WO2015186667A1 - 共役ジエン系重合体、その製造方法及びそれを含む組成物 - Google Patents
共役ジエン系重合体、その製造方法及びそれを含む組成物 Download PDFInfo
- Publication number
- WO2015186667A1 WO2015186667A1 PCT/JP2015/065787 JP2015065787W WO2015186667A1 WO 2015186667 A1 WO2015186667 A1 WO 2015186667A1 JP 2015065787 W JP2015065787 W JP 2015065787W WO 2015186667 A1 WO2015186667 A1 WO 2015186667A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conjugated diene
- compound
- polymer
- diene polymer
- weight
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 208
- 150000001993 dienes Chemical class 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 125000003368 amide group Chemical group 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 85
- 229920001971 elastomer Polymers 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 150000002900 organolithium compounds Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 238000004737 colorimetric analysis Methods 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 56
- 238000006116 polymerization reaction Methods 0.000 description 42
- 238000005984 hydrogenation reaction Methods 0.000 description 41
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- -1 and then extruded Substances 0.000 description 36
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 28
- 229920002554 vinyl polymer Polymers 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 20
- 239000005060 rubber Substances 0.000 description 19
- 229920005992 thermoplastic resin Polymers 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- 229920001955 polyphenylene ether Polymers 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 16
- 229920001400 block copolymer Polymers 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 11
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 239000011976 maleic acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 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
- 150000003672 ureas Chemical class 0.000 description 3
- 0 **(CC#[N+][N-]C*(*)I)[N+](*)[O-] Chemical compound **(CC#[N+][N-]C*(*)I)[N+](*)[O-] 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- YVLJEXBGMVDKBR-UHFFFAOYSA-N 1,10-dichloro-7-methyldec-1-ene Chemical compound ClCCCC(C)CCCCC=CCl YVLJEXBGMVDKBR-UHFFFAOYSA-N 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- NFJSYLMJBNUDNG-UHFFFAOYSA-N 1,3-dipropylimidazolidin-2-one Chemical compound CCCN1CCN(CCC)C1=O NFJSYLMJBNUDNG-UHFFFAOYSA-N 0.000 description 1
- XFPRAPMGYIQRIT-UHFFFAOYSA-N 1-butyl-3-methylimidazolidin-2-one Chemical compound CCCCN1CCN(C)C1=O XFPRAPMGYIQRIT-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- UZXXRFKXXJEKJA-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidin-2-one Chemical compound CCN1CCN(C)C1=O UZXXRFKXXJEKJA-UHFFFAOYSA-N 0.000 description 1
- BTXWBRFMGNZXBM-UHFFFAOYSA-N 1-methyl-3-propylimidazolidin-2-one Chemical compound CCCN1CCN(C)C1=O BTXWBRFMGNZXBM-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- UYQYTUYNNYZATF-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethyl)cyclohexa-1,3-dien-1-ol Chemical compound CCCCCCCCSCC1=CC=C(O)C(C)(CSCCCCCCCC)C1 UYQYTUYNNYZATF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical compound O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical compound C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and 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
- C08F36/04—Homopolymers and 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
- C08F36/14—Homopolymers and 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 containing elements other than carbon and hydrogen
-
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- 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
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
-
- 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
- C08L9/06—Copolymers with styrene
Definitions
- the present invention relates to a conjugated diene polymer and a production method thereof.
- hydrogenated conjugated diene polymers having a nitrogen-containing functional group at the end are excellent in heat resistance and weather resistance in addition to excellent resilience, low temperature characteristics, and compatibility, and are therefore thermoplastic and rubbery. It is widely used as a modifier for polymers, in particular, high-molecular substances such as engineering resins having high heat distortion resistance.
- the present inventors have obtained a conjugated diene polymer having excellent color tone by having 40% or more of the terminals of the conjugated diene polymer have a specific structure.
- the composition of the conjugated diene polymer and a high-molecular substance such as a thermoplastic resin has excellent appearance properties such as mechanical properties (impact resistance, etc.) and color tone, and has an excellent balance of these properties.
- the step of polymerizing a monomer containing at least one conjugated diene monomer using an organolithium compound as an initiator, and the ratio of the polymerization initiator lithium and a urea derivative having a specific structure are within a specific range.
- the step of adding the urea derivative as described above a conjugated diene polymer having a main structure having an amino group having a specific structure and excellent mechanical properties and appearance characteristics can be obtained.
- the invention was completed. That is, the present invention is as follows.
- P represents a conjugated diene polymer containing at least one conjugated diene monomer
- R 1 and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
- P represents a conjugated diene polymer containing at least one conjugated diene monomer
- R 1 and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
- a process for producing a conjugated diene polymer comprising:
- FIG. 1 shows an example of the results of gas chromatographic measurement performed to determine the weight ratio (wt%) of compound (II) to the total of compound (II) and compound (III).
- the conjugated diene polymer in this embodiment contains at least one conjugated diene monomer.
- the conjugated diene monomer 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-heptadiene and the like can be used.
- the structure is, for example, as represented by the general formula (AB) n, (AB) nA, B- (AB) n (wherein A is vinyl) A polymer block mainly composed of an aromatic compound, and B is a polymer block mainly composed of a conjugated diene, and the boundary between the A block and the B block does not necessarily need to be clearly distinguished, and n is An integer of 1 or more, preferably an integer of 1 to 5.
- the polymer block A mainly composed of a vinyl aromatic compound is a copolymer block of a vinyl aromatic compound and a conjugated diene and / or a vinyl aromatic containing a vinyl aromatic compound of 50 wt% or more, preferably 70 wt% or more.
- the hydrocarbon homopolymer block is shown.
- the polymer block B mainly composed of a conjugated diene is a copolymer block of a conjugated diene and a vinyl aromatic compound and / or a conjugated diene homopolymer block containing 50 wt% or more, preferably 60 wt% or more of a conjugated diene. .
- the vinyl aromatic compound in the copolymer block may be distributed uniformly or in a tapered shape.
- copolymer block part a part where the vinyl aromatic compound is uniformly distributed and / or a part where the vinyl aromatic compound is distributed in a tapered shape may coexist. Furthermore, a plurality of portions having different vinyl aromatic compound contents may coexist in the copolymer block portion.
- the block copolymer used in the present invention may be an arbitrary mixture of block copolymers represented by the above general formula.
