JPS63297437A - Vibration-insulation rubber composition - Google Patents
Vibration-insulation rubber compositionInfo
- Publication number
- JPS63297437A JPS63297437A JP13389987A JP13389987A JPS63297437A JP S63297437 A JPS63297437 A JP S63297437A JP 13389987 A JP13389987 A JP 13389987A JP 13389987 A JP13389987 A JP 13389987A JP S63297437 A JPS63297437 A JP S63297437A
- Authority
- JP
- Japan
- Prior art keywords
- isoprene
- rubber
- vibration
- rare earth
- component
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000005060 rubber Substances 0.000 title claims abstract description 23
- 238000009413 insulation Methods 0.000 title 1
- 229920001194 natural rubber Polymers 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 13
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- -1 lanthanide rare earth metal Chemical class 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 11
- 229910052779 Neodymium Inorganic materials 0.000 description 10
- 150000001993 dienes Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000013016 damping Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000021355 Stearic acid Nutrition 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
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002603 lanthanum Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 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
- MPZXOLLYZDBITA-UHFFFAOYSA-K 2-methylprop-2-enoate;neodymium(3+) Chemical compound [Nd+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O MPZXOLLYZDBITA-UHFFFAOYSA-K 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 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
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IMHQFVGHBDXALM-UHFFFAOYSA-N 2,2-diethylhexanoic acid Chemical compound CCCCC(CC)(CC)C(O)=O IMHQFVGHBDXALM-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QBKTXRLYEHZACW-UHFFFAOYSA-K 2-ethylhexanoate;neodymium(3+) Chemical compound [Nd+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QBKTXRLYEHZACW-UHFFFAOYSA-K 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000722 Didymium Inorganic materials 0.000 description 1
- 241000224487 Didymium Species 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- LUAVDAACVADYSN-UHFFFAOYSA-N [S].C1(CCCCC1)C1=CC=CC2=C1N=C(S2)SN Chemical compound [S].C1(CCCCC1)C1=CC=CC2=C1N=C(S2)SN LUAVDAACVADYSN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- HUDSKKNIXMSHSZ-UHFFFAOYSA-N dihexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCCCCCC HUDSKKNIXMSHSZ-UHFFFAOYSA-N 0.000 description 1
- BXVQCOZKKYBAQR-UHFFFAOYSA-N dihexyl sulfite Chemical compound CCCCCCOS(=O)OCCCCCC BXVQCOZKKYBAQR-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000010690 paraffinic oil 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
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GGFBICGBDXVAGX-UHFFFAOYSA-N propylaluminum Chemical compound [Al].[CH2]CC GGFBICGBDXVAGX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ランタン系列希土類金属触媒の存在下に重合
して得られるイソプレン−ブタジエン共重合体と天然ゴ
ムおよび／またはポリイソプレンゴムとからなる振動吸
収特性および耐疲労特性に優れた防振ゴム組成物に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a method comprising an isoprene-butadiene copolymer obtained by polymerization in the presence of a lanthanum series rare earth metal catalyst, and natural rubber and/or polyisoprene rubber. This invention relates to a vibration-proof rubber composition with excellent vibration absorption properties and fatigue resistance properties.
従来、一般用防振ゴムは、天然ゴム、ジエン系合成ゴム
の単体あるいはブレンドにより製造されている。Conventionally, general-purpose anti-vibration rubbers have been manufactured using natural rubber, diene-based synthetic rubber alone or as a blend.
ところで、近年に至り、自動車工業の発展にともない、
防振ゴムの性能はより大きな振動吸収特性を要求される
ようになっており、特に低振動数の振動をも防振する要
求が高まっている。By the way, in recent years, with the development of the automobile industry,
The performance of anti-vibration rubber has come to require greater vibration-absorbing properties, and in particular there has been an increasing demand for anti-vibration properties even against low-frequency vibrations.
この一つの解決策として、ガラス転移温度（Ｔｇ）の低
いゴム成分を配合することが知られている。As one solution to this problem, it is known to blend a rubber component with a low glass transition temperature (Tg).
例えば、シリコンゴムまたはポリブタジェンゴムと、天
然ゴムとをブレンドすることにより、防振特性を改良す
る試みがなされている。For example, attempts have been made to improve vibration damping properties by blending silicone rubber or polybutadiene rubber with natural rubber.
しかしながら、これらのゴムあるいはゴム組成物により
、低振動数の防振特性は改良されるが、従来のシリコン
ゴムまたはポリブタジェンゴムを配合したものでは、疲
労特性に劣り実用に供しえない。However, although these rubbers or rubber compositions improve the vibration damping properties at low frequencies, those containing conventional silicone rubber or polybutadiene rubber have inferior fatigue properties and cannot be put to practical use.
本発明は、前記従来の技術的課題を背景になされたもの
で、防振特性および疲労特性の両者を満足する防振ゴム
組成物を提供することを目的とする。The present invention was made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a vibration-proof rubber composition that satisfies both vibration-proof properties and fatigue properties.
