CN105778002A - Method for preparing carboxylated styrene-butadiene rubber by emulsion polymerization - Google Patents
Method for preparing carboxylated styrene-butadiene rubber by emulsion polymerization Download PDFInfo
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- CN105778002A CN105778002A CN201410806498.0A CN201410806498A CN105778002A CN 105778002 A CN105778002 A CN 105778002A CN 201410806498 A CN201410806498 A CN 201410806498A CN 105778002 A CN105778002 A CN 105778002A
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- unsaturated carboxylic
- carboxylic acid
- emulsifying agent
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- acid
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 69
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 25
- 239000000344 soap Substances 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- 229940072033 potash Drugs 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 17
- 235000015320 potassium carbonate Nutrition 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- -1 anhydride ester Chemical class 0.000 claims description 6
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229940114930 potassium stearate Drugs 0.000 claims description 4
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229940096992 potassium oleate Drugs 0.000 claims 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 description 3
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical group C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 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 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 32
- 239000005060 rubber Substances 0.000 abstract description 32
- 239000002253 acid Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229920001577 copolymer Polymers 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 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 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000004816 latex Substances 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- 238000001514 detection method Methods 0.000 description 16
- 239000003292 glue Substances 0.000 description 16
- 238000013019 agitation Methods 0.000 description 15
- 208000012839 conversion disease Diseases 0.000 description 15
- 230000018044 dehydration Effects 0.000 description 15
- 238000006297 dehydration reaction Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 12
- 239000000693 micelle Substances 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- QHOWYOKUKZPTPL-KVVVOXFISA-N (z)-octadec-9-enoic acid;potassium Chemical compound [K].CCCCCCCC\C=C/CCCCCCCC(O)=O QHOWYOKUKZPTPL-KVVVOXFISA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for preparing carboxylic styrene butadiene rubber by emulsion polymerization, which comprises the steps of adding styrene, an emulsifier, a regulator and an initiator into a polymerization kettle, adding butadiene, carrying out emulsion polymerization under stirring, and adding unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride thereof into the polymerization kettle at the later stage of reaction. The carboxyl styrene-butadiene rubber prepared by the method has low gel content, controllable combined acid index, double-layer molecular structure, easy formation of three-dimensional net-shaped structure in the processing process, good physical and mechanical properties of rubber products, improved Mooney viscosity after processing, good crosslinking degree of finished products and especially obviously improved elongation at break.
Description
Technical field
The present invention relates to a kind of method that emulsion polymerization prepares carboxylic styrene-butadiene rubber, in more detail, be a kind of method adopting emulsion polymerization to produce surface grafting carboxylic styrene-butadiene rubber raw material.
Background technology
At present, relevant emulsion method is prepared butadiene-styrene rubber method and is had multiple, as with continuous polymerization method manufacture and batchwise polymerization method etc..
CN200710042967.6 discloses a kind of styrene-butadiene emulsion and its preparation method and application, preparation method comprises the following steps: the aqueous solution of the mixture of carboxylic acid monomer, divinylic monomer, (methyl) styrene monomer, molecular weight regulator, emulsifying agent and initiator is carried out free radical emulsion copolymerization, 3～10 hours response time, product alkaline matter is regulated pH=7～10, through being filtrated to get emulsion.The styrene-butadiene emulsion of this invention is a kind of product that can meet building coating, papermaking paint high-performance, environmental protection.This product uses in building coating, papermaking paint, can significantly improve the resistance to water of paint coatings and the adhesive force between base material.
CN200610112521.1 relates to a kind of rubbery copolymer particle being applied to transparent rubber modified thenylethylene resin composition component and preparation method thereof, includes by its composition weight portion: the shell copolymer of the stratum nucleare copolymer of 20～80 parts and 80～20 parts；Its stratum nucleare copolymer size of rubber particles that wherein rubbery copolymer is formed is generally 100～1000nm；Wherein stratum nucleare copolymer includes by its composition weight portion: the diene monomer of the styrenic monomers of 5～50 parts and 95～50 parts, the gel content of stratum nucleare copolymer emulsion is 65～85%；Wherein shell copolymer includes by its composition weight portion: (methyl) acrylic ester monomer of the styrenic monomers of 10～70 parts and 90～30 parts, by adjusting the composition of the composition of stratum nucleare copolymer emulsion, particle diameter, particle size distribution, gel content and rubbery copolymer particle in rubbery copolymer particle, transparent rubber modified thenylethylene resin is made to have good transparent, higher resistance to impact.
