CN102498139A - 纳米尺寸的基于二烯的聚合物胶乳粒子 - Google Patents
纳米尺寸的基于二烯的聚合物胶乳粒子 Download PDFInfo
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- CN102498139A CN102498139A CN2010800379041A CN201080037904A CN102498139A CN 102498139 A CN102498139 A CN 102498139A CN 2010800379041 A CN2010800379041 A CN 2010800379041A CN 201080037904 A CN201080037904 A CN 201080037904A CN 102498139 A CN102498139 A CN 102498139A
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- Prior art keywords
- diene
- aforementioned
- polymkeric substance
- hydrogenation
- latex
- Prior art date
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- Granted
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 41
- 229920000126 latex Polymers 0.000 title claims abstract description 38
- 239000004816 latex Substances 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 36
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012966 redox initiator Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 ester alkylsulfate Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920013649 Paracril Polymers 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical group OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical class CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 1
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylcyclohexane Chemical compound OO.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 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
- 150000002978 peroxides Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- 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
-
- 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
- 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
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及具有以d90-值测量的粒径小于60nm的基于二烯的不饱和聚合物胶乳粒子及其生产方法。还公开了在减少凝胶形成的情况下用于将基于二烯的胶乳用作橡胶的方法以及用于转化为氢化聚合物的方法。
Description
技术领域
本发明涉及纳米尺寸的基于二烯的聚合物胶乳粒子(纳米级二烯类聚合物乳胶颗粒或微粒,nano-sized diene-based polymer latex particle)、一种用于生产这样的粒子的方法以及将它们用作橡胶以及用于转化为氢化聚合物(hydrogenated polymer)的方法。
背景技术
基于二烯的不饱和聚合物,例如通过丙烯腈和丁二烯的聚合而产生的丁腈橡胶,也称为NBR,在本领域是熟知的。用于共聚丙烯腈和丁二烯的方法例如在US-A-3 690 349和US-A-5 770 660中进行了描述。取决于生产条件,这样的聚合物可以作为在水性介质中的胶乳获得。不饱和的基于二烯的聚合物如NBR用于各种工业目的,此外,用于氢化这样的不饱和聚合物的方法在本领域是熟知的。
已经知晓,在催化剂存在下,通过用氢处理有机溶液中的聚合物而可以成功地氢化基于二烯的聚合物中的碳-碳双键,从而生产最终使用性能显著改善的饱和聚合物。这样的方法可以选择性地氢化双键,以使例如芳基或环烷基(脂环烃基团,naphthenic group)中的双键不会被氢化,并且碳和其他原子如氮或氧之间的双键或三键不会受到影响。本技术领域包含许多适用于这样的氢化的催化剂实例,包括基于钴、镍、铑、钌、锇、和铱的催化剂。催化剂的适用性取决于所需氢化度、氢化反应的速率以及聚合物中存在或不存在诸如羧基和氰基(腈基,nitrile group)的其他基团。
