtain transformation efficiency is 94%, and solid content is about 40%, and median size is the rubber latex of 100nm; (E) under certain polymerization degree, add initiator, promptly behind 60 ℃ of following initiated polymerizations, transformation efficiency reaches 65%, and when polymerization temperature is elevated to 65 ℃, add initiator and deionized water, polymerization is after 26 hours, and can obtain median size is 185nm, admittedly contain is 50.4%, and transformation efficiency is 88% polybutadiene latex (EP271684); (F) add the monomer divinyl in batches, at first in 10 absolute pressures of ability, add water in the withstand voltage still of steel of band leg and leaf agitator, use nitrogen replacement, and be heated to 65 ℃, then 0.5 part of tert-dodecyl mercaptan and 16.6 parts of divinylic monomers are added in the still, begin to add 83.3 parts of monomer divinyl in to 5 hours in back 1 hour in polyreaction, and back 5 hours of the reinforced end of divinyl, just together with above-mentioned altogether 11 hours the time, add 0.5 part of tert-dodecyl mercaptan once more, after duration of the reaction amounts to 19 hours, just can obtain monomer conversion is 96%, solid content is 39.2%, and median size is the polybutadiene latex of 100～150nm.In above-mentioned synthetic method, not in polymerization process, to add comonomer, when being aggregated to certain transformation efficiency, add initiator exactly, troublesome poeration, the cost height, and also generated time is still longer.
The object of the present invention is to provide the method for a kind of quick ABS of preparation with latex of polybutadiene in small grain size, in polymerization process, do not add comonomer, and reaction monomers once feeds intake, and need not to add, and just can make the latex of polybutadiene in small grain size that particle diameter is 80～120nm in 8～11 hours.
ABS of the present invention is raw material with the divinyl with latex of polybutadiene in small grain size, and emulsion is polymerized under water-soluble thermal decomposition initiating, anionic compound emulsifying agent, highly basic, chain-transfer agent, electrolytical effect.Suitable water-soluble thermal decomposition initiating of the present invention comprises Potassium Persulphate, ammonium persulphate, and its consumption is 0.2～0.5 part (the present invention serves as to calculate benchmark with divinyl consumption 100 weight parts all except that particularly pointing out).Suitable anionic compound emulsifying agent is that disproportionated rosin acid soap or potassium oleate and alkyl-sulphate or alkylsulfonate carry out composite, its composite ratio is 10～30, and its consumption is 2～6 parts, and alkyl-sulphate commonly used has sodium lauryl sulphate, potassium octadecyl sulfate etc.; Alkylsulfonate commonly used has Sodium dodecylbenzene sulfonate, sodium laurylsulfonate etc.Can add highly basic in the emulsion polymerization systems of the present invention the pH value of latex is regulated, make the pH value of latex be adjusted to 8～11, suitable highly basic has potassium hydroxide, sodium hydroxide, and its consumption is 0.04～0.08 part.Molecular weight and distribution thereof that the present invention also adopts chain-transfer agent to come telomerized polymer, available chain-transfer agent have tert-dodecyl mercaptan, acetic acid just-lauryl mercaptan ester, ethylene glycol, neopentanoic acid, dithiazole thioether etc., its consumption is 0.1～0.5 part.It is considered herein that in the emulsion polymerization systems an amount of ionogen of adding can play improves polymerization rate, increases STABILITY OF POLYMER EMULSION and improves the effects such as flowability of polymer emulsion, available ionogen has Repone K, sodium-chlor, trisodium phosphate, sodium phosphite, sodium bicarbonate, sal enixum, vitriolate of tartar, Sodium Tetraborate, salt of wormwood, sodium iodate, sodium bromate etc., they can use separately, also can compositely use, its consumption is 1-6 part.The consumption of deionized water is 1～2.5 times of monomer divinyl consumption in the emulsion polymerization systems of the present invention.At first various auxiliary agents are mixed with solution with the part deionized water, then remaining deionized water and the various compounding agent solutions that prepare are joined in the withstand voltage polymeric kettle, replace with nitrogen, and the back that is evacuated adds the monomer divinyl, open this moment and stir, begin after ten minutes to heat up, in 1--1.5 hour, be warming up to temperature of reaction 60-70 ℃.React after 8-11 hour, transformation efficiency reaches 93-99%, cooling discharge, and can obtain particle diameter is that 80-120nm, solid content are the ABS latex of polybutadiene in small grain size of 30-50%.