CN01108322.0 relates to a kind of copolymer latex for reinforcing oil well and preparation method thereof.The dispersed phase polymer particle of this copolymer emulsion has nucleocapsid structure, this structure is containing nucleated copolymer district and shell copolymer district, wherein: the comonomer in (1) core copolymer district includes: (a) single-ethenyl aromatic compound, (b) unsaturated carboxylic acid, (c) sulfonate；(2) comonomer in shell copolymer district includes: (a) conjugated diene, (b) single-ethenyl aromatic compound.Additionally, shell copolymer district can also contain: (c) unsaturated carboxylic acid monomer and (d) sulfonate monomer.
CN200480019016.1 provides and a kind of uses micro-emulsion polymerization to prepare homogeneous size and the method for shape, monodispersed microcapsule.In the microcapsule prepared by the method, the liquid or solid core encapsulated by polymer shell occupies the volume of the 10～80% of microcapsule.Owing to the microemulsion microgranule prepared at the commitment of the method is stable, therefore, being dissolved in monomer particle preferably and having the organic substance of the higher interfacial tension with water relative to polymer shell to be placed in polymer beads equably.And then, when adding cross-linking agent in polymerization, it is possible to obtain single-core microcapsules.It addition, the use of oil-soluble initiator is possible to prevent the formation of the second granule, and in polymerization, add the productivity that the second initiator can improve the microcapsule of homogeneous size and shape.
CN200480012933.7 relates to a kind of method preparing styrene-butadiene latexes.This styrene-butadiene latexes is characterised by, owing to promoting being formed thus having splendid adhesion of early stage thin film by regulating outermost gel content and molecular weight, and owing to keeping being formed thus there is fast black rate of drying and high breathability of paper thin film.Because the mechanical stability of latex and chemical stability are splendid, thus it can by very stably for paper coating.
CN201010529997.1 relates to a kind of inflaming retarding copolymer latex and production method thereof.Dispersion phase-the polymer particle of this copolymer emulsion has nucleocapsid structure, this structure is containing nucleated copolymer district and shell copolymer district, wherein: the comonomer in (1) core copolymer district includes: (a) single-ethenyl aromatic compound, (b) unsaturated carboxylic acid monomer；(2) comonomer in shell copolymer district includes: (a) vinyl halides, (b) conjugated diene, (c) single-ethenyl aromatic compound.Additionally, shell copolymer district can also contain: (d) unsaturated carboxylic acid monomer.
Current butadiene-styrene rubber adopts butadiene, St copolymerization forms, the carboxylic styrene-butadiene rubber of ternary polymerization owing to causing gel content high on main chain containing the structure such as more ehter bond and unsaturated bond, after the processing of product, physical and mechanical properties is poor, and characterize data instability, the way of existing change butadiene-styrene rubber performance is the purpose that in mixing formula, the polymer added containing carboxyl moieties reaches to improve butadiene-styrene rubber goods physical and mechanical properties, process is complicated, device requirement is many, pollute, energy consumption is high, final products mixing is uneven, physical and mechanical properties is unstable, application is restricted.
nullCarboxylic rubber is due to the existence of the unsaturated bond of acrylic compounds，Especially easy formation gel in polymerization process，Owing to gel has formed the solid netted macromole of rubber before rubber processing，Rubber processing process is not dissolved in rubber solutions，Easily cause the heterogencity of the molecular structure of rubber，Sulfurating strength can be affected，Molecule chain break can be caused in stress and deformation process，Product surface chaps，Have a strong impact on quality and the service life of goods，Rubber molecule is reduced in the probability of stress and deformation process molecular chain rupture，The macromole content of the stereochemical structure not readily dissolved in rubber solutions increases，Mooney viscosity improves，Cause the hot strength of product、Elongation at break、100% stress at definite elongation reduces，The difficulty that the course of processing becomes，So preparing low gel，Carboxyl-content and the controlled carboxylic styrene-butadiene rubber of distribution on strand to the processed and applied of rubber to energy-conservation、Reduce processing pollution，The physical and mechanical properties etc. improving product of rubber and plastic has very real meaning.