すなわち、本発明は、（イ）ランタン系列希土類金属触
媒の存在下で重合して得られるシス−１゜４結合を９０
％以上含有するイソプレン−ブタジエン系共重合体２０
〜９０ｆ！量部と、（ロ）天然ゴムおよび／またはポリ
イソプレンゴム８０〜１０重量部とを含むことを特徴と
する防振ゴム組成物を提供するものである。That is, in the present invention, (a) the cis-1°4 bond obtained by polymerization in the presence of a lanthanum series rare earth metal catalyst is
Isoprene-butadiene copolymer containing 20% or more
~90f! and (b) 80 to 10 parts by weight of natural rubber and/or polyisoprene rubber.
本発明の（イ）イソプレン−ブタジエン系共重合体の製
造に使用されるランタン系列希土類金属触媒は、例えば
（ａ）一般式ＬｎＹ＝ （式中、Ｌｎは周期律表の原
子番号５７〜７１の金属であり、Ｙは−Ｒ，−ＯＲ，Ｓ
Ｒ，ＮＲｔ 、リン酸塩、亜リン酸塩、ＸまたはＲＣＯ
Ｏ−であり、ここでＲは炭素数１〜２０の炭化水素基、
Ｘはハロゲン原子を示す）で表されるランタン系列希土
類金属化合物（以下「（ａ）成分」という）と、（ｂ）
一般式ＡｆＲ’ Ｒ” Ｒ” （式中、Ｒ１，Ｒ１お
よびＲ３は同一または異なり、水素原子または炭素数１
〜８の炭化水素基であり、全てが水素原子ではない）で
表される有機アルミニウム化合物（以下「（ｂ）成分」
という）よりなる触媒系である。The lanthanum series rare earth metal catalyst used in the production of (a) isoprene-butadiene copolymer of the present invention has, for example, (a) the general formula LnY= (wherein, Ln has an atomic number of 57 to 71 in the periodic table). metal, Y is -R, -OR,S
R, NRt, phosphate, phosphite, X or RCO
O-, where R is a hydrocarbon group having 1 to 20 carbon atoms,
(X represents a halogen atom) (hereinafter referred to as "component (a)"), and (b)
General formula AfR'R"
-8 hydrocarbon groups, not all of which are hydrogen atoms) (hereinafter referred to as "component (b)")
It is a catalyst system consisting of
これは、必要に応じて（Ｃ）ルイス酸（以下「（Ｃ）成
分」という）および／または（ｄ）ルイス塩基（以下「
（ｄ）成分」という）を含有することができる。(C) Lewis acid (hereinafter referred to as "component (C)") and/or (d) Lewis base (hereinafter referred to as "component (C)") as necessary.
(d) component").
まず、（ａ）成分において、Ｌｎは、周期律表の原子番
号が５７〜７１のランタン系列希土類元素であり、なか
でもセリウム、ランタン、プラセオジウム、ネオジムお
よびガドリウムが好ましく、特にネオジムが工業的に入
手し易いので好ましい。First, in component (a), Ln is a lanthanum series rare earth element with an atomic number of 57 to 71 in the periodic table, and among them, cerium, lanthanum, praseodymium, neodymium, and gadolinium are preferable, and especially neodymium is industrially available. This is preferred because it is easy to do.
これらの希土類元素は、２種以上の混合物であってもよ
い。These rare earth elements may be a mixture of two or more.
また、Ｙとしては、アルキル、アルコキサイド、チオア
ルコキサイド、アミド、リン酸塩、亜リン酸塩、ハロゲ
ンおよびカルボン酸塩の形であり、特にアルコキサイド
、ハロゲン化物、カルボン酸塩が好ましい。Furthermore, Y is in the form of alkyl, alkoxide, thioalkoxide, amide, phosphate, phosphite, halogen, and carboxylate, with alkoxide, halide, and carboxylate being particularly preferred.
このうち、ランタン系列希土類元素のアルキル型化合物
としては、ＬｎＲｚで表され、Ｒとしてはベンジル基、
フェニル基、ブチル基、シクロペンタジェニル基などの
炭素数１〜２０の炭化水素基を挙げることができる。Among these, alkyl type compounds of lanthanum series rare earth elements are represented by LnRz, where R is a benzyl group,
Examples include hydrocarbon groups having 1 to 20 carbon atoms such as phenyl group, butyl group, and cyclopentagenyl group.
アルコール型化合物（アルコキサイド）としては、一般
式Ｌｎ （ＯＲ）ｘ （式中、ＬｎおよびＲは前記に
同じ）で表され、好ましいアルコールとしては２−エチ
ル−ヘキシルアルコール、オレイルアルコール、ステア
リルアルコール、フェノール、ベンジルアルコールなど
が挙げられる。The alcohol type compound (alkoxide) is represented by the general formula Ln (OR) x (wherein Ln and R are the same as above), and preferable alcohols include 2-ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, and phenol. , benzyl alcohol and the like.
チオアルコール型化合物（チオアルコキサイド）として
は、一般式Ｌｎ （ＳＲ）ｓ Ｃ式中、ＬｎおよびＲ
は前記に同じ）で表され、好ましいチオアルコールとし
てはチオフェノールが挙げられる。As a thioalcohol type compound (thioalkoxide), the general formula Ln (SR)s C, in which Ln and R
is the same as above), and preferred thioalcohols include thiophenol.