如果使用有机金属催化剂或一些特殊的金属盐催化剂和高压气态氢,则基于二烯的聚合物的氢化已经非常成功。这样的成功已经在溶液氢化、整体氢化(本体氢化,bulk hydrogenation)及直接胶乳氢化中实现。对于基于二烯的聚合物的溶液氢化,将聚合物首先溶解在有机溶剂中,然后进行氢化;在氢化后,施加后处理以再循环该有机溶剂及回收金属催化剂。在该领域中,已经存在很多专利以及本领域提交的专利申请,如USA-6,410,657、USA6,020,439、USA-5,705,571、USA5,057,581以及USA-3,454,644。
在直接胶乳氢化中,将催化剂直接添加到基于二烯的聚合物胶乳中用于氢化操作。许多基于二烯的聚合物、共聚物或三元共聚物通过乳液聚合方法制得,并且在它们从聚合反应器中排放出来时为胶乳形式。因此,非常期望直接氢化胶乳形式的基于二烯的聚合物,基于二烯的聚合物在近十年来受到了越来越多的关注。已经进行过很多努力来实现这样的方法。美国专利7,385,010已经公开了一种通过使用有机金属催化剂和高压气态氢来直接氢化基于二烯的聚合物胶乳的方法。
在整体氢化中,使催化剂直接与基于二烯的聚合物混合,或者将催化剂包埋在聚合物中,然后进行氢化。美国专利7,345,115教导了一种在高于100℃的温度条件下使用有机金属催化剂和高压气态氢来氢化整体基于二烯的聚合物的方法,其中该聚合物直接与粒子催化剂混合。
以上方法的一个显著特征在于,它们都涉及与贵金属相关的催化剂,它们都需要高压氢气以及它们可能都需要相对较长的反应时间。
为了避免使用这些贵金属并且避免在高压条件下进行操作,已经特别关注使用肼或肼的衍生物作为还原剂连同氧化剂如氧气、空气或过氧化氢一起进行C=C键的氢化。然后用于使C=C键饱和的氢源作为氧化还原反应的结果而原位产生,其中二酰亚胺还作为中间物形成。在US-A-4,452,950中,使用水合肼(hydrazine hydrate)/过氧化氢(或氧)氧化还原体系进行胶乳氢化而原位产生二酰亚胺。CuSO4或FeSO4用作催化剂。US-A-5,039,737和US-A-5,442,009提供了更精炼的胶乳氢化方法,其利用臭氧处理氢化的胶乳以破坏在使用二酰亚胺方法进行胶乳氢化期间或之后形成的交联聚合物链。US 6,552,132B2公开了可以在胶乳氢化之前、期间或之后添加一种化合物,以破坏使用二酰亚胺氢化方法进行氢化期间形成的交联。该化合物可以选自伯胺或仲胺、羟胺、亚胺、吖嗪、腙和肟。US 6,635,718B2描述了在作为催化剂的包含处于至少4的氧化态的金属原子(如诸如Ti(IV)、V(V)、Mo(VI)和W(VI))的金属化合物存在下,通过使用肼和氧化性化合物(oxidizing compound)来氢化水分散体形式的不饱和聚合物的C=C键的方法。在Applied Catalysis A:General 276(2004)123-128和Journal of Applied Polymer Science Vol.96,(2005)1122-1(应用催化A:概述276(2004)123-138和应用聚合物科学杂志,第96卷(2005)1122-1125)中提出了涉及经由利用二酰亚胺氢化途径来氢化丁腈橡胶胶乳的详细研究,其涵盖考察氢化效率和氢化度。
已经发现,在胶乳粒子界面(中间相,interphase)处和聚合物相内存在副反应,其产生自由基以引发胶乳形式的聚合物的交联。使用自由基清除剂没有显示出有助于抑制凝胶形成程度的任何证据。尽管存在开发用于减少交联的一些方法,但是上述二酰亚胺途径依然遇到凝胶形成的问题,尤其是在实现高氢化转化时。因此,由于其肉眼可见的三维交联结构,所以所得到的氢化橡胶团块(橡胶基质,rubber mass)难以加工,或者不适合进一步使用。
发明内容
本发明的一个目的是提供新的基于二烯的不饱和聚合物,其在减少凝胶形成的情况下能够易于被氢化。本发明的另一个目的的提供生产该不饱和聚合物的方法。
本发明提供新的胶乳形式的纳米尺寸的基于二烯的不饱和聚合物粒子,其中这些粒子具有的以d90-值(d90-value)测量的粒径小于60nm,优选小于40nm,更优选小于30nm,最优选为20nm。在一个实施方式中,该基于二烯的不饱和聚合物为丙烯腈/丁二烯聚合物。
此外,本发明提供一种用于生产胶乳形式的基于二烯的不饱和聚合物的方法,包括:
a)使至少一种二烯D和可选地至少一种可共聚单体A聚合,
b)在水性介质,优选水中,
c)在表面活性剂,优选烷基硫酸盐(烷基硫酸酯,alkylsulfate)存在下,其中
d)二烯D和可选地至少一种可共聚单体A连续地,优选以缓慢且稳定的进料速度,加料到含有该水性介质、聚合引发剂和该表面活性剂的反应器中。
在一个优选实施方式中,二烯D和可选地单体A连续且缓慢地添加。添加的时间长度取决于反应条件,其原则上不允许单体D和A聚集成小液滴且通常至少为10分钟。在又一个优选实施方式中,维持反应器内水相中少于1%(以重量计,基于水的量),优选少于0.1%(以重量计,基于水的量)的未反应的二烯D和可选地单体A。
在又一个优选实施方式中,使用少量的氧化还原聚合引发剂,其基于单体的总量按重量计为在0.05%至5%,优选为0.1%至1%的范围内。