The present invention is owing to chosen special emulsifying agent, and heat-up rate is controlled in strictness in polymerization process, therefore not adding under the situation of comonomer, once feeds intake, in 8-11 hour, promptly obtained the latex of polybutadiene in small grain size of 80-120nm, simple to operate and the gained latex stability is good.
Embodiment one
Prescription
100 parts of divinyl
0.3 part of Potassium Persulphate
3 parts of RA rosin acids
0.16 part of sodium lauryl sulphate
0.06 part in potassium hydroxide
0.3 part of tert-dodecyl mercaptan
4 parts of vitriolate of tartar
230 parts of deionized waters
According to above prescription, water is joined in the withstand voltage polymeric kettle, replace three times with nitrogen, be evacuated then, add the monomer divinyl.Open and stir, begin after ten minutes to heat up.In 1 hour, temperature is risen to 65 ℃, and temperature of reaction is maintained 65 ℃, once contain admittedly, and calculate monomer conversion every survey in two hours.After the polyreaction 9 hours, transformation efficiency reaches 93%, cooling discharge, just can be contained admittedly be 30%, particle diameter is the latex of polybutadiene in small grain size of 112.6nm.
Embodiment two
Prescription
100 parts of divinyl
0.4 part of Potassium Persulphate
3.5 parts of RA rosin acids
0.12 part of Sodium dodecylbenzene sulfonate
0.08 part in sodium hydroxide
0.3 part of ethylene glycol
2 parts of trisodium phosphates
3 parts in Repone K
182 parts of deionized waters
According to above prescription, water is joined in the withstand voltage polymeric kettle, replace three times with nitrogen, be evacuated then, add the monomer divinyl.Open and stir, begin after ten minutes to heat up.In 1.5 hours, temperature is risen to 66 ℃, once contain admittedly, and calculate monomer conversion every survey in two hours.After the polyreaction 8 hours, transformation efficiency reaches 95%, cooling discharge, just can be contained admittedly be 34.6%, particle diameter is the latex of polybutadiene in small grain size of 104.9nm.
Embodiment three
Prescription
100 parts of divinyl
0.25 part of ammonium persulphate
4 parts of potassium oleates
0.2 part of sodium laurylsulfonate
0.07 part in potassium hydroxide
0.4 part of neopentanoic acid
3 parts in sodium-chlor
146 parts of deionized waters
According to above prescription, water is joined in the withstand voltage polymeric kettle, replace three times with nitrogen, be evacuated then, add the monomer divinyl.Open and stir, begin after ten minutes to heat up.In 1 hour 15 minutes, temperature is risen to 66 ℃, once contain admittedly, and calculate monomer conversion every survey in two hours.After the polyreaction 10 hours, transformation efficiency reaches 97%, cooling discharge, just can be contained admittedly be 41.8%, particle diameter is the latex of polybutadiene in small grain size of 92nm.
Embodiment four
Prescription
100 parts of divinyl
0.25 part of Potassium Persulphate
5 parts of potassium oleates
0.2 part of Sodium dodecylbenzene sulfonate
0.04 part in potassium hydroxide
0.5 part of tert-dodecyl mercaptan
1.5 parts in sodium sulfate
118 parts of deionized waters
According to above prescription, water is joined in the withstand voltage polymeric kettle, replace three times with nitrogen, be evacuated then, add the monomer divinyl.Open and stir, begin after ten minutes to heat up.In 1 hour, temperature is risen to 67 ℃, once contain admittedly, and calculate monomer conversion every survey in two hours.After the polyreaction 11 hours, transformation efficiency reaches 99%, cooling discharge, just can be contained admittedly be 46.8%, particle diameter is the latex of polybutadiene in small grain size of 83nm.