アミド型化合物（アミド）としては、一般式Ｌｎ （Ｎ
Ｒｚ ） ｓ （式中、ＬｎおよびＲは前記に同じ）
で表され、好ましいアミンとしてはジオクチルアミン、
ジオクチルアミンが挙げられる。As an amide type compound (amide), the general formula Ln (N
Rz ) s (wherein, Ln and R are the same as above)
Preferred amines include dioctylamine,
Dioctylamine is mentioned.
前記希土類元素のリン酸塩としては、
一般式 ０Ｒ
Ｌｎ（ＯＰ）３
Ｒ′
（式中、Ｌｎは前記に同じであり、またＲ、Ｒ’は同一
または異なり、前記Ｒに同じ）で表され、好ましくはト
リス（リン酸ジヘキシル）ネオジム、トリス（リン酸ジ
フェニル）ネオジムが挙げられる。The rare earth element phosphate is represented by the general formula 0R Ln(OP)3 R' (wherein, Ln is the same as above, and R and R' are the same or different, and are the same as R above). Preferred examples include tris(dihexyl phosphate) neodymium and tris(diphenyl phosphate) neodymium.
前記希土類元素の亜リン酸塩としては、−７″ｔ
、Ｒ
Ｌｎ（ＯＰ）ｓ
Ｒ′
（式中、Ｌｎ％Ｒ％Ｒ’は前記に同じ）で表され、好ま
しくはトリス（亜すン酸ジヘキシル）ネオジム、トリス
〔亜すン酸ジ（２−エチルヘキシル）〕ネオジムが挙げ
られる。As the rare earth element phosphite, −7″t
, R Ln(OP)s R' (in the formula, Ln%R%R' is the same as above), preferably tris(dihexylsulfite) neodymium, tris[di(2-sulfurous acid) ethylhexyl)] neodymium.
ハロゲン型化合物としては、一般式ＬｎＸ。The halogen type compound has the general formula LnX.
（式中、Ｌｎは前記に同じ、Ｘはハロゲン原子を示す）
で表され、ハロゲン原子としては好ましくは塩素原子、
臭素原子、ヨウ素原子である。(In the formula, Ln is the same as above, and X represents a halogen atom)
The halogen atom is preferably a chlorine atom,
They are bromine and iodine atoms.
前記希土類元素のカルボン酸塩としては、一般式（ＲＣ
ＯＯ）ｉＬｎで表され、Ｒとしては、炭素数１〜２０の
炭化水素基であり、好ましくは飽和および不飽和のアル
キル基であり、かつ直鎖状、分岐状あるいは環状であり
、カルボキシル基は１級、２級または３級の炭素原子に
結合しているものである。具体的に好ましいカルボン酸
の例としては、オクタン酸、２−エチル−ヘキサン酸、
オレイン酸、ステアリン酸、安息香酸、ナフテン酸が挙
げられる。The rare earth element carboxylate has the general formula (RC
OO)iLn, R is a hydrocarbon group having 1 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group, and is linear, branched or cyclic, and the carboxyl group is It is bonded to a primary, secondary or tertiary carbon atom. Specific examples of preferred carboxylic acids include octanoic acid, 2-ethyl-hexanoic acid,
Examples include oleic acid, stearic acid, benzoic acid, and naphthenic acid.
これら（ａｌ成分の具体例としては、例えば三塩化ネオ
ジム、三塩化ジジム（ネオジム７２重量％、ランタン２
０ｊｉｉｆ％、プラセオジム８重量％の希土類金属の三
塩化物の混合物）、２−エチルヘキサン酸・ネオジム、
２−エチルヘキサン酸・ジジム、ナフテン酸・ネオジム
、２，２−ジエチルヘキサン酸・ネオジム、ネオジムト
リメタクレート、ネオジムトリメタクリレートの重合体
などが挙げられる。Specific examples of these (Al components include neodymium trichloride, didymium trichloride (neodymium 72% by weight, lanthanum 2
0jiif%, praseodymium 8% by weight mixture of rare earth metal trichlorides), 2-ethylhexanoate/neodymium,
Examples include polymers of 2-ethylhexanoic acid/didimium, naphthenic acid/neodymium, 2,2-diethylhexanoic acid/neodymium, neodymium trimethacrylate, neodymium trimethacrylate.
Ｃｂ）成分である有機アルミニウム化合物は、前記一般
式ＡＩＲ’ Ｒ” Ｒ’ （ここで、Ｒ１，Ｒ１およ
びＲ３は同一または異なり、水素原子または炭素数１〜
８の炭化水素基であり、全てが水素原子ではない）で表
される化合物であり、具体的にはトリメチルアルミニウ
ム、トリエチルアルミニウム、トリイソプロピルアルミ
ニウム、トリブチルアルミニウム、トリイソブチルアル
ミニウム、トリヘキシルアルミニウム、トリシクロヘキ
シルアルミニウム、ジイソブチルアルミニウムハイドラ
イド、ジエチルアルミニウムハイドライド、ジプロピル
アルミニウムハイドライド、エチルアルミニウムシバイ
ドライド、プロピルアルミニウムシバイドライド、イソ
ブチルアルミニウムシバイドライドなどが挙げられる。The organoaluminum compound which is component Cb) has the general formula AIR'R''R' (where R1, R1 and R3 are the same or different, and has a hydrogen atom or a carbon number of 1 to 1).
