JP6688319B2 - イタコナート/ブタジエン共重合体型のバイオエンジニアリングゴム及びその調製方法 - Google Patents
イタコナート/ブタジエン共重合体型のバイオエンジニアリングゴム及びその調製方法 Download PDFInfo
- Publication number
- JP6688319B2 JP6688319B2 JP2017557307A JP2017557307A JP6688319B2 JP 6688319 B2 JP6688319 B2 JP 6688319B2 JP 2017557307 A JP2017557307 A JP 2017557307A JP 2017557307 A JP2017557307 A JP 2017557307A JP 6688319 B2 JP6688319 B2 JP 6688319B2
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- JP
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- Prior art keywords
- itaconate
- rubber
- sodium
- butadiene
- butadiene copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 136
- 229920001971 elastomer Polymers 0.000 title claims description 112
- 239000005060 rubber Substances 0.000 title claims description 110
- 229920001577 copolymer Polymers 0.000 title claims description 75
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims description 51
- 238000002360 preparation method Methods 0.000 title description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000000344 soap Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008117 stearic acid Substances 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 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 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 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 6
- 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 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 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 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 4
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000006378 damage Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 3
- 239000012936 vulcanization activator Substances 0.000 claims description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000013040 rubber vulcanization Methods 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 claims description 2
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- DYYFCJRYZVHEKQ-UHFFFAOYSA-N 3-butoxycarbonylbut-3-enoic acid Chemical compound CCCCOC(=O)C(=C)CC(O)=O DYYFCJRYZVHEKQ-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 229920000126 latex Polymers 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- 244000043261 Hevea brasiliensis Species 0.000 description 10
- 229920003052 natural elastomer Polymers 0.000 description 10
- 229920001194 natural rubber Polymers 0.000 description 10
- 239000004816 latex Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PPPIIDSEUCJLLC-UHFFFAOYSA-N 3-(3-methylbutoxycarbonyl)but-3-enoic acid Chemical compound CC(C)CCOC(=O)C(=C)CC(O)=O PPPIIDSEUCJLLC-UHFFFAOYSA-N 0.000 description 5
- RTTAGBVNSDJDTE-UHFFFAOYSA-N 4-ethoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCOC(=O)CC(=C)C(O)=O RTTAGBVNSDJDTE-UHFFFAOYSA-N 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 238000010057 rubber processing Methods 0.000 description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- VKJQZSSBQZSTIM-UHFFFAOYSA-N hydroxymethanesulfonic acid;sodium Chemical compound [Na].OCS(O)(=O)=O VKJQZSSBQZSTIM-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- RTIRICWZVNTCND-UHFFFAOYSA-N 3-pentoxycarbonylbut-3-enoic acid Chemical compound CCCCCOC(=O)C(=C)CC(O)=O RTIRICWZVNTCND-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- -1 sodium fatty acid Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- NRSMWHGLCNBZSO-UHFFFAOYSA-N 2-ethylidenebutanedioic acid Chemical compound CC=C(C(O)=O)CC(O)=O NRSMWHGLCNBZSO-UHFFFAOYSA-N 0.000 description 1