对于本发明的目的,术语“将二烯D和可选地至少一种可共聚单体A连续加料到反应器中”是指在反应刚开始时,不将全部或几乎全部量的反应物一起放入反应器中。该术语包括以大致相同进料速率和浓度进料反应物,包括增加和降低该速率。此外,该术语包括在反应期间添加小部分的反应物。
根据本发明的方法可用于生产根据本发明的具有以d90-直径(d90-diameter)测量的粒径小于60nm的纳米尺寸的粒子。
对于本发明的目的,d90-直径是指90%的粒子具有小于指定值的直径。
具体实施方式
基于二烯的胶乳粒子是基于至少一种二烯单体,优选为至少一种共轭单体D。二烯D可以具有任何性质。在一个实施方式中,使用(C4-C6)共轭单体。优选为1,3-丁二烯、异戊二烯、1-甲基丁二烯、2,3-二甲基丁二烯、戊间二烯、氯丁二烯、或它们的混合物。具体优选为1,3-丁二烯和异戊二烯或它们的混合物。特别优选为1,3-丁二烯。
适合的可共聚单体A包括丙烯腈、甲基丙烯腈、苯乙烯、α-甲基苯乙烯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯,以及选自富马酸、马来酸、丙烯酸和甲基丙烯酸的不饱和羧酸。
根据本发明,共轭二烯D形成按重量计约15%至约100%的胶乳形式的含碳-碳双键的聚合物。如果使用可共聚单体A且选自苯乙烯和α-甲基苯乙烯,则该苯乙烯和/或甲基苯乙烯单体优选形成按重量计约15%至约60%的聚合物。如果使用其他可共聚单体A且选自丙烯腈和甲基丙烯腈,则该丙烯腈和/或甲基丙烯腈单体优选形成按重量计约15至约50%的聚合物,其中共轭二烯形成按重量计约50%至约85%的聚合物。
如果使用其他可共聚单体A且选自丙烯腈和甲基丙烯腈及另外选自不饱和羧酸,该丙烯腈或甲基丙烯腈形成按重量计约15%至约50%的聚合物,该不饱和羧酸形成按重量计约1%至约10%的聚合物,并且该共轭二烯形成按重量计约40%至约85%的聚合物。
优选产物包括无规或嵌段型的苯乙烯-丁二烯聚合物、丁二烯-丙烯腈聚合物和丁二烯-丙烯腈-甲基丙烯酸聚合物。优选的丁二烯-丙烯腈聚合物的丙烯腈含量按重量计为约25%至约45%。
特别适合用于本发明的共聚物为腈橡胶(丁腈橡胶,也简称为“NBR”),这是一种α,β-不饱和腈(特别优选丙烯腈)和共轭二烯(特别优选1,3-丁二烯)以及可选地一种或多种其他可共聚单体(如α,β-不饱和一元羧酸或二元羧酸、它们的酯或酰胺)的共聚物。
作为这样的腈橡胶中的α,β-不饱和一元羧酸或二元羧酸,优选是富马酸、马来酸、丙烯酸和甲基丙烯酸。
作为这样的腈橡胶中的α,β-不饱和羧酸的酯,优选使用它们的烷基酯和烷氧基烷基酯。具体地,特别优选的α,β-不饱和羧酸的烷基酯是丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、以及丙烯酸辛酯。特别优选的α,β-不饱和羧酸的烷氧基烷基酯是(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、以及(甲基)丙烯酸甲氧基乙酯。也可以使用例如上述的烷基酯和例如上述形式的烷氧基烷基酯的混合物。
根据本发明的优选三元共聚物是丙烯腈、1,3-丁二烯和选自由富马酸、马来酸、丙烯酸、甲基丙烯酸、丙烯酸正丁酯和丙烯酸叔丁酯组成的组中的第三单体的三元共聚物。
该聚合物的合成可以胶乳形式进行。根据本发明生产的聚合物是胶乳中的纳米粒子。
本发明的合成方法可利用化学氧化还原引发剂如过硫酸铵(APS)实现。其他聚合引发剂包括热引发剂(如过硫酸钾、二烷基过氧化物或偶氮化合物)以及氧化还原引发剂例如烷基氢过氧化物(如二异丙苯氢过氧化物、对-薄荷烷(p-menthane)氢过氧化物及蒎烷氢过氧化物),可选地与胆酸盐和适当的还原剂组合。
可使用少量引发剂。基于单体的重量,APS相对于总的单体的量按重量计为在0.05至5%,优选0.1%至1%的范围内。
本发明的合成方法优选在表面活性剂如十二烷基硫酸钠(SDS)下进行。基于所使用的总单体量,表面活性剂的量按重量计为约0.1%至约15%,优选为0.1%至1%。
在本发明的一个优选实施方式中,水用作介质。基于所使用的单体的量,水的量按重量计为约2倍至约30倍,优选为5倍至10倍。
本发明的合成方法可在装备有温度调节和单体进料及搅拌装置的适当反应器中进行。
一般地,根据本发明,适合本发明的反应温度为约0℃至约100℃,优选为约15℃至约70℃。
根据本发明的一个优选实施方式,在反应过程期间,取决于操作条件,反应时间为约15分钟至约100小时,优选为约1小时至20小时。
根据本发明的一个优选实施方式,在反应过程期间,取决于操作条件,单体进料时间为约15分钟至约50小时,优选为约1小时至10小时。
根据本发明的一个优选实施方式,在反应过程期间,在单体进料完成后,优选有一个老化时间(熟化时间,aging time),并且取决于操作条件,该老化时间为约15分钟至约50小时,优选为约1小时至10小时。
根据本发明的一个优选实施方式,当反应完成到所需程度时,可冷却反应容器(如适用)并获得聚合物胶乳。
在一个优选实施方式中,所得到的胶乳可与本领域已知的添加剂(例如抗氧化剂)掺混,并可以转移至凝结和洗涤容器,其中充分搅拌以防止结块。随后,产物可以进料到最终脱水装置中,造粒、涂覆分配剂(partitioning agent)并转移到适当的干燥器中。
聚合可在本领域已知的反应器内进行。在一个实施方式中,反应器至少是设置有搅拌器、用于测量聚合过程的温度传感装置以及至少一个用于连续添加单体的进口的容器。此外,存在调节流速对反应器体积比的装置以提供单体的充分且连续添加速率。