8 hydrocarbon groups, not all of which are hydrogen atoms), specifically trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexyl Examples include aluminum, diisobutylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, ethylaluminum sibide, propylaluminum sibide, isobutylaluminum sibide, and the like.
（Ｃ１成分であるルイス酸としては、例えば一般式Ａｊ
！Ｒ’ 、Ｘ＊−−（式中、Ｒ４は炭素数１〜８の炭化
水素基、ｍはＯ〜３の整数、Ｘは前記に同じ）で表され
るハロゲン化アルミニウム化合物、ハロゲン元素および
スズ、チタンなどのハロゲン化物が挙げられる。(As the Lewis acid that is the C1 component, for example, the general formula Aj
! An aluminum halide compound represented by R', X*-- (wherein R4 is a hydrocarbon group having 1 to 8 carbon atoms, m is an integer of O to 3, and X is the same as above), a halogen element, and tin , halides such as titanium.
このうち、特に好ましいのは、ジメチルアルミニウムク
ロライド、ジエチルアルミニウムクロライド、ジプチル
アルミニウムクロライド、メチルアルミニウムセスキク
ロライド、エチルアルミニウムセスキブロマイド、エチ
ルアルミニウムジクロライド、およびこれらのブロマイ
ド、アイオダイド化合物などである。Among these, particularly preferred are dimethylaluminum chloride, diethylaluminum chloride, diptylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum dichloride, and bromide and iodide compounds thereof.
（ｄ）成分であるルイス塩基としては、アセチルアセト
ン、テトラヒドロフラン、ピリジン、Ｎ、 Ｎ−ジメチ
ルホルムアミド、チオフェン、ジフェニルエーテル、ト
リエチルアミン、有機リン化合物、１価または２価のア
ルコール類が挙げられる。Examples of the Lewis base as component (d) include acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds, and monohydric or dihydric alcohols.
本発明で使用されるランタン系列希土類金属触媒の組成
は、通常、次の通りである。The composition of the lanthanum series rare earth metal catalyst used in the present invention is usually as follows.
（ｂ）成分／（ａ）成分（モル比）は、１０〜１５０゜
好ましくは１５〜１００であり、１０未満では重合活性
が低く、一方１５０を超えても重合活性への影響は少な
く、経済的に不利である。The molar ratio of component (b)/component (a) is 10 to 150°, preferably 15 to 100. If it is less than 10, the polymerization activity is low, while if it exceeds 150, there is little effect on the polymerization activity and it is economical. This is disadvantageous.
また、（Ｃ１成分／（ａ）成分（モル比）は、０〜６、
好ましくは０．５〜５．０であり、６を超えると重合活
性が低くなる。In addition, (C1 component/(a) component (molar ratio) is 0 to 6,
Preferably it is 0.5 to 5.0, and if it exceeds 6, the polymerization activity will decrease.
さらに、ｆｄ）成分／（ａ）成分（モル比）は、０〜２
０、好ましくは１〜１５であり、２ｏを超えると重合活
性が低くなり好ましくない。Furthermore, fd) component/(a) component (molar ratio) is 0 to 2
0, preferably 1 to 15, and if it exceeds 2o, the polymerization activity decreases, which is not preferable.
触媒成分として、前記（ａ）、（′ｂ）、（Ｃ１、（ｄ
ｌ成分のほかに、必要に応じて共役ジエンを（ａ）成分
であるランタン系列希土類元素化合物１モル当たり、０
〜５０モルの割合で用いてもよい。触媒調製に用いる共
役ジエンは、イソプレン、１，３−ブタジェン、１．３
−ペンタジェンなどが用いられる。As catalyst components, the above (a), ('b), (C1, (d
In addition to component (a), if necessary, 0 conjugated diene may be added per mole of the lanthanum series rare earth element compound (a).
It may be used in a proportion of ~50 moles. Conjugated dienes used for catalyst preparation are isoprene, 1,3-butadiene, 1.3
- Pentagene etc. are used.
触媒成分としての共役ジエンは必須ではないが、これを
併用することにより触媒成分の触媒活性が一段と向上す
る。Although the conjugated diene is not essential as a catalyst component, the catalytic activity of the catalyst component is further improved by using it in combination.