Summary of the invention
Present invention aim at providing the emulsion polymerisation process of a kind of high pressure resistant, high strength heat resistant rubber.
The method of the present invention at least includes following process:
By styrene, emulsifying agent, regulator, initiator adds polymeric kettle, after adding butadiene, it is stirred emulsion polymerization, adopt the phase after the reaction, when in polyreaction, monomer conversion reaches 52～62% (preferably 55～60%), one or many adds emulsifying agent and one or more mixture formed in unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides or emulsifying agent, the mixture of one or more and regulator (i.e. " molecular weight regulator " described in the art) in unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, terminator is added when polymerization conversion reaches 64～72% (preferably 64～68%), as being the general terminators such as sodium nitrite in aqueous solution；The addition of unsaturated carboxylic acid and/or its anhydride ester derivs is 0.05～4.5 part, it is preferred to 0.3～3.5 part.
The mode added is adopted to be mainly reaction speed and the generation type of rubber molecule structure, the diffusion utilizing solubilization micelle makes the molecule of unsaturated carboxylic acid diffuse into and be grafted on the strand group surface of the butadiene-styrene rubber formed, and forms double-deck micel.
In the present invention, emulsifying agent needs more than twice addition, and at least part of emulsifying agent adds together with unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides.Preferably it always adds the 70～85% of quality to emulsifying agent initial incremental amount.The emulsifying agent that different opportunitys add can be different.
The present invention is not special in add restriction to the kind of emulsifying agent, total addition, use emulsifying agent well known in the art, addition, can adopt single or compound, preferably with two or more emulsifying agents, both can be the different emulsifying agent of twice addition, can also being be simultaneously introduced different emulsifying agents, emulsifying agent can be sodium lauryl sulphate, ten alkyl sodium sulfates, DBSA acid sodium, potassium stearate, potassium oleate, synthetic fatty acid potash soap, disproportionated rosin potassium soap etc..Add up to 100 mass parts in butadiene, styrene, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride monomer, be butt amount, as follows.The consumption of emulsifying agent is typically in 2.5～4.5 parts.
nullThe present invention is it is specifically recommended that the phase adds emulsifying agent employing synthetic fatty acid potash soap after the reaction，Utilize its " critical micelle concentration " more much lower than other emulsifying agents，Namely in water, concentration is easy for relatively low forming micelle，Namely soap molecule required for forming each micelle is less，And what formed is the micelle of minor diameter，Solubilizing effect is good，It is particularly well-suited to the polymerization environment that reaction late monomer concentration is low，Thus use synthetic fatty acid potash soap that polymerization speed can be made to accelerate，But it has low-temperature stability poor，Easily analyse glue，Should not be used alone，So the polymeric emulsification system of the present invention is preferably with compound emulsifying agent，Multiple elements design soap，The kind of emulsifying agent is multiple，I.e. two or more emulsifying agents，Both can be the different emulsifying agent of twice addition，Can also be simultaneously introduced different emulsifying agents，Reaching both can graft polymerization response speed，Also can effectively improve the low-temperature stability of latex system simultaneously.
The present invention is not special in add restriction to initiator type, addition, use initiator generally in the art, addition, as being dicumyl peroxide, cumyl peroxide, ammonium persulfate, the one of potassium peroxydisulfate etc. or composite initiation system or oxidation-reducting system initiator.Initiator amount is preferably 0.01～0.5 part.
Regulator kind, total addition equally not especially to add restriction, are used regulator generally in the art by the present invention, as being tert-dodecyl mercaptan, dodecyl mercaptan carbon etc., it is possible to be one or more.In the present invention, regulator can once add, it is also possible to is add several times, and preferably it always adds quality 60～80% to regulator initial incremental amount, and the regulator that different opportunitys add can be different.
Unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides that the present invention adopts can be methacrylic acid, acrylic acid, acrylic anhydride, itaconic acid, fumaric acid, maleic anhydride, equisetic acid, mesaconic acid, sinapic acid, 9-undecylenic acid, angelic acid etc., it is possible to be one or more of which.The present invention be also not excluded for not pointing out other be suitable to the use of the auxiliary agent such as initiator and emulsifying agent, unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides, regulator.The addition of unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides is preferably 0.05～4.5 part, particularly 0.3～3.5 part.
Emulsifying agent and unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides, regulator mixture in each material additional proportion be not particularly limited, as long as unsaturated carboxylic acid obtains fully emulsified just passable, the addition of emulsifying agent can according to unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides, regulator addition be adjusted.Unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides that different opportunitys add can be different.
The present invention recommend auxiliary agent make consumption with total monomer amount for 100 mass parts for benchmark: the consumption of emulsifying agent is at 2.5～4.5 parts, initiator amount is at 0.01～0.5 part, regulator consumption is between 0.03～0.8 part, and unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride consumption are at 0.05～4.5 part.
What the present invention adopted is general emulsion polymerisation process, and reaction temperature condition controls at 0～30 DEG C, it is adaptable to the emulsion polymerization way of cold process and hydrothermal condition.To the terminator present invention also without special restriction, adopt current techique.
The present invention both can use in intermittence type polymerization reacts, it is also possible to the use in continuous polymerization reactive mode.Through the carboxylic styrene-butadiene rubber gel content of preparation of the present invention between 0～2%, combinated styrene content can between 18～28%, and combined acid content can between 0.01～3%, and compression set is between 7～9%, and ML100 DEG C of 1+4 of Mooney viscosity is between 50～70.
In the present invention, styrene, the addition of divinylic monomer and step, the condition present invention except present invention special requirement are not any limitation as, carboxylic styrene-butadiene rubber of the prior art is the general preparation condition present invention can be suitable for, the emulsifying agent added together with unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides acts primarily as solubilising peptizaiton, emulsifying agent addition is not specially limited, and can be adjusted according to the addition of unsaturated carboxylic acid.The unsaturated carboxylic acid recommended and/or the Adding Way of unsaturated carboxylic acid anhydrides are to add after emulsifying in the emulsifying agent that critical micelle concentration formation condition is little.
nullSpecial recommendation method of the present invention is to adopt at last stage reaction, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides are added polymeric kettle，Namely the phase adds emulsifying agent after the reaction、Unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides，Or add regulator to terminate to reaction，The purpose reaching growth and the branching controlling strand is spread by solubilising，Add emulsifying agent、Unsaturated carboxylic acid、The purpose of the mixture of unsaturated carboxylic acid anhydrides and regulator is in that to form new micelle，Utilize and produce new solubilization micelle，Consume the unreacted carboxylic acid monomer containing unsaturated bond，Control the unsaturated carboxylic acid monomer molecule containing free radical to the diffusion in the micelle forming oligomer molecules，Graft reaction is carried out on the rubber molecule core surface formed，So both consume unsaturated carboxylic acid monomer molecule，Complete again the probability in the conversion that the rubber molecule formed further increases or the branching formation end of the chain contains carboxyl structure，Thus it is low to obtain gel content，Internal layer is the micel of butadiene-styrene rubber，Outer layer is the rubber molecule structure of the double-deck macromole containing carboxyl unsaturated bond.Adding unsaturated carboxylic acid at last stage reaction is for the generation type of reaction speed and rubber molecule structure, reach first reaction and form butadiene-styrene rubber kernel, then in the outer grafting of core, contain the graft polymers of carboxyl, reach to improve every physical and mechanical properties of rubber.The number of times present invention added is not any limitation as especially.