- the conjugated diene polymer preferably includes a terminal having a structure represented by the following formula (I) as the terminal having the amino group and the amide group. 40% or more of the terminals may have a structure represented by the following formula (I).
- the terminal structure of the conjugated diene polymer can be analyzed by the GPC method described later.
- the ratio (A) of compound (II) to the total of compound (II) and compound (III) is preferably 0.6% by weight or less, more preferably 0.3% by weight or less, and 0.15% by weight or less. Further preferred.
- Compound (II) and compound (III) may be added after the start of polymerization of the monomer constituting the conjugated diene polymer.
- the monomer It is preferable to carry out after the polymerization reaction has progressed and before hydrogenation.
- a supported heterogeneous hydrogen catalyst (2) a so-called Ziegler type using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum
- a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used.
- Specific examples of hydrogenation catalysts include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Patent Publication No. 2-9041 can be used.
- Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.
- the total hydrogenation rate in the hydrogenated conjugated diene polymer can be arbitrarily selected according to the purpose and is not particularly limited.
- 70% or more, more preferably 80% or more, particularly preferably 95% or more of the unsaturated double bond based on the conjugated diene compound in the conjugated diene polymer may be hydrogenated or only partly. May be hydrogenated.
- the hydrogenation rate be 10% or more and less than 70%, or 15% or more and less than 65%, or 20% or more and less than 60% as desired.
- the hydrogenation rate of the hydrogenated conjugated diene polymer is measured by a nuclear magnetic resonance apparatus (NMR).
- the polymer composition of this embodiment has a structure in which 40% or more of the terminals have an amino group and an amide group, and a conjugated diene having a yellowness index b * value of 15 or less measured by a colorimetric color difference meter.
- a component (a) which is a polymer, and at least one component (b) selected from the group consisting of a thermoplastic resin and a rubber-like polymer.
- the composition ranges from 1 to 99 parts by weight of component (a) and 99 to 1 part by weight of component (b), preferably 5 to 95 parts by weight of component (a) and 95 to 5 parts by weight of component (b). It is a range and the range suitable for various molding materials can be selected.
- thermoplastic resins and rubbery polymers may be used in combination of two or more as required.
- thermoplastic resin components or the rubber-like polymer components may be used, or the thermoplastic resin and the rubber-like polymer may be used in combination.
- the conjugated diene polymer corresponding to the component (a) does not correspond to the component (b).
- additives can be blended as necessary.
- the type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
- metal hydroxides silica-based inorganic fillers, inorganic fillers such as metal oxides, organic fillers, antioxidants, UV absorbers and light stabilizers, stearic acid, behenic acid, zinc stearate, calcium stearate , Lubricants such as magnesium stearate and ethylene bisstearamide, mold release agents, paraffin, plasticizers, flame retardants, antistatic agents, reinforcing materials such as organic fibers, carbon fibers, metal whiskers, pigments, colorants, etc. .
- the method for producing the polymer composition of the present invention is not particularly limited, and a known method can be used.
- a melt kneading method using a general mixer such as a Banbury mixer, a short screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., each component dissolving or dispersing mixer, solvent heating The removal method is used.
- a melt kneading method using an extruder is preferred from the viewpoint of productivity and good kneading properties.
- a pellet form, a sheet form, a strand form, a chip form etc. can be mentioned.
- it can also be directly molded after melt-kneading.
- the polymer composition of the present invention can be used as it is or as a composition in which various additives are blended.
- extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum It can be processed into a practically useful molded product by molding, rotational molding, powder slush molding, foam molding, laminate molding, calendar molding, blow molding, and the like. If necessary, processing such as firing, powder, stretching, adhesion, printing, painting, plating, etc. may be performed.
- This molding method can be used as a wide variety of molded products such as sheets, films, injection molded products of various shapes, hollow molded products, vacuum molded products, extrusion molded products, foamed molded products, nonwoven fabrics and fibrous molded products, and synthetic leather.
- molded products include food packaging materials, medical instrument materials, household electrical appliances and parts thereof, electronic devices and parts thereof, automobile parts, industrial parts, household goods, materials such as toys, footwear materials, and adhesive / adhesive materials. It can be used for materials and asphalt modifiers.
- Bonded styrene content depends on the styrene-butadiene block copolymer before hydrogenation as a specimen, the sample as a chloroform solution, and the phenyl group of styrene.
- the bound styrene content was measured by UV 254 nm absorption.
- the weight average molecular weight and the number average molecular weight were obtained from the obtained GPC chromatogram, and the molecular weight distribution value was obtained.
- the coupling rate was determined by using polybutadiene before addition of the nitrogen-containing cyclic compound as a specimen, and a polystyrene gel column (column: PLgel MiniMix-C ⁇ 3, column oven temperature 35 ° C .: 865-CO manufactured by JASCO Corporation)
- a chromatograph of GPC WATERS 2695
- THF flow rate 0.35 mL
- sample concentration 0.1% by weight
- injection amount of 50 ⁇ L an injection amount of 50 ⁇ L
- an RI detector Waters 2414
- Ratio in which the terminal is an amino group having a specific structure wt%
- a sample solution containing a sample and standard polystyrene having a molecular weight of 5000 (polystyrene does not adsorb to the column) is applied to a GPC column using silica-based gel as a packing material by applying the property of adsorbing a component having an amino group having a specific structure at the end.
- the sample was dissolved in 10 mL of 20 mL of THF together with 5 mg of standard polystyrene and measured by injecting 100 ⁇ L.
- it calculated from the following formula from the area (%) measured with a polystyrene gel column and a silica gel column.
- a Area (%) of the total polymer measured with polystyrene gel (PLgel)
- b Area (%) of low molecular weight internal standard PS (polystyrene) measured with polystyrene gel (PLgel)
- c Area (%) of total polymer measured with silica-based column (Zorbax)
- d Area (%) of low molecular weight internal standard PS measured with a silica-based column (Zorbax)
- Odor sensory evaluation of conjugated diene polymer 20 g of block copolymer composition is put in a glass bottle, covered with aluminum foil, heated at 160 ° C. for 30 minutes in a heat dryer, and then heated in a dryer. The product was taken out from the cap, capped with a heat resistant lid, and allowed to stand at room temperature (about 25 ° C.) for 30 minutes.
- the odor level of the odor of the polymer 8 described later was set to 5.
- the relative odor level of the polymer as compared to this reference material was evaluated between 1 (weak odor) and 10 (strong odor).