根据本发明获得的纳米尺寸的基于二烯的聚合物通常可用于与作为橡胶或橡胶中间物的更高粒径的基于二烯的胶乳粒子一样的技术用途,显示出关于对热、氧和臭氧的降解的抗性的改进性能。
此外,该纳米尺寸的基于二烯的胶乳粒子,尤其是基于丙烯腈和丁二烯,可以很容易被氢化,用于生产例如氢化NBR(称为HNBR)。
实施例
反应和分析中使用的材料列于表1。
表1-材料的规格
以下实施例举例说明了本发明的范围,但并不用来限制本发明的范围。
实施例1:
将0.1份的KPS、0.5份的SDS、0.05份的n-DDM和40份的水放入一个300mL的装配有桨叶搅拌器、加入管和热电偶的不锈钢高压反应器(Parr Instruments)。在温度升到85℃后,将1.5份的丙烯腈和3份的丁二烯的混合物在150分钟的时间内作为多个小部分添加。在加入该单体混合物之后,将反应混合物在80-85℃的温度下保持另外的20分钟,然后冷却以停止反应。
固体含量通过称重法确定,并以90Plus粒径分析仪(BrookhavenInstrument Corporation)利用动态光散射法测量z均粒径。数均粒径用Natrac150(Microtrac Inc.)测量。共聚物组成用IR技术测量。使用Bio-RadFTS 300X光谱仪。通过将来自MEK溶液的聚合物浇注到氯化钠盘上而制备红外样品。这样获得的聚合物的粒径为30nm。
实施例2:
采用与实施例1中所述的相同条件和步骤,只是反应温度为90℃,并且反应时间为35分钟,以及老化时间为25分钟。所得NBR的粒径为19.3nm。
实施例3:
采用与实施例1中所述的相同条件和过程,只是n-DDM的量为0.025份,反应温度为70℃,并且反应时间为135分钟,以及老化时间为60分钟。所得NBR的粒径为19.1nm。
实施例4:
采用与实施例1中所述的相同条件和过程,只是反应温度为70℃和单体进料时间为180分钟,以及陈化时间为25分钟。所得NBR的粒径为23.5nm。
尽管为了举例说明的目的在上文中已经详细描述了本发明,但应该理解,这样的细节仅用于举例说明的目的,并且在不背离由所附权利要求限定的本发明的精神和范围的情况下,本领域技术人员可以对本发明进行各种变形。
Claims (11)
1.具有以d90-值测量的粒径小于60nm的基于二烯的不饱和聚合物胶乳粒子。
2.根据权利要求1所述的胶乳粒子,其中,所述基于二烯的胶乳粒子是丙烯腈/丁二烯聚合物。
3.用于生产胶乳形式的基于二烯的不饱和聚合物的方法,包括:
a)使至少一种二烯D和可选地至少一种可共聚单体A聚合,
b)在水性介质,优选水中,
c)在表面活性剂,优选烷基硫酸盐存在下,其中
d)将二烯D和可选地至少一种可共聚单体A连续加料到含有所述水性介质、聚合引发剂和所述表面活性剂的反应器中,优选以缓慢且稳定的进料速度。
4.根据权利要求3所述的方法,其中,所述二烯D为1,3-丁二烯,并且其中至少一种可共聚单体A发生反应。
5.根据前述权利要求中任一项所述的方法,其中,所述可共聚单体A是丙烯腈。
6.根据前述权利要求中任一项所述的方法,其中,所述聚合在以基于所用总单体量的按重量计为0.1%至1%的量的表面活性剂存在下进行。
7.根据前述权利要求中任一项所述的方法,其中,所述获得的基于二烯的胶乳粒子具有的以d90-值测量的粒径小于60nm。
8.根据前述权利要求中任一项所述的方法,其中,所述聚合引发剂是氧化还原引发剂,优选过硫酸盐。
9.根据前述权利要求中任一项所述的方法,其中,所述表面活性剂是烷基硫酸盐。
10.用于氢化不饱和的基于二烯的聚合物的方法,其中,氢化根据前述权利要求中任一项所述的基于二烯的胶乳粒子。
11.根据前述权利要求中至少一项所述的聚合物作为橡胶或橡胶中间体的用途。
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EP09168713.7 | 2009-08-26 | ||
EP09168713A EP2289991A1 (en) | 2009-08-26 | 2009-08-26 | Nano-sized diene-based polymer latex particles |
PCT/IB2010/053844 WO2011024140A1 (en) | 2009-08-26 | 2010-08-26 | Nano-sized diene-based polymer latex particles |
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CN102498139A true CN102498139A (zh) | 2012-06-13 |
CN102498139B CN102498139B (zh) | 2016-10-19 |
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US (2) | US20110184120A1 (zh) |
EP (2) | EP2289991A1 (zh) |
JP (1) | JP5696145B2 (zh) |
KR (1) | KR101749362B1 (zh) |
CN (1) | CN102498139B (zh) |
BR (1) | BR112012004119A2 (zh) |
CA (1) | CA2772200A1 (zh) |
MX (1) | MX2012002303A (zh) |
SG (1) | SG178574A1 (zh) |