Comparative Examples one
Prescription
100 parts of divinyl
0.25 part of Potassium Persulphate
1.2 parts of RA rosin acids
0.1 part of Sodium dodecylbenzene sulfonate
0.04 part in potassium hydroxide
0.5 part of tert-dodecyl mercaptan
4 parts in sodium-chlor
118 parts of deionized waters
Carry out polymerization by embodiment 1, when polyreaction to 6 hour, find that latex is paste, the consumption of analyzing reason and be compound emulsifying agent very little due to.
Comparative Examples two
Prescription
100 parts of divinyl
0.25 part of Potassium Persulphate
1.8 parts of RA rosin acids
0.2 part of Sodium dodecylbenzene sulfonate
0.04 part in potassium hydroxide
0.5 part of tert-dodecyl mercaptan
2 parts in Repone K
118 parts of deionized waters
Heating mode is with embodiment 1, and temperature of reaction is maintained 65 ℃, and polyreaction is after 14 hours, and transformation efficiency reaches 94%, and the median size of latex is 180nm.The consumption that compound emulsifying agent is described can be kept the stable of polymerization system, but the proportioning ratio of compound emulsifying agent is less, the content that is the primary emulsion that plays a major role in the compound emulsifying agent is less, cause the number of the emulsion particle that this primary emulsion generates on the low side, that is to say that reacting environment is less, cause polymerization time longer, particle diameter is too big.
Claims (4)
1. an acrylonitrile-butadiene-styrene copolymer is with the preparation method of latex of polybutadiene in small grain size, mainly by 100 weight parts of butadiene, 0.2～0.5 weight parts water dissolubility thermal decomposition initiating, 2～6 weight part emulsifying agents, 0.04～0.08 weight part highly basic, 0.1～0.5 weight part chain-transfer agent, 1～6 weight part electrolyte emulsion is polymerized, it is characterized in that described emulsifying agent is the compound emulsifying agent of disproportionated rosin acid soap or potassium oleate and alkyl-sulphate or alkylsulfonate, its composite ratio is 10～30, described various component is once to add polymeric kettle, reinforced finishing, be warming up to 60～70 ℃ of temperature of reaction in 1-1.5 hour, reaction made the latex of 80～120nm in 8～11 hours.
2. acrylonitrile-butadiene-styrene copolymer according to claim 1 is with the preparation method of latex of polybutadiene in small grain size, it is characterized in that described chain-transfer agent comprise tert-dodecyl mercaptan, acetic acid just-lauryl mercaptan ester, ethylene glycol, neopentanoic acid, dithiazole thioether.
3. acrylonitrile-butadiene-styrene copolymer according to claim 1 is characterized in that with the preparation method of latex of polybutadiene in small grain size described ionogen comprises Repone K, sodium-chlor, trisodium phosphate, sodium phosphite, sodium bicarbonate, sal enixum, vitriolate of tartar, Sodium Tetraborate, salt of wormwood, sodium iodate, sodium bromate.