触媒を調製するには、例えば溶媒に溶解した（ａ）〜（
ｄ）成分、さらに必要に応じて共役ジエンを反応させる
ことよりなる。その際、各成分の添加順序は、任意でよ
い。これらの各成分は、あらかじめ混合、反応させ、熟
成させることが重合活性の向上、重合開始誘導期間の短
縮の意味から好ましいが、重合に際し溶媒およびモノマ
ー中に直接触媒各成分を順次添加してもよい。To prepare the catalyst, for example, (a) to (
It consists of reacting component d) and, if necessary, a conjugated diene. At that time, the order of addition of each component may be arbitrary. It is preferable to mix, react, and age each of these components in advance in order to improve polymerization activity and shorten the polymerization initiation induction period. good.
重合溶媒としては、不活性の有機溶媒であり、例えばベ
ンゼン、トルエン、キシレンなどの芳香族炭化水素溶媒
、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ブタ７、シクロヘ
キサンなどの脂肪族炭化水素溶媒、メチルシクロベンク
ン、シクロヘキサンなどの脂環族炭化水素溶媒、二塩化
エチレン、クロルベンゼンなどのハロゲン化炭化水素溶
媒およびこれらの混合物が使用できる。Examples of the polymerization solvent include inert organic solvents, such as aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-buta7, and cyclohexane, and methyl. Alicyclic hydrocarbon solvents such as cyclobencune and cyclohexane, halogenated hydrocarbon solvents such as ethylene dichloride and chlorobenzene, and mixtures thereof can be used.
重合温度は、通常、−２０℃〜１５０℃で、好ましくは
３０〜１２０℃である。重合反応は、回分式でも、連続
式でもよい。The polymerization temperature is usually -20°C to 150°C, preferably 30 to 120°C. The polymerization reaction may be carried out batchwise or continuously.
なお、溶媒中の単量体濃度は、通常、５〜５０重量％、
好ましくは１０〜３５重景％である。Note that the monomer concentration in the solvent is usually 5 to 50% by weight,
Preferably it is 10-35%.
このようにして得られるイソプレン−ブタジエン系共重
合体のミクロ構造は、イソプレン構造単位およびブタジ
ェン構造単位のシス−１，４結合がそれぞれ９０％以上
であることが必要であり、９０％未満では（ロ）天然ゴ
ムとの相溶性が悪く、破壊特性が低下しやす（、ガラス
転移温度が上昇し、さらに充分な防振特性が得られない
場合がある。The microstructure of the isoprene-butadiene copolymer obtained in this way requires that the cis-1,4 bonds of the isoprene structural unit and the butadiene structural unit are each 90% or more; less than 90% ( (b) Compatibility with natural rubber is poor, and fracture properties tend to deteriorate (the glass transition temperature may rise, and sufficient vibration damping properties may not be obtained).
なお、本発明の（イ）成分であるイソプレン−ブタジエ
ン系共重合体中のイソプレンとブタジェンとの共重合割
合は、通常、イソプレン／ブタジェン（モル比）＝２０
／８０〜９５１５、好ましくは３０／７０〜９０／１０
程度である。Note that the copolymerization ratio of isoprene and butadiene in the isoprene-butadiene copolymer that is component (a) of the present invention is usually isoprene/butadiene (molar ratio) = 20.
/80-9515, preferably 30/70-90/10
That's about it.
また、本発明で使用されるイソプレン−ブタジエン系共
重合体の分子量は、広い範囲にわたって変化させること
ができるが防振ゴム製品として用いる場合、そのムーニ
ー粘度（ＭＬ１＋４．１００℃）は、通常、１０〜１２
０、好ましくは１５〜１００の範囲であるが、特に限定
されるものではない。Further, the molecular weight of the isoprene-butadiene copolymer used in the present invention can be varied over a wide range, but when used as a vibration-proof rubber product, its Mooney viscosity (ML1 + 4.100°C) is usually 10 ~12
0, preferably in the range of 15 to 100, but is not particularly limited.
本発明で使用される（イ）イソプレン−ブタジエン系共
重合体は、必要に応じてクロロプレン、２．３−ジメチ
ル−１，３−ブタジェン、１．３−ペンタジェン、ミル
センなどのその他の共役ジエンを１０重量％以下程度共
重合したゴムであってもよい。(a) Isoprene-butadiene copolymer used in the present invention may optionally contain other conjugated dienes such as chloroprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and myrcene. It may be a copolymerized rubber of about 10% by weight or less.
以上のような（イ）イソプレン−ブタジエン系共重合体
と、（ロ）天然ゴムおよび／または合成ポリイソプレン
ゴム（ＩＲ）との重量割合は、（イ）２０〜９０重量部
、好ましくは３０〜８０重量部、（ロ）８０〜１０重量
部、好ましくは７０〜２０重量部であり、（イ）成分が
２０重量部未満では防振特性の充分な改良効果がみられ
ず、一方（イ）成分が９０重量部を超えると防振特性の
改良効果は飽和しており、逆に耐疲労特性が悪くなる。The weight ratio of the above (a) isoprene-butadiene copolymer to (b) natural rubber and/or synthetic polyisoprene rubber (IR) is (a) 20 to 90 parts by weight, preferably 30 to 90 parts by weight. 80 parts by weight, (b) 80 to 10 parts by weight, preferably 70 to 20 parts by weight, and if component (a) is less than 20 parts by weight, sufficient improvement effect on vibration damping properties will not be seen; If the amount of the component exceeds 90 parts by weight, the effect of improving vibration damping properties is saturated, and on the contrary, fatigue resistance becomes worse.