TW (1) | TWI525116B (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106866885A (zh) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | 一种小粒径聚丁二烯胶乳的制备方法 |
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CN115667418B (zh) * | 2020-05-19 | 2024-07-12 | 毕克化学有限公司 | 热固性聚合物粉末 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4508862A (en) * | 1981-12-04 | 1985-04-02 | Bayer Aktiengesellschaft | Process for the production of fluid aqueous dispersions of polymers of conjugated dienes |
US5651995A (en) * | 1994-09-30 | 1997-07-29 | Nippon Zeon Co., Ltd. | Highly saturated nitrile rubber, process for producing same, vulcanizable rubber composition, aqueous emulsion and adhesive composition |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3454644A (en) | 1966-05-09 | 1969-07-08 | Shell Oil Co | Homogeneous hydrogenation process employing a complex of ruthenium or osmium as catalyst |
US3600349A (en) | 1969-05-01 | 1971-08-17 | Copolymer Rubber & Chem Corp | Method for controlling reaction rate in aqueous emulsion polymerization to form elastomeric polymers |
US3690349A (en) | 1971-03-15 | 1972-09-12 | American Eng Co Ltd | Reinforcing rod machine |
US3759859A (en) * | 1971-07-19 | 1973-09-18 | Union Oil Co | Emulsion copolymerization |
US4082714A (en) * | 1972-11-30 | 1978-04-04 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the emulsion polymerization of conjugated dienes |
DE2418419C3 (de) * | 1974-04-17 | 1987-07-09 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung carboxylgruppenhaltiger Latices |
JPS55120614A (en) * | 1979-03-12 | 1980-09-17 | Japan Synthetic Rubber Co Ltd | Unsaturated nitrile-conjugated diene copolymer |
US4378272A (en) * | 1981-06-24 | 1983-03-29 | Gaf Corporation | Water purifying latex binder |
US4452950A (en) | 1983-02-22 | 1984-06-05 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form |
JPS6163794A (ja) * | 1984-08-31 | 1986-04-01 | 日本ゼオン株式会社 | 紙塗被用組成物 |
JPS6183093A (ja) | 1984-09-29 | 1986-04-26 | Japan Synthetic Rubber Co Ltd | 感圧複写紙用塗被組成物 |
JP2717229B2 (ja) * | 1988-06-21 | 1998-02-18 | 旭化成工業株式会社 | 樹脂補強用ゴム粒子及び補強樹脂組成物 |
JP2732273B2 (ja) * | 1988-12-29 | 1998-03-25 | 日本ゼオン株式会社 | ニトリル基含有水素化重合体の製造方法 |
EP0430349A3 (en) | 1989-11-27 | 1991-10-16 | Stamicarbon B.V. | Process for the polymerization and recovery of nitrile rubber containing high bound acrylonitrile |