Have very big different from common carboxyl group nitrile rubber of the prior art in the present invention, although what add is all unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, but the difference due to purposes, make its adition process, act on different from generic case, unsaturated carboxylic acid in the present invention, unsaturated carboxylic acid anhydrides is used to carry out molecular surface graft polymerization reaction, belong to secondary response, the rubber molecule main chain made or side chain termination branch form the more structure containing unsaturated carboxylic acid, therefore feed postition be different from copolyreaction frequently with mode, addition is also different from general addition, consumption closer to regulator.Addition is too high can aggravate cross-linking reaction, causes that gel content increases, also can affect the formation of rubber molecule structure, and temperature when increasing mixing affects melting effect, affects the degree of cross linking of rubber and the opportunity of cross-linking reaction, causes that physical and mechanical properties declines.
The method have the characteristics that and in the course of the polymerization process the microstructure of rubber molecule has been controlled and regulated so that it is having reached low gel, combined acid index can control within the specific limits.Double-deck micel makes rubber physical mechanical property be obviously improved, and the range of application of product has had bigger lifting.
Use the carboxylic styrene-butadiene rubber gel content that the inventive method prepares low, combined acid index is controlled, there is bilayer molecules structure, the course of processing is easily formed solid netted body structure, the physical and mechanical properties of rubber is good, after processing, Mooney viscosity improves, finished product crosslinking degree is good, homogeneity is good, make the compression set of product, shore a hardness, tearing strength, hot strength, elongation at break, 100% stress at definite elongation improves accordingly than common carboxylic rubber, use ASTM standard NO:7# white carbon black can detect the stress at definite elongation of 300% and not pull apart, the test of this former carboxylic rubber cannot complete effectively detection, elongation at break significantly improves, and the stress at definite elongation of 300% is higher than other butadiene-styrene rubber kinds.This is that cross-linking reaction tropism is good, and the structure comparison formed in sulfuration and fabricated product process is homogeneous, and stress relaxation phenomenon is slight owing to carboxylic group is evenly distributed on strand group surface, so the good stability of the dimension of goods.
Detailed description of the invention
Illustrate by embodiment below, but the invention is not limited in these embodiments.In embodiment unless specifically stated otherwise outside, " % " refers both to mass percent.All in grams, the amount of auxiliary below indicated is amount of solution to the amount of auxiliary used in embodiment, comparative example, is the compounding agent solution amount calculated according to concentration.Emulsifying agents in embodiment etc. are as described below:
Embodiment 1
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 467 grams，Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.4726 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 55%、25.65 grams of acrylic acid、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 1 after the detection of glue sample:
Table 1
Embodiment 2
At 3M3Reactor adds water 1600 kg water, add 67.25 kilograms of potassium stearate solution and 61.39 kilograms of oleic acid potassium solutions, Klorvess Liquid 20 kilograms, diffusion agent N solution 14.28 kilograms, under agitation dispersing and dissolving, dodecyl mercaptan carbon 2.6 kilograms, add styrene 254 kilograms, ammonium persulfate solution 46 kilograms, butadiene 576 kilograms, temperature control is to 7.5～8.5 DEG C of reactions, reaction is continued after adding emulsifying agent synthesis fat acid potassium solution 25.5 kilograms and methacrylic acid 17.22 kilograms after when conversion ratio reaches 52%, when reaction conversion ratio reaches addition terminator sodium nitrite solution 38 kilograms after more than 70%, flash liberation after 30 minutes, obtain latex, then it is condensed, washing, dehydration, dry, result such as table 2 after the detection of glue sample:
Table 2
Embodiment 3