かくて、本発明では、（イ）イソプレン−ブタジエン系
共重合体、ならびに（ロ）天然ゴムおよび／またはＩＲ
に、さらに乳化重合スチレン−ブタジェン共重合体、溶
液重合スチレン−ブタジェン共重合体、低シス−１，４
−ポリブタジェン、高シス−１，４−ポリブタジェン、
エチレン−プロピレン−ジエン共重合体、クロロブレン
、ハロゲン化ブチルゴム、ＮＢＲなどとブレンドして使
用され、必要ならば芳香族系、ナフテン系、パラフィン
系などのオイルで油展し、次いでカーボンブラック、シ
リカ、炭酸マグネシウム、炭酸カルシウム、ガラス繊維
などの充填剤、ステアリン酸、亜鉛華、老化防止剤、加
硫促進剤ならびに加硫剤などの通常の加硫ゴム配合剤を
加え、防振ゴム組成物となすことができる。Thus, in the present invention, (a) an isoprene-butadiene copolymer, and (b) natural rubber and/or IR
Furthermore, emulsion polymerized styrene-butadiene copolymer, solution polymerized styrene-butadiene copolymer, low cis-1,4
- polybutadiene, high cis-1,4-polybutadiene,
It is used by blending with ethylene-propylene-diene copolymer, chlorobrene, halogenated butyl rubber, NBR, etc. If necessary, it is extended with aromatic, naphthenic, or paraffinic oil, and then carbon black, silica, Add ordinary vulcanized rubber compounding agents such as fillers such as magnesium carbonate, calcium carbonate, and glass fiber, stearic acid, zinc white, anti-aging agents, vulcanization accelerators, and vulcanizing agents to form a vibration-proof rubber composition. be able to.
得られるゴム組成物は、成形加工後、加硫を行い、自動
車のエンジン廻り、船舶用の防舷材、組み立てラインの
精密位置決め用ストッパーなどの防振用などの広い範囲
の防振用途に好適に使用することができる。After molding, the resulting rubber composition is vulcanized and is suitable for a wide range of vibration-isolating applications, including vibration-isolating applications such as around automobile engines, fenders for ships, and stoppers for precision positioning on assembly lines. It can be used for.
以下、本発明を実施例を挙げてさらに具体的に説明する
が、本発明はその要旨を超えない限り、以下の実施例に
何ら制約されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
なお、実施例中、部および％は、特に断らない限り、重
量部および重量％を意味する。In the examples, parts and % mean parts by weight and % by weight unless otherwise specified.
また、実施例中の各種の測定は、下記の方法に拠った・
ムーニー粘度は、予熱１分、測定４分、温度１００℃で
測定した（ＪＩＳ Ｋ６３００に準じた）。In addition, various measurements in the examples were performed according to the following methods. Mooney viscosity was measured at a temperature of 100° C. with 1 minute of preheating and 4 minutes of measurement (according to JIS K6300).
重合体のミクロ構造は、赤外吸収スペクトル法（モレロ
法）によって求めた。The microstructure of the polymer was determined by infrared absorption spectroscopy (Morello method).
引張特性および硬さは、下記配合処方によりゴム組成物
を加硫し、ＪＴＳ Ｋ６３０１に準じて測定した。The tensile properties and hardness were measured according to JTS K6301 after vulcanizing a rubber composition according to the following formulation.
伸長疲労試験は、デマッチャ屈曲試験機を用い、０．７
龍の切り込みを入れ、５０％または１００％伸長で繰り
返し伸長屈曲させ、切断までの回数、ならびに切り込み
なしで１００％伸長で繰り返し伸長屈曲させ、切断まで
の回数で評価した。The extension fatigue test was carried out using a Dematcher bending tester with a
A dragon cut was made and the material was repeatedly stretched and bent at 50% or 100% elongation, and evaluation was made based on the number of times it took to break, as well as the number of times it was made to repeatedly extend and bend at 100% elongation without making a cut until it was cut.
回数の大きいほど良好である。The larger the number of times, the better.
防振特性の評価は、加硫物をＪＩＳ Ｋ６３０１によ
り静的剪断弾性率Ｇｓを求め、また■岩本制作所製の粘
弾性スペクトロメーターを用い、振動数５Ｈｚで測定し
た複素動的ヤング率の実数部（Ｅ’ （５Ｈｚ））と
振動数１００Ｈｚで測定した複素動的ヤング率の実数部
（Ｅ’ （１００Ｈｚ））との比（静動比）（Ｅ’
（１００Ｈｚ）／Ｅ’（５Ｈ２））で表し、Ｇｓが大
きいほど、また静動比＝ （Ｅ’ （１００Ｈｚ）／
Ｅ’ （５Ｈｚ））が小さいほど良好である。The vibration damping properties were evaluated by determining the static shear modulus Gs of the vulcanizate according to JIS K6301, and by determining the real number of complex dynamic Young's modulus measured at a frequency of 5 Hz using a viscoelastic spectrometer manufactured by Iwamoto Seisakusho. (Static dynamic ratio) (E'
(100Hz)/E'(5H2)), and the larger Gs is, the static dynamic ratio = (E'(100Hz)/
E' (5Hz)) is smaller, the better.