- the sensory evaluation was performed by 10 or more persons, and if the average value of the odor level was 3.0 or less, it was judged that the performance was practically excellent, and if it was 4.8 or less, the performance was practically sufficient.
- Components of polymer composition, etc. (1) Component (a) -thermoplastic resin, functional group-containing PPE (2) Component (b) -conjugated diene polymer Hydrogenated polymer: Polymer 1, Polymer 7, Polymer 11, Polymer 12 (3) Component (c) -thermoplastic resin Polyamide 6: Ube nylon 6-1013B (manufactured by Ube Industries, Ltd.)
- styrene After the styrene is completely polymerized, 640 g of styrene and 1200 g of 1,3-butadiene are added simultaneously, and 5 minutes later, 3600 g of 1,3-butadiene is continuously added over 10 minutes. Butadiene was completely copolymerized and 1120 g of styrene was added to completely polymerize styrene. Next, 17.3 g of 1,3-dimethyl-2-imidazolidinone containing 0.12 wt% of 1,3-dimethyl-2-imidazolinone was added, and 4.84 g of methanol was added after 15 minutes to complete the polymerization. I let you.
- Example 3 Comparative Example 2 (Preparation of polymer 3) Copolymerization was performed in the order of the polymerization operation steps described in Table 1, using a stirrer having an internal volume of 100 liters and a tank reactor with a jacket. 29400 g of purified cyclohexane, 4.4 g of tetrahydrofuran (THF), 1.68 g of tetramethylethylenediamine, 720 g of styrene and 5040 g of 1,3-butadiene were mixed and stirred at 100 rpm to adjust the polymerization start temperature to 40 ° C.
- THF tetrahydrofuran
- Example 5 Comparative Example 4 (Preparation of polymer 5) Copolymerization was carried out in the order of the polymerization operation steps described in Table 1, using a stirrer having an internal volume of 12 liters and a jacketed tank reactor. 4000 g of purified cyclohexane, 0.60 g of tetrahydrofuran (THF) and 1100 g of 1,3-butadiene were charged, mixed and stirred at 100 rpm, and the polymerization start temperature was adjusted to 55 ° C. 20% by weight of n-butyllithium in cyclohexane (1.09 g of n-butyllithium) was added to initiate the polymerization.
- THF tetrahydrofuran
- Hydrogenation catalyst I was added to the obtained copolymer in an amount of 130 ppm by weight as titanium with respect to the weight of the copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. 1g of methanol was added after completion
- Example 7 Comparative Example 5, Reference Example 3, Reference Example 4
- a poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight of 22,000 and a polymer one-end chain having a phenolic hydroxyl group was synthesized, and 1 weight of maleic anhydride per 100 weight parts of the polyphenylene ether.
- the mixture was melt kneaded using a twin-screw extruder with a vent port (ZSK-25; made by WERNER & PFLIDEERER, Germany) heated to 250 to 300 ° C, and unreacted maleic anhydride was removed under reduced pressure.
- the conjugated diene polymer according to the present invention has an excellent color tone, and 40% or more of its terminals have an amino group and an amide group.
- the conjugated diene polymer and a thermoplastic resin or rubbery polymer Compositions with other polymer substances such as the above are excellent in appearance such as color tone, and mechanical properties such as impact resistance and molding processability. Utilizing these characteristics, food packaging materials, medical instrument materials, home appliances and parts thereof, electronic devices and parts thereof, automotive parts, industrial parts, household goods, materials such as toys, footwear materials, adhesives and adhesives Can be used for materials and asphalt modifiers.
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)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
その為、これら共役ジエン系重合体と熱可塑性樹脂などの高分子物質との組成物を用い、優れた機械的特性、色調などの外観特性(透明感、或いは白色度の強い)を有し、かつこれらの物性バランスに優れた着色成型体を安定的に得るのは困難な状況であり、未だ改善すべき余地がある。