JP2700499B2 (ja) * | 1989-12-26 | 1998-01-21 | 三井東圧化学株式会社 | 塗被紙用組成物 |
US5039737A (en) | 1990-02-22 | 1991-08-13 | The Goodyear Tire & Rubber Company/Olin Corp. | Ozonolysis of hydrogenated latices |
US5057581A (en) | 1990-05-02 | 1991-10-15 | University Of Waterloo | Polymer hydrogenation process |
FR2712296B1 (fr) * | 1993-11-10 | 1996-01-12 | Rhone Poulenc Chimie | Liant latex pour composition de revêtement. |
US5424356A (en) | 1994-03-21 | 1995-06-13 | The Goodyear Tire & Rubber Company | Process for the preparation of hydrogenated rubber |
KR100201228B1 (ko) | 1995-10-17 | 1999-06-15 | 박찬구 | 리빙중합체의 수첨방법 |
US5705571A (en) | 1996-05-17 | 1998-01-06 | Taiwan Synthetic Rubber Corporation | Process for selective hydrogenation of conjugated diene polymer |
WO2000009568A1 (en) | 1998-08-11 | 2000-02-24 | Dsm N.V. | Process for the hydrogenation of a polymer composed of diene monomer units and nitrile group containing monomer units and hydrogenated polymer |
KR100348761B1 (ko) | 1999-11-26 | 2002-08-13 | 금호석유화학 주식회사 | 공액디엔을 포함하는 중합체의 선택적 수소화 방법 |
NL1014197C2 (nl) | 2000-01-27 | 2001-07-30 | Dsm Nv | Werkwijze voor de hydrogenering van een polymeer dat is opgebouwd uit dieenmonomeereenheden en monomeereenheden die een nitrilgroep bevatten. |
DE10008418A1 (de) * | 2000-02-23 | 2001-08-30 | Bayer Ag | ABS-Formmassen mit verbesserter Verarbeitbarkeit und hohem Glanz |
EP1215251B1 (en) * | 2000-12-12 | 2005-06-15 | Konica Corporation | Pigment dispersion liquid for ink jetting |
US20040242800A1 (en) * | 2001-09-21 | 2004-12-02 | Kazuhiro Takahashi | Method of hydrogenating conjugated diene polymer, hydrogenation catalyst system, and composition of basic conjugated diene polymer |
WO2003027157A1 (en) * | 2001-09-24 | 2003-04-03 | Dow Global Technologies Inc. | Improved carpet backing latex |
JP3907992B2 (ja) * | 2001-10-10 | 2007-04-18 | 旭化成ケミカルズ株式会社 | 新規な共重合体ラテックスの製造方法 |
US7345115B2 (en) | 2005-03-18 | 2008-03-18 | Lanxess Inc. | Organic solvent-free hydrogenation of diene-based polymers |
CA2501203A1 (en) * | 2005-03-18 | 2006-09-18 | Lanxess Inc. | Hydrogenation of diene-based polymer latex |
US7385010B2 (en) | 2005-03-18 | 2008-06-10 | Lanxess Inc. | Hydrogenation of diene-based polymer latex |
EP2289947A1 (en) * | 2009-08-26 | 2011-03-02 | University Of Waterloo | Nano-sized hydrogenated diene-based latex particles |