ｙ企処方 （部）ポリマー
１００ＦＥＦカーボンブ
ラツク ３゜亜鉛華
５ステアリン酸
ｌ加硫促進剤ＣＺ
２（シクロヘキシル−ベンゾチアゾール−スルフェ
ンアミド）
イオウ ２参考例
１
内容積５１の攪拌機付きオートクレーブにチン素雰囲気
下でシクロヘキサン２．５００ｇ、イソプレン３５０ｇ
および１．３−ブタジェン１５０ｇを仕込み、６０℃に
調節した。y Planned recipe (part) Polymer 100FEF carbon black 3゜zinc white
5 stearic acid
l Vulcanization accelerator CZ
2 (Cyclohexyl-Benzothiazole-Sulfenamide) Sulfur 2 Reference Example 1 2.500 g of cyclohexane and 350 g of isoprene were placed in an autoclave with an internal volume of 51 mm and equipped with a stirrer under a tin atmosphere.
and 150 g of 1,3-butadiene were charged and the temperature was adjusted to 60°C.
別容器に、（ａ）２−エチルヘキサン酸ネオジム／（ト
））トリイソブチルアルミニウム／（Ｃ）ジエチルアル
ミニウムクロライド／（ｄ）アセチルアセトン（モル比
）＝１／４０／４／２の割合で添加混合し、少量のイソ
プレンの存在下、５０’Ｃで３０分間熟成して触媒を調
製した。In a separate container, add and mix (a) neodymium 2-ethylhexanoate/(t)) triisobutylaluminum/(C) diethylaluminum chloride/(d) acetylacetone (molar ratio) = 1/40/4/2. The catalyst was prepared by aging at 50'C for 30 minutes in the presence of a small amount of isoprene.
この熟成触媒を、イソプレン、１，３−ブタジェンのモ
ノマー１．２Ｘ１０’モルに対してネオジム原子１モル
となるように前記オートクレーブ中に仕込み、６０℃で
７時間重合反応を行った。This aged catalyst was charged into the autoclave in an amount of 1 mole of neodymium atoms per 1.2×10' moles of monomers of isoprene and 1,3-butadiene, and a polymerization reaction was carried out at 60° C. for 7 hours.
重合転化率が１００％であることを確認したのち、２，
６−ジーｔ−ブチルカテコール４ｇをメタノール５ ｍ
ｊ２に溶かした溶液を添加して反応を終了させた。After confirming that the polymerization conversion rate is 100%, 2.
4 g of 6-di-t-butylcatechol to 5 m of methanol
The reaction was terminated by adding a solution dissolved in j2.
次いで、得られたポリマー溶液をメタノール中に注ぎ、
ポリマーを回収し、次いで６０℃の真空乾燥機でポリマ
ーを乾燥し、ポリマー４８０ｇを得た。このポリマーの
ムーニー粘度（Ｍ Ｌ ＋や４．１００℃）は、５０で
あった。The resulting polymer solution was then poured into methanol,
The polymer was collected and then dried in a vacuum dryer at 60° C. to obtain 480 g of polymer. The Mooney viscosity (M L + or 4.100° C.) of this polymer was 50.
得られたポリマー（以下「ポリマーＡ」という）の組成
およびミクロ構造を第１表に示す。Table 1 shows the composition and microstructure of the obtained polymer (hereinafter referred to as "Polymer A").
参考例２〜５
１．３−ブタジェンとイソプレンとの量を変える以外は
、参考例１と同様にして重合反応を実施し、ポリマーＢ
−Ｅを得た。得られた各ポリマーのムーニー粘度、ミク
ロ構造を、あわせて第１表に示す。Reference Examples 2 to 5 A polymerization reaction was carried out in the same manner as in Reference Example 1 except that the amounts of 1,3-butadiene and isoprene were changed, and polymer B
-E was obtained. The Mooney viscosity and microstructure of each of the obtained polymers are also shown in Table 1.
参考例６
参考例１と同様の方法により、イソプレン単独重合体（
ポリマーＦ）を得た。このポリマーのムーニー粘度、ミ
クロ構造を、第１表に示す。Reference Example 6 Isoprene homopolymer (
Polymer F) was obtained. The Mooney viscosity and microstructure of this polymer are shown in Table 1.
実施例１〜４
参考例１〜４で得られたポリマーＡ−Ｄと、天然ゴム（
ＮＲ）とを、前記配合処方に従って加硫し、その加硫物
の加硫物性を第２表に示す。Examples 1 to 4 Polymers A-D obtained in Reference Examples 1 to 4 and natural rubber (
NR) was vulcanized according to the above-mentioned formulation, and the vulcanized physical properties of the vulcanized product are shown in Table 2.