また、有機リチウム化合物を開始剤として少なくとも一種の共役ジエン単量体を含有する単量体を重合させる工程と、重合開始剤のリチウムと特定の構造を有する尿素誘導体の比率が特定範囲内となるように該尿素誘導体を添加する工程と、を含む方法によって、その主たる末端が特定構造のアミノ基を有し、機械的物性や外観特性に優れる共役ジエン系重合体が得られることを見出し、本発明を完成するにいたった。
すなわち、本発明は、以下の通りである。
下記式(II)で表される化合物(II)と下記式(III)で表される化合物(III)を添加する工程と、
を含む共役ジエン系重合体の製造方法であって、
[式中、R5とR6は各々独立に炭素数1~20の炭化水素基を表す。]
数式1に示されるように、化合物(II)と化合物(III)の合計に対する化合物(II)の重量比率(%)を(A)とし、数式2に示されるように、重合開始剤のリチウムに対する化合物(II)と化合物(III)のモル比を(B)としたときに、数式3に示されるように、(A)×(B)が0.5以下となるように、重合開始剤、化合物(II)、及び/又は化合物(III)の添加量を調節する、製造方法。
数式1:(A)=(化合物(II)/(化合物(II)+化合物(III)))×100
数式2:(B)=([化合物(II)]+[化合物(III)])/[Li]
数式3:(A)×(B)≦0.5
(b)熱可塑性重合体及び/又はゴム状重合体99~1重量部と、
を含む重合体組成物。
本実施形態における共役ジエン系重合体は、少なくとも一種の共役ジエン単量体を含む。共役ジエン単量体としては、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3ブタジエン、1,3-ペンタジエン、1,3-ヘプタジエンなどを用いることができる。
b*値は、前述の式(IV)で表される変性共役ジエン系重合体の含有量を減らすことにより、制御することができる。式(IV)で表される変性共役ジエン系重合体の含有量は、後述する化合物(II)と化合物(III)を添加する工程において、化合物(II)の添加量を調整することにより制御できる。
黄色度の指標b*値は測色色差計で測定され、具体的には、3mm厚みの共役ジエン系重合体サンプルを、スガ試験機製の測色計SM-7型(45°拡散方式)を用いて測定することができる。
上述した本実施形態の共役ジエン系重合体は、以下の製造方法により製造することができる。即ち、有機リチウム化合物を開始剤として、少なくとも一種の共役ジエン単量体を含有する単量体を重合させる工程と、下記式(II)で表される化合物(II)と下記式(III)で表される化合物(III)を添加する工程と、を含み、
数式1:(A)=(化合物(II)/(化合物(II)+化合物(III)))×100
数式2:(B)=([化合物(II)]+[化合物(III)])/[Li]
数式3:(A)×(B)≦0.5
本実施形態の重合体組成物は、末端の40%以上がアミノ基及びアミド基を有する構造を有し、かつ測色色差計で測定される黄色度の指標b*値が15以下の共役ジエン系重合体である成分(a)と、熱可塑性樹脂及びゴム状重合体からなる群より選ばれる少なくとも一種の成分(b)と、を含む。その組成は、成分(a)1~99重量部、成分(b)99~1重量部の範囲であり、好ましくは成分(a)5~95重量部、成分(b)95~5重量部の範囲であり、各種成型材料に適した範囲を選択することができる。
化合物(II)と化合物(III)の合計に対する化合物(II)の重量比率(wt%)は、下記ガスクロマトグラフ測定条件により測定し(測定結果の一例を図1に示す。)、ピーク面積の比から算出した。
ガスクロマトグラフ測定条件を以下に示す。
装 置 : 島津製作所社ガスクロマトグラフ(GC-2014、検出器:FID)
カラム : J&W社キャピラリーカラム
(DB-WAX 30m×025mm、0.25μm)
スプリット比: 1/20
注入量 : 2μL
線速度 : 25cm/sec
昇温条件 : 200℃(10min保持)
注入口温度 : 200℃
検出器温度 : 200℃
(1)結合スチレン含有量
結合スチレン含有量は、水添前のスチレン・ブタジエンブロック共重合体を検体として、試料をクロロホルム溶液とし、スチレンのフェニル基によるUV254nmの吸収により結合スチレン含有量(wt%)を測定した。(JASCO製:V-550)
(2)ブタジエン部のビニル量
試料を二硫化炭素溶液とし、溶液セルを用いて赤外線スペクトルを600~1000cm-1の範囲で測定して所定の吸光度より、スチレン・ブタジエンブロック共重合体はハンプトン法、ポリブタジエンはモレロ法の計算式に従いブタジエン部分のミクロ構造を求め、ブタジエン部のビニル量を求めた。IRスペクトル分析装置としては「パーキンエルマー社製:Spectrum100」を用いた。
(3)ピーク分子量
ピーク分子量は、窒素含有環状化合物添加前の共重合体を検体として、ポリスチレン系ゲルカラム(カラム:PLgel MiniMix-C×3本、カラムオーブン温度35℃:日本分光製865-CO、THF流量0.35mL、試料濃度0.1重量%、注入量50μL、RI検出器:Waters製2414)のGPC(WATERS製2695)のクロマトグラフを測定した。また、分子量が既知の市販の標準単分散ポリスチレンを用いて作成した検量線を使用し、得られたGPCクロマトグラムから、重量平均分子量、数平均分子量を求めて、分子量分布値を得た。
(4)カップリング率
カップリング率は、窒素含有環状化合物添加前のポリブタジエンを検体として、ポリスチレン系ゲルカラム(カラム:PLgel MiniMix-C×3本、カラムオーブン温度35℃:日本分光製865-CO、THF流量0.35mL、試料濃度0.1重量%、注入量50μL、RI検出器:Waters製2414)のGPC(WATERS製2695)のクロマトグラフを測定した。カップリングしていない(低分子量側のピーク)ピーク面積とカップリングされた(高分子量側のピーク)ピーク面積の比率から算出した。
(1)ポリブタジエン部の水素付加量(水添率:重量%)
核磁気共鳴装置(BRUKER社製、DPX-400)を用いて測定した。
シリカ系ゲルを充填材としたGPCカラムに、末端が特定構造のアミノ基である成分が吸着する特性を応用し、試料及び分子量5000の標準ポリスチレン(ポリスチレンはカラムに吸着しない)を含む試料溶液を用いて、ポリスチレン系ゲルカラム(カラム:PLgel MiniMix-C×3本、カラムオーブン温度35℃:日本分光製865-CO、THF流量0.35mL、RI検出器:Waters製2414)のGPC(WATERS製2695)と、シリカ系ゲルカラム(カラム:ZorbaxPSM1000-S1本とPSM300-S1本とPSM60-Sを1本の計3本、カラムオーブン温度35℃:日本分光製865-CO、THF流量0.7mL/分、RI検出器:Waters製2414)のGPC(WATERS製2695)の両クロマトグラムを、RI検出器を用いて測定し、それらの差分よりシリカカラムへの吸着量を測定し、上記式(I)で示されるアミノ基である末端及び式(IV)で示されるアミノ基である末端の合計の比率を求めた。以下、式(I)で示されるアミノ基及び式(IV)で示されるアミノ基のことを、「特定構造のアミノ基」と記載することもある。
試料は、20mLのTHFに対して10mgを標準ポリスチレン5mgとともに溶解し、100μL注入して測定した。具体的な手順としては、ポリスチレン系ゲルカラム及びシリカ系ゲルカラムで測定した面積(%)から、下記式により算出した。
a:ポリスチレン系ゲル(PLgel)で測定した全重合体の面積(%)
b:ポリスチレン系ゲル(PLgel)で測定した低分子量内部標準PS(ポリスチレン)の面積(%)
c:シリカ系カラム(Zorbax)で測定した全重合体の面積(%)
d:シリカ系カラム(Zorbax)で測定した低分子量内部標準PSの面積(%)
スガ試験機製の測色計SM-7型(45°拡散方式)を用いて測定した。
水添反応に用いた水添触媒は、下記の方法で調製した。
(1)水添触媒I
窒素置換した反応容器に乾燥、精製したシクロヘキサン1リットルを仕込み、ジクロロビス(η5-2,4-シクロペンタジエン-1-イル)チタニウム100ミリモルを添加し、十分に攪拌しながらトリメチルアルミニウム200ミリモルを含むn-ヘキサン溶液を添加して、室温にて約3日間反応させた。
(2)水添触媒II
窒素置換した反応容器に乾燥、精製したシクロヘキサン2リットルを仕込み、ビス(η5-シクロペンタジエニル)チタニウムジ-(p-トリル)40ミリモルと分子量が約1,000の1,2-ポリブタジエン(1,2ビニル結合量約85%)150グラムを溶解した後、n-ブチルリチウム60ミリモルを含むシクロヘキサン溶液を添加して室温で5分反応させ、直ちにn-ブタノールを添加攪拌して室温で保存した。
20gのブロック共重合体組成物をガラス製のビンに入れ、アルミホイル等で蓋をし、加熱乾燥機にて160℃、30分加熱した後、加熱乾燥機から取り出し耐熱性のある蓋でキャップし、室温(約25℃)にて30分静置した。基準物質としては、後述する重合体8の臭気の臭気レベルを5とした。この基準物質と比較したときの重合体の相対的な臭気レベルを1(臭気弱)~10(臭気強)の間で評価した。官能評価は10人以上で行い、臭気レベルの平均値が3.0以下であれば実用上優れた性能、4.8以下であれば、実用上十分な性能であると判断した。