-
2009
- 2009-08-26 EP EP09168713A patent/EP2289991A1/en not_active Withdrawn
-
2010
- 2010-08-24 US US12/862,058 patent/US20110184120A1/en not_active Abandoned
- 2010-08-26 KR KR1020127007532A patent/KR101749362B1/ko active IP Right Grant
- 2010-08-26 BR BR112012004119A patent/BR112012004119A2/pt not_active IP Right Cessation
- 2010-08-26 WO PCT/IB2010/053844 patent/WO2011024140A1/en active Application Filing
- 2010-08-26 MX MX2012002303A patent/MX2012002303A/es unknown
- 2010-08-26 US US13/392,117 patent/US9359490B2/en not_active Expired - Fee Related
- 2010-08-26 CA CA2772200A patent/CA2772200A1/en not_active Abandoned
- 2010-08-26 EP EP10811355.6A patent/EP2470577B1/en not_active Not-in-force
- 2010-08-26 TW TW099128677A patent/TWI525116B/zh not_active IP Right Cessation
- 2010-08-26 SG SG2012013413A patent/SG178574A1/en unknown
- 2010-08-26 JP JP2012526174A patent/JP5696145B2/ja not_active Expired - Fee Related
- 2010-08-26 CN CN201080037904.1A patent/CN102498139B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4508862A (en) * | 1981-12-04 | 1985-04-02 | Bayer Aktiengesellschaft | Process for the production of fluid aqueous dispersions of polymers of conjugated dienes |
US5651995A (en) * | 1994-09-30 | 1997-07-29 | Nippon Zeon Co., Ltd. | Highly saturated nitrile rubber, process for producing same, vulcanizable rubber composition, aqueous emulsion and adhesive composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106866885A (zh) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | 一种小粒径聚丁二烯胶乳的制备方法 |
CN106866885B (zh) * | 2015-12-11 | 2019-09-03 | 中国石油天然气股份有限公司 | 一种小粒径聚丁二烯胶乳的制备方法 |
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SG178574A1 (en) | 2012-03-29 |
MX2012002303A (es) | 2012-06-01 |
TW201113300A (en) | 2011-04-16 |
JP2013503232A (ja) | 2013-01-31 |
CN102498139B (zh) | 2016-10-19 |
JP5696145B2 (ja) | 2015-04-08 |
US20110184120A1 (en) | 2011-07-28 |
EP2470577A1 (en) | 2012-07-04 |
KR101749362B1 (ko) | 2017-06-20 |
EP2470577A4 (en) | 2013-04-17 |
US20120270047A1 (en) | 2012-10-25 |
BR112012004119A2 (pt) | 2016-03-15 |
EP2470577B1 (en) | 2018-03-14 |
US9359490B2 (en) | 2016-06-07 |
EP2289991A1 (en) | 2011-03-02 |
WO2011024140A1 (en) | 2011-03-03 |
KR20120068884A (ko) | 2012-06-27 |
CA2772200A1 (en) | 2011-03-03 |
TWI525116B (zh) | 2016-03-11 |
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