比較例１〜３
参考例５で得られたポリマーＥ、参考例６で得られたポ
リマーＦ、市販のポリブタジェン（日本合成ゴム側製、
ＢＲＯＩ）を、前記配合処方に従って加硫し、その加硫
物の加硫物性を第２表に示す。Comparative Examples 1 to 3 Polymer E obtained in Reference Example 5, Polymer F obtained in Reference Example 6, commercially available polybutadiene (manufactured by Japan Synthetic Rubber Co., Ltd.,
BROI) was vulcanized according to the above-mentioned formulation, and the vulcanized physical properties of the vulcanized product are shown in Table 2.
実施例１〜４と比較例１〜３とから、本発明のイソプレ
ン−ブタジエン系共重合体を配合したゴム組成物は、従
来のポリブタジェン、ポリイソプレンに比較して伸長疲
労が同等以上であり、制動比が優れていることが分かる
。From Examples 1 to 4 and Comparative Examples 1 to 3, the rubber composition blended with the isoprene-butadiene copolymer of the present invention has the same or higher elongation fatigue compared to conventional polybutadiene and polyisoprene. It can be seen that the braking ratio is excellent.
比較例４
参考例１で得られたポリマーＡを１０重量部と・天然ゴ
ム９０重量部とをゴム成分として用い、第２表の配合処
方に従って加硫し・その加硫物０加硫物性を第２表に示
す。Comparative Example 4 Using 10 parts by weight of Polymer A obtained in Reference Example 1 and 90 parts by weight of natural rubber as rubber components, the vulcanized product was vulcanized according to the formulation shown in Table 2. Shown in Table 2.
（以下余白）
〔発明の効果〕
本発明は、ランタン系列希土類金属触媒を用いて得られ
るイソプレン−ブタジエン系共重合体と天然ゴムおよび
／またはポリイソプレンゴムとを特定の割合で含有する
ゴム組成物であり、公知の共役ジエン系重合体に比較し
て振動吸収特性および耐疲労特性に優れた加硫物が得ら
れる。(The following is a blank space) [Effects of the Invention] The present invention provides a rubber composition containing an isoprene-butadiene copolymer obtained using a lanthanum series rare earth metal catalyst and natural rubber and/or polyisoprene rubber in a specific ratio. Therefore, a vulcanizate having superior vibration absorption properties and fatigue resistance properties compared to known conjugated diene polymers can be obtained.
Claims (1)
合して得られるシス−１，４結合を９０％以上含有する
イソプレン−ブタジエン系共重合体２０〜９０重量部と
、（ロ）天然ゴムおよび／またはポリイソプレンゴム８
０〜１０重量部とを含むことを特徴とする防振ゴム組成
物。(1) (a) 20 to 90 parts by weight of an isoprene-butadiene copolymer containing 90% or more of cis-1,4 bonds obtained by polymerization in the presence of a lanthanum-based rare earth metal catalyst; and (b) a natural Rubber and/or polyisoprene rubber8
A vibration-proof rubber composition comprising 0 to 10 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62133899A JPH0774291B2 (en) | 1987-05-29 | 1987-05-29 | Anti-vibration rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62133899A JPH0774291B2 (en) | 1987-05-29 | 1987-05-29 | Anti-vibration rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63297437A true JPS63297437A (en) | 1988-12-05 |
| JPH0774291B2 JPH0774291B2 (en) | 1995-08-09 |
Family
ID=15115706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62133899A Expired - Lifetime JPH0774291B2 (en) | 1987-05-29 | 1987-05-29 | Anti-vibration rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774291B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294663A (en) * | 1992-08-28 | 1994-03-15 | General Tire, Inc. | Tire tread compositions of isoprene-styrene/butadiene emulsion polymers with 1,4 cis-polyisoprene rubber |
| WO2005003226A1 (en) * | 2003-07-01 | 2005-01-13 | Bridgestone Corporation | Rubber composition and tire using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5821434A (en) * | 1981-07-31 | 1983-02-08 | Japan Synthetic Rubber Co Ltd | Polybutadiene rubber composition |
| JPS59122531A (en) * | 1982-12-28 | 1984-07-16 | Japan Synthetic Rubber Co Ltd | Rubber composition having improved strength |
-
1987
- 1987-05-29 JP JP62133899A patent/JPH0774291B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5821434A (en) * | 1981-07-31 | 1983-02-08 | Japan Synthetic Rubber Co Ltd | Polybutadiene rubber composition |
| JPS59122531A (en) * | 1982-12-28 | 1984-07-16 | Japan Synthetic Rubber Co Ltd | Rubber composition having improved strength |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294663A (en) * | 1992-08-28 | 1994-03-15 | General Tire, Inc. | Tire tread compositions of isoprene-styrene/butadiene emulsion polymers with 1,4 cis-polyisoprene rubber |
| WO2005003226A1 (en) * | 2003-07-01 | 2005-01-13 | Bridgestone Corporation | Rubber composition and tire using the same |
| US9033014B2 (en) | 2003-07-01 | 2015-05-19 | Bridgestone Corporation | Rubber composition and tire using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774291B2 (en) | 1995-08-09 |
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