null10 liters of reactors add 4449 milliliters of water of water，Add emulsifying agent A473.56 gram and reducing agent B15.37 gram，Under agitation dispersing and dissolving，Add styrene 454.59 grams，Tert-dodecyl mercaptan 4.75 grams，Sodium dithionite 0.179 gram，After nitrogen inflation-vacuum displacement，Add cumyl peroxide 0.856 gram，Add butadiene 1440 grams，Temperature control is to 4.5～5.5 DEG C of reactions，Emulsifying agent synthesis fat acid potassium solution 75 grams is added after when conversion ratio reaches 60%、Fumaric acid 25.9 grams、Reaction is continued after tert-dodecyl mercaptan 0.35 gram，When reaction conversion ratio reaches addition terminator 35 grams after more than 72%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 3 after the detection of glue sample:
Table 3
Embodiment 4
At 3M3nullReactor adds water 1600 kg water，Add 136.5 kilograms of isproportionated potassium rosinate solution，Klorvess Liquid 20 kilograms，Diffusion agent N solution 14.28 kilograms，Under agitation dispersing and dissolving，Dodecyl mercaptan carbon 2.6 kilograms，Add styrene 225 kilograms，Hydrogen phosphide cumene solution 296 kilograms，Butadiene 576 kilograms，Temperature control is to 7.5～8.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 23.5 kilograms is added after when conversion ratio reaches 52%、Isproportionated potassium rosinate solution 2 kilograms、Reaction is continued after the mixture that itaconic acid is 8 kilograms，Emulsifying agent synthetic fatty acid potash soap 1.2 kilograms is added after when conversion ratio reaches 62%、Isproportionated potassium rosinate solution 0.8 kilogram、Reaction is continued after the mixture that itaconic acid is 4 kilograms，When reaction conversion ratio reaches addition terminator 50 kilograms after more than 70%，Flash liberation after 30 minutes，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 4 after the detection of glue sample:
Table 4
Embodiment 5
null10 liters of reactors add 5100 milliliters of water of water，Add potassium oleate solution 412 grams and reducing agent B9.15 gram，Under agitation dispersing and dissolving，Add styrene 474 grams，Dodecyl mercaptan carbon 5.08 grams，Sodium dithionite 0.1792 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.5726 gram，Add butadiene 1283 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Synthetic fatty acid potash soap 109 grams is added after when conversion ratio reaches 58%、Maleic anhydride 53 grams、Temperature control is continued to 7.5～8.5 DEG C of reactions after tert-dodecyl mercaptan 0.49 gram，When reaction conversion ratio reaches addition terminator 35 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 5 after the detection of glue sample:
Table 5
Embodiment 6
At 3M3Reactor adds water 1600 kg water, add 67.25 kilograms of potassium stearate solution and 61.39 kilograms of oleic acid potassium solutions, Klorvess Liquid 20 kilograms, under agitation dispersing and dissolving, dodecyl mercaptan carbon 2.6 kilograms, add styrene 254 kilograms, ammonium persulfate solution 46 kilograms, butadiene 576 kilograms, temperature control is to 7.5～8.5 DEG C of reactions, reaction is continued after adding emulsifying agent synthetic fatty acid potassium solution 18.0 kilograms and angelic acid 7.5 kilograms after when conversion ratio reaches 56%, when reaction conversion ratio reaches addition terminator 48 kilograms after more than 65%, flash liberation after 30 minutes, obtain latex, then it is condensed, washing, dehydration, dry, result such as table 6 after the detection of glue sample:
Table 6
Embodiment 7
null10 liters of reactors add 4449 milliliters of water of water，Add emulsifying agent A473.56 gram and reducing agent B15.37 gram，Under agitation dispersing and dissolving，Add styrene 464.59 grams，Tert-dodecyl mercaptan 4.75 grams，Sodium dithionite 0.17 gram，After nitrogen inflation-vacuum displacement，Add cumyl peroxide 0.856 gram，Add butadiene 1440 grams，Temperature control is to 4.5～5.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 90 grams is added after when conversion ratio reaches 60%、Tert-dodecyl mercaptan 0.35 gram、Reaction is continued after 9-undecylenic acid 47.6 grams，When reaction conversion ratio reaches addition terminator 35 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 7 after the detection of glue sample:
Table 7
Embodiment 8
10 liters of reactors add 5100 milliliters of water of water, add emulsifying agent A503.09 gram and reducing agent B8.5 gram, under agitation dispersing and dissolving, add styrene 467 grams, tert-dodecyl mercaptan 4.65 grams, sodium dithionite 0.1692 gram, after nitrogen inflation-vacuum displacement, add dicumyl peroxide 0.4726 gram, add butadiene 1243 grams, temperature control is to 11.5～12.5 DEG C of reactions, emulsifying agent CP-1055 gram is added after when conversion ratio reaches 55%, reaction is continued after sinapic acid 12.55 grams, when reaction conversion ratio reaches addition terminator 32 grams after more than 66%, after 30 minutes degassed, obtain latex, then it is condensed, washing, dehydration, dry, result such as table 8 after the detection of glue sample:
Table 8
Product main performance:
Product is mainly lamellar or bulk, large grained, fugitive constituent≤1.0%, total ash≤0.8%, and other indexs are otherwise varied with the difference of product grade.