(1)数平均分子量
GPC(装置はWATERS社製、カラムは昭和電工製Shodex、溶媒はクロロホルム)を用い、官能基含有PPE0.05gをクロロホルム50gに溶解した溶液サンプルをポリフェニレンエーテルの検知波長283nmの紫外線検出器にて分子量を測定した。また、分子量が既知の市販の標準単分散ポリスチレンを用いて作成した検量線を使用し、得られたGPCクロマトグラムから、数平均分子量を求めた。
(2)無水マレイン酸付加率
官能基含有PPE5gを100mlのクロロホルムに溶解後、300mlのアセトンを少量滴下しながらポリマーを析出させ、ガラスフィルターを用いて濾別した。この操作を3回繰り返した後、140℃に設定した真空乾燥機で2時間真空乾燥を行った。次にこの官能基含有PPEを1gとり、内側からポリテトラフロロエチレンシート、アルミシート、鉄板の順に重ねたものの間にはさみ、280℃に温度設定したプレス成形機を用い、100kg/cm2で圧縮成形しフィルムを得た。得られたフィルムそれぞれについて、日本分光社製FT/IR-420型フーリエ変換赤外分光光度計を用いて、赤外分光測定を行った。
官能基含有PPEフィルムに対する測定では、1790cmに、ポリフェニレンエーテルに付加したマレイン酸由来のピークが観測された。PPEとマレイン酸の混合物を用いて、あらかじめ作成しておいた検量線式から計算されたマレイン酸の付加率(PPE100重量部に対する付加量:重量部)を求めた。
(1)成分(a)-熱可塑性樹脂
官能基含有PPE
(2)成分(b)-共役ジエン系重合体
水添系重合体:重合体1、重合体7、重合体11、重合体12
(3)成分(c)-熱可塑性樹脂
ポリアミド6:ウベナイロン6-1013B(宇部興産(株)製)
(重合体1の調製)
内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン4600g、テトラヒドロフラン(THF)0.69g、テトラメチルエチレンジアミン(TMEDA)0.69g、スチレン132gを仕込み、100rpmで混合攪拌し重合開始温度を60℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム1.36g)を添加し、スチレンの重合を開始した。スチレンが完全に重合してから、1,3-ブタジエン544gを添加し、1,3-ブタジエンを完全に重合させ、スチレン124gを添加し、スチレンを完全に重合させた。
次に、化合物(II)に該当する1,3-ジメチル-2-イミダゾリノンを0.12wt%含有する1,3-ジメチル-2-イミダゾリジノン(化合物(III))を3.15g添加し、15分後にメタノール0.74gを添加し重合終了させた。
得られた共重合体に水添触媒Iを共重合体の重量に対してチタンとして130重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール1gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.3重量%添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体1)を得、乾燥処理を行った。
1,3-ジメチル-2-イミダゾリノンを0.6wt%含有する1,3-ジメチル-2-イミダゾリジノンを使用して、重合体1と同様に、内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。重合体の特性を表2に示す。
1,3-ジメチル-2-イミダゾリノンを0.12wt%含有する1,3-ジメチル-2-イミダゾリジノン(化合物(III))を0.92g添加した以外は、重合体1の調製と同様にして、共重合を行った。重合工程順を表1、重合体の特性を表2に示す。
(重合体2の調製)
内容積が100リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン26800g、テトラヒドロフラン(THF)4.0g、スチレン1440gを仕込み、100rpmで混合攪拌し重合開始温度を45℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム10.8g)を添加し、スチレンの重合を開始した。スチレンが完全に重合してから、スチレン640gと1,3-ブタジエン1200gを同時に添加し、その5分後に1,3-ブタジエン3600gを10分間かけて連続的に添加し、スチレンと1,3-ブタジエンを完全に共重合させて、スチレン1120gを添加し、スチレンを完全に重合させた。
次に、1,3-ジメチル-2-イミダゾリノンを0.12wt%含有する1,3-ジメチル-2-イミダゾリジノンを17.3g添加し、15分後にメタノール4.84gを添加し重合終了させた。得られた共重合体に水添触媒Iを共重合体の重量に対してチタンとして100重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール20gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.3重量%と2,4-ビス(オクチルチオメチル)-o-クレゾールを重合体の重量に対して0.1重量%添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体2)を得、乾燥処理を行った。重合体の特性を表2に示す。
(重合体3の調製)
内容積が100リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン29400g、テトラヒドロフラン(THF)4.4g、テトラメチルエチレンジアミン1.68g、スチレン720gと1,3-ブタジエン5040gを仕込み、100rpmで混合攪拌し重合開始温度を40℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム5.44g)を添加し、重合を開始した。スチレンと1,3-ブタジエンが完全に重合してから、スチレン2240gを添加し、スチレンを完全に重合させた。
次に、1,3-ジメチル-2-イミダゾリノンを0.5wt%含有する1,3-ジメチル-2-イミダゾリジノンを8.7g添加し、15分後にメタノール2.3gを添加し重合終了させた。得られた共重合体に水添触媒Iを共重合体の重量に対してチタンとして100重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール3gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.3重量%と2,4-ビス(オクチルチオメチル)-o-クレゾールを重合体の重量に対して0.1重量%を添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体3)を得、乾燥処理を行った。
1,3-ジメチル-2-イミダゾリノンを0.5wt%含有する1,3-ジメチル-2-イミダゾリジノンを10.7g添加した以外は、重合体3と同様に、内容積が100リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。重合体の特性を表2に示す。
(重合体4の調製)
内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン4300g、テトラヒドロフラン(THF)0.65g、1,3-ブタジエン704gを仕込み、100rpmで混合攪拌し重合開始温度を55℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム1.49g)を添加し、重合を開始した。1,3-ブタジエンが完全に重合してから、スチレン176gを添加し、スチレンを完全に重合させた。
次に、1,3-ジメチル-2-イミダゾリノンを0.2wt%含有する1,3-ジメチル-2-イミダゾリジノンを2.12g添加し、15分後にメタノール0.67gを添加し重合終了させた。得られた共重合体に水添触媒IIを共重合体の重量に対してチタンとして50重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール1gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.3重量%と2,4-ビス(オクチルチオメチル)-o-クレゾールを重合体の重量に対して0.1重量%を添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体4)を得、乾燥処理を行った。
1,3-ジメチル-2-イミダゾリノンを1.0wt%含有する1,3-ジメチル-2-イミダゾリジノンを使用して、重合体4と同様に、内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。重合体の特性を表2に示す。
(重合体5の調製)