- KUDZDPMCQYHSSJ-UHFFFAOYSA-N 2-pentylidenebutanedioic acid Chemical compound CCCCC=C(C(O)=O)CC(O)=O KUDZDPMCQYHSSJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- SAJLIOLJORWJIO-UHFFFAOYSA-N hydroxymethanesulfinic acid;sodium Chemical compound [Na].OCS(O)=O SAJLIOLJORWJIO-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/16—Esters having free carboxylic acid groups, e.g. monoalkyl maleates or fumarates
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
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- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
Description
重合装置内にイタコナート、乳化剤、電解質、活性剤、脱イオン水を加え、重合装置を密封し、まず真空引きしてから窒素ガスを吹き込み、1〜5回操作し;最終回の窒素ガスを吹き込んだ後ブタジエン、脱酸素剤及び開始剤を重合装置内に加え、1〜20℃、0.1〜5MPaの圧力条件下で5〜15時間反応させ;停止剤を加えて反応を停止させる。イタコナート、ブタジエン、乳化剤、電解質、活性剤、脱酸素剤、開始剤、停止剤及び脱イオン水の質量比が100:1〜100:1〜10:0.1〜5:0.01〜5:0.1〜5:0.01〜5:1〜10:100〜1000である。乳化液は乳化破壊や乾燥を経てイタコナート/ブタジエン共重合体型のバイオエンジニアリングエラストマーの生ゴムが得られ、生ゴムの数平均分子量が53000〜1640000で、重量平均分子量が110000〜2892000である。
硫黄を架橋剤とし、従来の加硫系の加硫剤/促進剤を利用し、140〜160℃において金型でプレス加硫してイタコナート/ブタジエン共重合体型のバイオエンジニアリングゴムが製造される。
スチレンブタジエンゴム(SBR1502)100g、酸化亜鉛5g、ステアリン酸2g、硫黄1g、促進剤M0.7g、促進剤CZ1g、シリカ60g及びSi696gをオープンロール機上で均一に混合して混練物が得られ、混練物が150℃において金型でプレス加硫してシリカ/スチレンブタジエンゴム複合材料が調製された。
天然ゴム(雲標1#)100g、酸化亜鉛5g、ステアリン酸2g、硫黄1g、促進剤M0.7g、促進剤CZ1g、カーボンブラックN33060gをオープンロール機上で均一に混合して混練物が得られ、混練物が150℃において金型でプレス加硫してカーボンブラック/天然ゴム複合材料が調製された。
(実施例9〜実施例15)
スチレンブタジエンゴム(SSBR2503)100g、酸化亜鉛5g、ステアリン酸2g、硫黄1g、促進剤M0.7g、促進剤CZ1g、シリカ60g及びSi696gをオープンロール機上で均一に混合して混練物が得られ、混練物が150℃において金型でプレス加硫してシリカ/スチレンブタジエンゴム複合材料が調製された。
天然ゴム(スモークシートゴム)100g、酸化亜鉛5g、ステアリン酸2g、硫黄1g、促進剤M0.7g、促進剤CZ1g、カーボンブラックN33060gをオープンロール機上で均一に混合して混練物が得られ、混練物が150℃において金型でプレス加硫してカーボンブラック/天然ゴム複合材料が調製された。
Claims (4)
- イタコナート/ブタジエン共重合体型のバイオエンジニアリングゴムであって、イタコナートとブタジエンを乳化重合によって成る共重合体が化学架橋を経て成り、前記イタコナート/ブタジエン共重合体の数平均分子量が53000〜1640000で、重量平均分子量が110000〜2892000であるイタコナート/ブタジエン共重合体型のバイオエンジニアリングゴムの調整方法であって、その製造ステップは、次通りとし、
A:イタコナートとブタジエンの乳化重合反応
重合装置内にイタコナート、乳化剤、電解質、活性剤、脱イオン水を加え、重合装置を密封し、まず真空引きしてから窒素ガスを吹き込み、1〜5回操作し;最終回の窒素ガスを吹き込んだ後ブタジエン、脱酸素剤及び開始剤を重合装置内に加え、1〜20℃、0.1〜5MPaの圧力条件下で5〜15時間反応させ;停止剤を加えて反応を停止させ;イタコナート、ブタジエン、乳化剤、電解質、活性剤、脱酸素剤、開始剤、停止剤及び脱イオン水の質量比は、100:1〜100:1〜10:0.1〜5:0.01〜5:0.1〜5:0.01〜5:1〜10:100〜1000であり;乳化液は乳化破壊・乾燥を経てイタコナート/ブタジエン共重合体型のバイオエンジニアリングエラストマーの生ゴムが得られ、生ゴムの数平均分子量が53000〜1640000で、重量平均分子量が110000〜2892000であり;
前記イタコナートの分子式は、下式で表わし、
式中、R1、R2は、H原子或いはC1〜10のアルキルであり、R1、R2が同一又は異なり;
B、ゴム加硫プロセス
硫黄を架橋剤とし、加硫活性剤と加硫促進剤を利用し、140〜160℃において金型でプレス加硫してイタコナート/ブタジエン共重合体型のバイオエンジニアリングゴムが製造され、
この時、
前記乳化剤としては、不均斉化ロジンのナトリウム石鹸、不均斉化ロジンのカリウム石鹸、脂肪酸ナトリウム石鹸、脂肪酸カリウム石鹸、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウムのうちのいずれか1種又は複数種の混合物であって、
前記加硫活性剤としては酸化亜鉛又はステアリン酸、加硫促進剤としては2−メルカプトベンゾチアゾール(以下、促進剤M)、N−シクロヘキシル−2−ベンゾチアゾールスルフェンアミド(以下、促進剤CZ)、又はジフェニルグアニジン(以下、促進剤D)のうちのいずれか1種又は複数種の混合物であって、
前記電解質としては、塩化カリウム、リン酸カリウム、エチレンジアミン四酢酸、ナトリウムメチルジナフタレンスルホネート(TAOM−L)、リン酸、水酸化カリウムのうちのいずれか1種又は複数種の混合物であって、
前記活性剤としては、ヒドロキシメタンスルホン酸ナトリウムとエチレンジアミン四酢酸鉄(EDTA−Fe)の混合物、或いはヒドロキシメタンスルホン酸ナトリウムとエチレンジアミン四酢酸鉄ナトリウム(EDTA−Fe・Na)の混合物が挙げられ;前記開始剤としては、パラメンタンハイドロパーオキサイド、tert−ブチルヒドロペルオキシド或いはクミルヒドロペルオキシドであって、
前記停止剤としては、ジメチルジチオカルバミン酸ナトリウム、ジエチルジチオカルバミン酸ナトリウム、ヒドロキシルアミン或いは多硫化ナトリウムであって、
前記調整方法において、
得られた生ゴムと、酸化亜鉛、ステアリン酸、硫黄、促進剤M、促進剤CZ、カーボンブラックN330の混練物を用いる
ことを特徴とする方法。 - R1、R2は、n-ブチル、n-ペンチル或いはイソペンチルであることを特徴とする請求項1に記載の方法。
- イタコナートとブタジエンモノマーの質量比は、100:10〜60であることを特徴とする請求項1に記載の方法。
- 前記イタコナート/ブタジエン共重合体型のバイオエンジニアリングゴムが、タイヤトレッド或いはベルトコンベアに用いられることを特徴とする請求項1ないし3のいずれか一項に記載の方法。
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