Comparative example 1:
According to the condition that embodiment 1 is identical, the difference is that adopting prior art, once add raw materials into reactor, and do not add acrylic acid, regulator and emulsifying agent, it does not have regulate through course of reaction, the physical index of gained rubber is close, but rubber molecule structure is different, and the rubber physical mechanical property after processing changes greatly, and has decline in various degree, after processing, the range of application of product diminishes, and added value reduces.
10 liters of reactors add 5100 milliliters of water of water, add emulsifying agent A438.09 gram and reducing agent B8.5 gram, synthetic fatty acid potash soap 105 grams, 25.65 grams of acrylic acid, under agitation dispersing and dissolving, add styrene 467 grams, tert-dodecyl mercaptan 5.1 grams, sodium dithionite 0.1692 gram, after nitrogen inflation-vacuum displacement, add dicumyl peroxide 0.4726 gram, add butadiene 1243 grams, temperature control is to 11.5～12.5 DEG C of reactions, when reaction conversion ratio reaches addition terminator 32 grams after more than 68%, after 30 minutes degassed, obtain latex, then it is condensed, washing, dehydration, dry, result such as table 9 after the detection of glue sample:
Table 9
Comparative example 2:
With embodiment 1, institute is the difference is that not adding emulsifying agent synthetic fatty acid potash soap in reaction, all the other conditions are constant, acquired results is that combined acid is relatively low, other indexs are close, and owing to not having the effect of the solubilization micelle of synthetic fatty acid potash soap, carboxyl is grafted on the position of rubber molecular chain and quantity is varied from, carboxyl skewness cause processing after rubber physical mechanical property change greatly, have decline in various degree.
10 liters of reactors add 5100 milliliters of water of water, add emulsifying agent A438.09 gram and reducing agent B8.5 gram, under agitation dispersing and dissolving, add styrene 467 grams, tert-dodecyl mercaptan 4.65 grams, sodium dithionite 0.1692 gram, after nitrogen inflation-vacuum displacement, add dicumyl peroxide 0.4726 gram, add butadiene 1243 grams, temperature control is to 11.5～12.5 DEG C of reactions, add after when conversion ratio reaches 55%, 25.65 grams of acrylic acid, reaction is continued after tert-dodecyl mercaptan 0.45 gram, when reaction conversion ratio reaches addition terminator 32 grams after more than 68%, after 30 minutes degassed, obtain latex, then it is condensed, washing, dehydration, dry, result such as table 10 after the detection of glue sample:
Table 10
Comparative example 3:
With embodiment 1, institute adds before the reaction the difference is that acrylic acid, and in reaction, conversion ratio is added without acrylic acid when reaching 55, and all the other conditions are constant, and due to carboxyl distribution difference, result also has very big difference.
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 467 grams，25.65 grams of acrylic acid、Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.4726 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 55%、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 11 after the detection of glue sample:
Table 11
Comparative example 4:
With embodiment 1, increase the difference is that the addition of carboxylic acid, all the other conditions are constant, and due to the gel group change that the different and free carboxyl-reactive group of carboxyl-content distribution causes, homogeneity is poor, poor processability, and result also has very big difference.
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 467 grams，Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.4726 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 55%、102.9 grams of acrylic acid、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 12 after the detection of glue sample:
Table 12
Comparative example 5:
With embodiment 1, the difference is that the addition of carboxylic acid different for opportunity, all the other conditions are constant, and due to the gel group change that the different and free carboxyl-reactive group of carboxyl binding capacity on micel causes, result also has very big difference.
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 467 grams，Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.4726 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 74%、25.65 grams of acrylic acid、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 80%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 13 after the detection of glue sample:
Table 13
Comparative example 6:
With embodiment 1, the difference is that the addition also gradation of initiator, all the other conditions are constant, and owing to the reaction mechanism mechanism of reaction changes, the gel group change that different and free carboxyl-reactive groups cause on molecular structure, result also has very big difference.