内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン4000g、テトラヒドロフラン(THF)0.60g、1,3-ブタジエン1100gを仕込み、100rpmで混合攪拌し重合開始温度を55℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム1.09g)を添加し、重合を開始した。1,3-ブタジエンが完全に重合してから、四塩化珪素0.29gを添加し、一部カップリングさせた。
次に、1,3-ジメチル-2-イミダゾリノンを0.5wt%含有する1,3-ジメチル-2-イミダゾリジノンを1.16g添加し、15分後にメタノール0.33gを添加し重合終了させた。得られた重合体に水添触媒Iを重合体の重量に対してチタンとして30重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール1gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.4重量%と2,4-ビス(オクチルチオメチル)-o-クレゾールを重合体の重量に対して0.15重量%を添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体4)を得、乾燥処理を行った。
1,3-ジメチル-2-イミダゾリノンを1.0wt%含有する1,3-ジメチル-2-イミダゾリジノンを使用して、重合体5と同様に、内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、重合を行なった。重合体の特性を表2に示す。
(重合体11の調製)
内容積が12リットルの攪拌装置及びジャケット付き槽型反応器を用いて、表1に記載の重合操作工程順にて、共重合を行なった。精製シクロヘキサン4600g、テトラヒドロフラン(THF)0.69g、テトラメチルエチレンジアミン(TMEDA)0.69g、スチレン132gを仕込み、100rpmで混合攪拌し重合開始温度を60℃に調整した。20重量%のn‐ブチルリチウムのシクロヘキサン溶液(n‐ブチルリチウム1.36g)を添加し、スチレンの重合を開始した。スチレンが完全に重合してから、1,3-ブタジエン544gを添加し、1,3-ブタジエンを完全に重合させ、スチレン124gを添加し、スチレンを完全に重合させた。そのスチレン重合時のピーキング温度から、10分後にメタノール0.74gを添加し重合終了させた。
得られた共重合体に水添触媒Iを共重合体の重量に対してチタンとして130重量ppm添加し、水素圧0.7MPa、温度65℃で水添反応を行った。反応終了後にメタノール1gを添加し、重合体を反応器より抜き出した。次に安定剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネートを重合体の重量に対して0.3重量%添加した。更に、得られた重合体ゴム溶液を攪拌下熱湯中に投下して、スチームストリッピングにより溶媒を除去しクラム状の部分水添スチレン・ブタジエンブロック共重合体ゴム(重合体11)を得、乾燥処理を行った。
(官能基含有ポリフェニレンエーテルの調製)
数平均分子量が22000、ポリマー片末端鎖がフェノール性水酸基を有するポリ(2,6-ジメチル-1,4-フェニレンエーテル)を合成し、このポリフェニレンエーテル100重量部に対して、無水マレイン酸1重量部を添加し、250~300℃に加熱したベントポート付き二軸押出機(ZSK-25;WERNER&PFLEIDERER社製、ドイツ国)を用いて溶融混練し、未反応の無水マレイン酸を減圧下で除去しながら押出を実施し、無水マレイン酸が0.4重量部付加した官能基含有ポリフェニレンエーテル(官能基含有PPE)を得た。
表3に示した配合処方に従って、(a)官能基含有ポリフェニレンエーテル(官能基含有PPE)および(b)水添共役ジエン系重合体を押出機の第1供給口から連続的に供給し、次いで、(c)ポリアミド6(ウベナイロン6-1013B)をその押出機の中央部に位置する第2供給口から連続供給する製造プロセスにて、300℃に設定したベントポート付き二軸押出機(ZSK-25;WERNER&PFLEIDERER社製、ドイツ国)を用いて溶融混練し組成物をペレットとして得た。このペレットを用いて240~300℃に設定した射出成形機(IS55EPN;東芝機械(株)製)に供給し、金型温度60℃~100℃の条件でIzod衝撃試験用テストピースおよび平板(50mm×90mm×2.5mm)を射出成形した。本発明の共役ジエン系重合体を使用した重合体組成物は、衝撃強度が高く、優れた色調を有していることがわかる(実施例7)。化合物(II)、(III)の添加量が本発明の範囲外である重合体7(比較例5)は、b*値が高く、末端が特定構造のアミノ基となっていない重合体11(参考例3)、末端の35%が変性された重合体12(参考例4)を使用した重合体組成物は、衝撃強度が劣る。
Claims (6)
- 少なくとも一種の共役ジエン単量体を含有する共役ジエン系重合体であって、その末端の40%以上がアミノ基及びアミド基を有する末端であり、かつ測色色差計で測定される黄色度の指標b*値が15以下である、共役ジエン系重合体。
- 前記b*値が9以下である、請求項1~3のいずれか一項に記載の共役ジエン系重合体。
- 有機リチウム化合物を開始剤として、少なくとも一種の共役ジエン単量体を含有する単量体を重合させる工程と、
下記式(II)で表される化合物(II)と下記式(III)で表される化合物(III)を添加する工程と、
を含む共役ジエン系重合体の製造方法であって、
[式中、R3とR4は各々独立に炭素数1~20の炭化水素基を表す。]
[式中、R5とR6は各々独立に炭素数1~20の炭化水素基を表す。]
数式1に示されるように、化合物(II)と化合物(III)の合計に対する化合物(II)の重量比率(%)を(A)とし、数式2に示されるように、重合開始剤のリチウムに対する化合物(II)と化合物(III)のモル比を(B)としたときに、数式3に示されるように、(A)×(B)が0.5以下となるように、重合開始剤、化合物(II)、及び/又は化合物(III)の添加量を調節する、製造方法。
数式1:(A)=(化合物(II)/(化合物(II)+化合物(III)))×100
数式2:(B)=([化合物(II)]+[化合物(III)])/[Li]
数式3:(A)×(B)≦0.5 - (a)請求項1~4のいずれか一項に記載の共役ジエン系重合体又は請求項5に記載の製造方法により得られた共役ジエン系重合体1~99重量部と、
(b)熱可塑性重合体及び/又はゴム状重合体99~1重量部と、
を含む重合体組成物。
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/315,445 US10316111B2 (en) | 2014-06-02 | 2015-06-01 | Conjugated diene-based polymer, method for producing the same, and composition including the same |
DK15802610.4T DK3150638T3 (en) | 2014-06-02 | 2015-06-01 | CONJUGATED DIENE POLYMER, METHOD OF PREPARING IT AND COMPOSITION THEREOF |
EP15802610.4A EP3150638B1 (en) | 2014-06-02 | 2015-06-01 | Conjugated diene polymer, method for producing same, and composition including same |
RU2016147172A RU2665426C2 (ru) | 2014-06-02 | 2015-06-01 | Полимер на основе сопряженного диена, способ его получения и композиция, содержащая данный полимер |
SG11201609761YA SG11201609761YA (en) | 2014-06-02 | 2015-06-01 | Conjugated diene-based polymer, method for producing the same, and composition including the same |
MYPI2016704430A MY182927A (en) | 2014-06-02 | 2015-06-01 | Conjugated diene-based polymer, method for producing the same, and composition including the same |
CN201580029174.3A CN106459226B (zh) | 2014-06-02 | 2015-06-01 | 共轭二烯系聚合物、其制造方法和包含该共轭二烯系聚合物的组合物 |
KR1020167033349A KR101847328B1 (ko) | 2014-06-02 | 2015-06-01 | 공액 디엔계 중합체, 그의 제조 방법 및 그것을 포함하는 조성물 |