4. acrylonitrile-butadiene-styrene copolymer according to claim 1 is characterized in that with the preparation method of latex of polybutadiene in small grain size described alkyl-sulphate or alkylsulfonate comprise sodium lauryl sulphate, potassium octadecyl sulfate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001071343A CN1163530C (en) | 2000-04-21 | 2000-04-21 | Preparation method of small grainsize polybutadiene latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001071343A CN1163530C (en) | 2000-04-21 | 2000-04-21 | Preparation method of small grainsize polybutadiene latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272503A true CN1272503A (en) | 2000-11-08 |
| CN1163530C CN1163530C (en) | 2004-08-25 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006039860A1 (en) * | 2004-10-12 | 2006-04-20 | China National Petroleum Corporation | A preparation method of small particle sized polybutadiene latex used for the production of abs |
| CN1313504C (en) * | 2004-10-12 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing latex of polybutadiene in small grain size |
| CN1331904C (en) * | 2004-10-12 | 2007-08-15 | 中国石油天然气集团公司 | Method for controlling reaction temperature to prepare latex of polybutadiene in small grain size |
| CN102443089A (en) * | 2010-09-30 | 2012-05-09 | 日本A&L株式会社 | Copolymer latex, composition for battery electrode and composition for paper coating |
| CN106866885A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of preparation method of latex of polybutadiene in small grain size |
| CN110144021A (en) * | 2019-04-26 | 2019-08-20 | 长春工业大学 | A kind of emulsifier and its preparation method and application |
| CN111848869A (en) * | 2020-07-23 | 2020-10-30 | 天津大沽化工股份有限公司 | Preparation method of small-particle-size high-crosslinking polybutadiene and copolymer latex thereof |
| CN112194764A (en) * | 2019-07-08 | 2021-01-08 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex |
| CN113388066A (en) * | 2021-05-07 | 2021-09-14 | 青岛科技大学 | Polybutadiene latex and preparation method thereof |
| CN113956491A (en) * | 2021-10-22 | 2022-01-21 | 东莞市米儿塑胶原料有限公司 | Preparation method of flexible waterborne polyurethane |
| CN115505063A (en) * | 2022-09-30 | 2022-12-23 | 中化国际聚合物(连云港)有限公司 | Process for preparing polybutadiene latex |
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2000
- 2000-04-21 CN CNB001071343A patent/CN1163530C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313504C (en) * | 2004-10-12 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing latex of polybutadiene in small grain size |
| CN1331904C (en) * | 2004-10-12 | 2007-08-15 | 中国石油天然气集团公司 | Method for controlling reaction temperature to prepare latex of polybutadiene in small grain size |
| WO2006039860A1 (en) * | 2004-10-12 | 2006-04-20 | China National Petroleum Corporation | A preparation method of small particle sized polybutadiene latex used for the production of abs |
| CN102443089A (en) * | 2010-09-30 | 2012-05-09 | 日本A&L株式会社 | Copolymer latex, composition for battery electrode and composition for paper coating |
| CN102443089B (en) * | 2010-09-30 | 2015-11-25 | 日本A&L株式会社 | Copolymer emulsion, battery electrode composition and paper coating composition |
| CN106866885B (en) * | 2015-12-11 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of preparation method of latex of polybutadiene in small grain size |
| CN106866885A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of preparation method of latex of polybutadiene in small grain size |
| CN110144021A (en) * | 2019-04-26 | 2019-08-20 | 长春工业大学 | A kind of emulsifier and its preparation method and application |
| CN112194764A (en) * | 2019-07-08 | 2021-01-08 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex |
| CN112194764B (en) * | 2019-07-08 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex |
| CN111848869A (en) * | 2020-07-23 | 2020-10-30 | 天津大沽化工股份有限公司 | Preparation method of small-particle-size high-crosslinking polybutadiene and copolymer latex thereof |
| CN113388066A (en) * | 2021-05-07 | 2021-09-14 | 青岛科技大学 | Polybutadiene latex and preparation method thereof |
| CN113956491A (en) * | 2021-10-22 | 2022-01-21 | 东莞市米儿塑胶原料有限公司 | Preparation method of flexible waterborne polyurethane |
| CN115505063A (en) * | 2022-09-30 | 2022-12-23 | 中化国际聚合物(连云港)有限公司 | Process for preparing polybutadiene latex |
| CN115505063B (en) * | 2022-09-30 | 2023-10-31 | 中化国际聚合物(连云港)有限公司 | Process for preparing polybutadiene latex |
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