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 467 grams，Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.3308 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 55%、Dicumyl peroxide 0.1418 gram、25.65 grams of acrylic acid、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 14 after the detection of glue sample:
Table 14
Comparative example 7:
With embodiment 1, institute is the difference is that cinnamic addition also gradation, and all the other conditions are constant, and owing to the reaction mechanism mechanism of reaction changes, the combinated styrene content gel group change that different and free carboxyl-reactive groups cause on molecular structure, result also has very big difference.
null10 liters of reactors add 5100 milliliters of water of water，Add emulsifying agent A438.09 gram and reducing agent B8.5 gram，Under agitation dispersing and dissolving，Add styrene 300 grams，Tert-dodecyl mercaptan 4.65 grams，Sodium dithionite 0.1692 gram，After nitrogen inflation-vacuum displacement，Add dicumyl peroxide 0.4726 gram，Add butadiene 1243 grams，Temperature control is to 11.5～12.5 DEG C of reactions，Emulsifying agent synthetic fatty acid potash soap 105 grams is added after when conversion ratio reaches 55%、25.65 grams of acrylic acid、Styrene 167 grams、Reaction is continued after tert-dodecyl mercaptan 0.45 gram，When reaction conversion ratio reaches addition terminator 32 grams after more than 68%，After 30 minutes degassed，Obtain latex，Then it is condensed，Washing、Dehydration、Dry，Result such as table 15 after the detection of glue sample:
Table 15
Claims (10)
1. the method that an emulsion polymerization prepares carboxylic styrene-butadiene rubber, it is characterized in that the method at least includes following process: by styrene, emulsifying agent, regulator, initiator adds polymeric kettle, after adding butadiene, it is stirred emulsion polymerization, in polyreaction, when monomer conversion reaches 52～62%, one or many adds emulsifying agent and one or more mixture formed in unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride or emulsifying agent, one or more pre-mixtures with molecular weight regulator in unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, terminator is added when polymerization conversion reaches 64～72%；With total monomer amount in reference count for 100 mass parts, the addition of unsaturated carboxylic acid and/or its anhydride ester derivs is 0.05～4.5 part.
2. method according to claim 1, it is characterised in that described emulsifying agent is one or more in sodium lauryl sulphate, ten alkyl sodium sulfates, dodecylbenzene sodium sulfonate, potassium stearate, potassium oleate, synthetic fatty acid potash soap or disproportionated rosin potassium soap；Preferably with two or more emulsifying agents, both can be the different emulsifying agent of twice addition, it is also possible to be simultaneously introduced different emulsifying agents.
3. method according to claim 1 and 2, it is characterised in that add up to 100 mass parts in total monomer, the consumption of emulsifying agent is 2.5～4.5 parts.
4. method according to claim 1, it is characterized in that, when monomer conversion reaches 55～60%, one or many adds one or more mixture formed in emulsifying agent and unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides or one or more pre-mixtures with molecular weight regulator in emulsifying agent, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides.
5. method according to claim 1, it is characterised in that add terminator when polymerization conversion reaches 64～68%.
6. method according to claim 1, it is characterised in that described initiator is dicumyl peroxide, cumyl peroxide, ammonium persulfate or one or more in potassium peroxydisulfate.
7. the method according to claim 1 or 6, it is characterised in that described initiator amount is 0.01～0.5 part.
8. method according to claim 1, it is characterised in that described unsaturated carboxylic acid is methacrylic acid, acrylic acid, itaconic acid, fumaric acid, equisetic acid, mesaconic acid, sinapic acid, 9-undecylenic acid or angelic acid；Described unsaturated carboxylic acid anhydride is acrylic anhydride, maleic anhydride.
9. method according to claim 1, it is characterised in that add up to 100 mass parts in total monomer, the addition of unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is 0.3～3.5 part.
10. according to described method arbitrary in claim 1 to 9, it is characterised in that adopting emulsion polymerisation process, reaction temperature condition controls at 0-30 DEG C.
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| CN115043996A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared silicon-containing thermoplastic resin |
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