ES15802610T ES2709980T3 (es) | 2014-06-02 | 2015-06-01 | Polímero de dieno conjugado, procedimiento para producir el mismo, y composición que incluye el mismo |
JP2016525163A JP6203391B2 (ja) | 2014-06-02 | 2015-06-01 | 共役ジエン系重合体、その製造方法及びそれを含む組成物 |
US16/363,154 US20190233546A1 (en) | 2014-06-02 | 2019-03-25 | Conjugated Diene-Based Polymer, Method for Producing the Same, and Composition Including the Same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014114329 | 2014-06-02 | ||
JP2014-114329 | 2014-06-02 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/315,445 A-371-Of-International US10316111B2 (en) | 2014-06-02 | 2015-06-01 | Conjugated diene-based polymer, method for producing the same, and composition including the same |
US16/363,154 Continuation US20190233546A1 (en) | 2014-06-02 | 2019-03-25 | Conjugated Diene-Based Polymer, Method for Producing the Same, and Composition Including the Same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015186667A1 true WO2015186667A1 (ja) | 2015-12-10 |
Family
ID=54766737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/065787 WO2015186667A1 (ja) | 2014-06-02 | 2015-06-01 | 共役ジエン系重合体、その製造方法及びそれを含む組成物 |
Country Status (13)
Country | Link |
---|---|
US (2) | US10316111B2 (ja) |
EP (1) | EP3150638B1 (ja) |
JP (1) | JP6203391B2 (ja) |
KR (1) | KR101847328B1 (ja) |
CN (1) | CN106459226B (ja) |
DK (1) | DK3150638T3 (ja) |
ES (1) | ES2709980T3 (ja) |
MY (1) | MY182927A (ja) |
RU (1) | RU2665426C2 (ja) |
SG (1) | SG11201609761YA (ja) |
TR (1) | TR201900819T4 (ja) |
TW (1) | TWI627196B (ja) |
WO (1) | WO2015186667A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017038528A1 (ja) * | 2015-09-02 | 2017-03-09 | Jsr株式会社 | 組成物及び成形体 |
JP2023521003A (ja) * | 2020-04-13 | 2023-05-23 | エルジー エナジー ソリューション リミテッド | 電極の品質評価方法および電極の製造方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3150638B1 (en) * | 2014-06-02 | 2018-11-07 | Japan Elastomer Co., Ltd. | Conjugated diene polymer, method for producing same, and composition including same |
KR102142351B1 (ko) | 2017-11-10 | 2020-08-07 | 아사히 가세이 가부시키가이샤 | 축전 디바이스용 세퍼레이터, 및 축전 디바이스 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61268702A (ja) * | 1985-05-24 | 1986-11-28 | Nippon Erasutomaa Kk | 新規なランダムスチレン−ブタジエン共重合体 |
JPS61296001A (ja) * | 1985-06-26 | 1986-12-26 | Nippon Erasutomaa Kk | 分岐状ランダムスチレン−ブタジエン共重合体 |
JPS6230104A (ja) * | 1985-04-19 | 1987-02-09 | Nippon Erasutomaa Kk | 新規な共役ジエン系重合体その製造方法およびその組成物 |
JP2005255942A (ja) * | 2004-03-15 | 2005-09-22 | Asahi Kasei Chemicals Corp | 弾性重合体 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6399257A (ja) | 1986-06-05 | 1988-04-30 | Asahi Chem Ind Co Ltd | 変性ブロック共重合体組成物 |
ES2456694T3 (es) * | 2000-10-25 | 2014-04-23 | Asahi Kasei Kabushiki Kaisha | Polímero hidrogenado |
US7329693B2 (en) * | 2001-05-22 | 2008-02-12 | Bridgestone Corporation | Adhesive composition and method for bonding to rubber |
JP4208176B2 (ja) | 2001-08-10 | 2009-01-14 | 旭化成ケミカルズ株式会社 | 官能基含有ブロック共重合体及びその組成物 |
JP3792189B2 (ja) | 2002-09-05 | 2006-07-05 | 旭化成ケミカルズ株式会社 | グラフト共重合体およびそれを含む樹脂組成物 |
JP2005272696A (ja) | 2004-03-25 | 2005-10-06 | Asahi Kasei Chemicals Corp | 脂肪族ポリエステル成形体 |
JP2008127481A (ja) * | 2006-11-21 | 2008-06-05 | Asahi Kasei Chemicals Corp | 難燃共重合体組成物及び樹脂シート |
JP5240984B2 (ja) * | 2007-11-06 | 2013-07-17 | 旭化成ケミカルズ株式会社 | ブロック共重合体組成物又はその水添物の製造方法 |
EP2382241B1 (en) | 2009-01-23 | 2016-11-23 | Bridgestone Corporation | Polymers functionalized with polycyano compounds |
JP5783797B2 (ja) * | 2011-05-25 | 2015-09-24 | 株式会社ブリヂストン | ゴム組成物の製造方法 |
WO2012165120A1 (ja) * | 2011-05-27 | 2012-12-06 | 旭化成ケミカルズ株式会社 | 水添共役ジエン系共重合体の製造方法 |
EA029016B1 (ru) | 2012-10-24 | 2018-01-31 | Асахи Касеи Кемикалз Корпорейшн | Способ получения каталитической композиции для гидрирования и каталитическая композиция для гидрирования |
EP3150638B1 (en) * | 2014-06-02 | 2018-11-07 | Japan Elastomer Co., Ltd. | Conjugated diene polymer, method for producing same, and composition including same |
-
2015
- 2015-06-01 EP EP15802610.4A patent/EP3150638B1/en active Active
- 2015-06-01 CN CN201580029174.3A patent/CN106459226B/zh active Active
- 2015-06-01 ES ES15802610T patent/ES2709980T3/es active Active
- 2015-06-01 JP JP2016525163A patent/JP6203391B2/ja active Active
- 2015-06-01 TR TR2019/00819T patent/TR201900819T4/tr unknown
- 2015-06-01 US US15/315,445 patent/US10316111B2/en active Active
- 2015-06-01 SG SG11201609761YA patent/SG11201609761YA/en unknown
- 2015-06-01 RU RU2016147172A patent/RU2665426C2/ru active
- 2015-06-01 MY MYPI2016704430A patent/MY182927A/en unknown
- 2015-06-01 DK DK15802610.4T patent/DK3150638T3/en active
- 2015-06-01 WO PCT/JP2015/065787 patent/WO2015186667A1/ja active Application Filing
- 2015-06-01 KR KR1020167033349A patent/KR101847328B1/ko active IP Right Grant
- 2015-06-02 TW TW104117833A patent/TWI627196B/zh active
-
2019
- 2019-03-25 US US16/363,154 patent/US20190233546A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6230104A (ja) * | 1985-04-19 | 1987-02-09 | Nippon Erasutomaa Kk | 新規な共役ジエン系重合体その製造方法およびその組成物 |
JPS61268702A (ja) * | 1985-05-24 | 1986-11-28 | Nippon Erasutomaa Kk | 新規なランダムスチレン−ブタジエン共重合体 |
JPS61296001A (ja) * | 1985-06-26 | 1986-12-26 | Nippon Erasutomaa Kk | 分岐状ランダムスチレン−ブタジエン共重合体 |
JP2005255942A (ja) * | 2004-03-15 | 2005-09-22 | Asahi Kasei Chemicals Corp | 弾性重合体 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017038528A1 (ja) * | 2015-09-02 | 2017-03-09 | Jsr株式会社 | 組成物及び成形体 |
JP2023521003A (ja) * | 2020-04-13 | 2023-05-23 | エルジー エナジー ソリューション リミテッド | 電極の品質評価方法および電極の製造方法 |
US11971344B2 (en) | 2020-04-13 | 2024-04-30 | Lg Energy Solution, Ltd. | Electrode quality evaluation method and electrode manufacturing method |
Also Published As
Publication number | Publication date |
---|---|
TWI627196B (zh) | 2018-06-21 |
SG11201609761YA (en) | 2016-12-29 |
RU2665426C2 (ru) | 2018-08-29 |
EP3150638B1 (en) | 2018-11-07 |
RU2016147172A (ru) | 2018-07-10 |
KR20170002501A (ko) | 2017-01-06 |
CN106459226A (zh) | 2017-02-22 |
US10316111B2 (en) | 2019-06-11 |
JP6203391B2 (ja) | 2017-09-27 |
TW201612201A (en) | 2016-04-01 |
US20190233546A1 (en) | 2019-08-01 |
EP3150638A4 (en) | 2017-05-10 |
TR201900819T4 (tr) | 2019-02-21 |
KR101847328B1 (ko) | 2018-04-09 |
CN106459226B (zh) | 2019-03-26 |
RU2016147172A3 (ja) | 2018-07-10 |
EP3150638A1 (en) | 2017-04-05 |
ES2709980T3 (es) | 2019-04-22 |
US20170190805A1 (en) | 2017-07-06 |
JPWO2015186667A1 (ja) | 2017-04-20 |
MY182927A (en) | 2021-02-05 |
DK3150638T3 (en) | 2018-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2716663B1 (en) | Method for manufacturing hydrogenated conjugated diene copolymer | |
US20100016508A1 (en) | Process for producing block copolymer, and block copolymer or hydrogenated product thereof | |
US20190233546A1 (en) | Conjugated Diene-Based Polymer, Method for Producing the Same, and Composition Including the Same | |
KR100746054B1 (ko) | 신발용 고무 조성물 | |
KR100463298B1 (ko) | 수소 첨가 중합체 | |
JP5288858B2 (ja) | 熱可塑性エラストマー組成物 | |
JP4911913B2 (ja) | 共重合体組成物及びそのフィルム | |
KR100577042B1 (ko) | 수소첨가 중합체 및 이의 제조 방법 | |
EP2042531B1 (en) | Block copolymer, composition for resin modification, and modified resin composition | |
EP1785437B1 (en) | Impact-resistant vinylaromatic hydrocarbon resin | |
CN113227174B (zh) | 官能化橡胶 | |
JP2008000985A (ja) | 極性樹脂層および、変性熱可塑性共重合体および/またはその組成物からなる層の積層体 | |
KR100795653B1 (ko) | 내충격성 비닐 방향족 탄화수소 수지 | |
JPH05345813A (ja) | 水添ブロック共重合体 | |
JP2024032575A (ja) | ブロック共重合体又はその水添物、粘接着剤組成物、アスファルト改質用組成物、及び熱可塑性樹脂改質用組成物。 | |
JPH02187404A (ja) | 重合体の回収方法 | |
JPH0270735A (ja) | 重合体組成物 | |
JPH08225616A (ja) | 環状共役ジエン系ブロック共重合体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15802610 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016525163 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015802610 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015802610 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20167033349 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15315445 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2016147172 Country of ref document: RU Kind code of ref document: A |