JPH03168234A - Propylene-based elastomer composition - Google Patents
Propylene-based elastomer compositionInfo
- Publication number
- JPH03168234A JPH03168234A JP30857389A JP30857389A JPH03168234A JP H03168234 A JPH03168234 A JP H03168234A JP 30857389 A JP30857389 A JP 30857389A JP 30857389 A JP30857389 A JP 30857389A JP H03168234 A JPH03168234 A JP H03168234A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- ethylene
- compound
- weight
- polypropylene
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 25
- 229920001971 elastomer Polymers 0.000 title claims description 20
- 239000000806 elastomer Substances 0.000 title claims description 13
- -1 polypropylene Polymers 0.000 claims abstract description 54
- 239000004743 Polypropylene Substances 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 150000004291 polyenes Polymers 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 51
- 238000000034 method Methods 0.000 description 51
- 238000006116 polymerization reaction Methods 0.000 description 48
- 239000007787 solid Substances 0.000 description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 239000011949 solid catalyst Substances 0.000 description 21
- 239000010936 titanium Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 16
- 150000001491 aromatic compounds Chemical class 0.000 description 15
- 150000003609 titanium compounds Chemical class 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 13
- 150000002681 magnesium compounds Chemical class 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical compound COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000012685 gas phase polymerization Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- GYPMBQZAVBFUIZ-UHFFFAOYSA-N 1,2-dimethoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1OC GYPMBQZAVBFUIZ-UHFFFAOYSA-N 0.000 description 2
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QSZCGGBDNYTQHH-UHFFFAOYSA-N 2,3-dimethoxyphenol Chemical compound COC1=CC=CC(O)=C1OC QSZCGGBDNYTQHH-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- OGJJVYFQXFXJKU-UHFFFAOYSA-N 3-methylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(C)=CC1C=C2 OGJJVYFQXFXJKU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 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
- GXJPKIGCMGAHTL-UHFFFAOYSA-N dipropyl benzene-1,4-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C(=O)OCCC)C=C1 GXJPKIGCMGAHTL-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229940030010 trimethoxybenzene Drugs 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- UHHCYAAVGADGGP-HTQZYQBOSA-N (1s,2s)-1,2-bis(ethenyl)cyclobutane Chemical compound C=C[C@@H]1CC[C@H]1C=C UHHCYAAVGADGGP-HTQZYQBOSA-N 0.000 description 1
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 1
- AGIQIOSHSMJYJP-UHFFFAOYSA-N 1,2,4-Trimethoxybenzene Chemical compound COC1=CC=C(OC)C(OC)=C1 AGIQIOSHSMJYJP-UHFFFAOYSA-N 0.000 description 1
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 1
- PYYCVJQREOKYDO-UHFFFAOYSA-N 1-[(1-carboxycyclohexyl)diazenyl]cyclohexane-1-carboxylic acid Chemical compound C1CCCCC1(C(O)=O)N=NC1(C(=O)O)CCCCC1 PYYCVJQREOKYDO-UHFFFAOYSA-N 0.000 description 1
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- BQMLWEKOSHSOFT-UHFFFAOYSA-N 1-ethoxy-2,2-dimethylpropane Chemical compound CCOCC(C)(C)C BQMLWEKOSHSOFT-UHFFFAOYSA-N 0.000 description 1
- POXXQVSKWJPZNO-UHFFFAOYSA-N 1-o-ethyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC(C)C POXXQVSKWJPZNO-UHFFFAOYSA-N 0.000 description 1
- LCICHIHLCDAKBX-UHFFFAOYSA-N 1-o-ethyl 3-o-(2-methylpropyl) benzene-1,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC(C)C)=C1 LCICHIHLCDAKBX-UHFFFAOYSA-N 0.000 description 1
- NCWRQKBPNFFHDA-UHFFFAOYSA-N 1-o-ethyl 4-o-(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 NCWRQKBPNFFHDA-UHFFFAOYSA-N 0.000 description 1
- HRJOMMSRROBCMQ-UHFFFAOYSA-N 1-o-methyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OCC(C)C HRJOMMSRROBCMQ-UHFFFAOYSA-N 0.000 description 1
- NOJDVBYTDSRQSU-UHFFFAOYSA-N 1-o-methyl 3-o-(2-methylpropyl) benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OCC(C)C)=C1 NOJDVBYTDSRQSU-UHFFFAOYSA-N 0.000 description 1
- WBNCJBMUOHNNSW-UHFFFAOYSA-N 1-o-methyl 4-o-(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 WBNCJBMUOHNNSW-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 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]
本発明はプロピレン系エラストマー組戒物に関する.
[従来の技術]
熱可塑性エラストマーは、省エネルギーあるいは省資源
タイプのエラストマーとして,特に加硫ゴムの代替品と
して,自動車部品,工業機械部品、電子・電気部品、建
材などに広く使用されている.
オレフィン系熱可塑性エラストマ−(TPO)は、一般
に、ポリプロピレンとエチレンープロピレンージエンゴ
ム(EPDM)とを過酸化物の存在下で混練する方法に
よって製造されている(例えば、特開昭61−2177
47号公報).シかしながら、この方法には、操作が煩
雑で製造コストが高いという欠点があった.
一方,前記TPOの力学的特性と同様の特性を有する高
分子重合体を重合段階で直接的に製造することにより、
低コスト化を図る試みが従来から種々行なわれてきた.
例えば2プロピレンーヘキセン共重合体(例えば、特開
昭49−53983号および特公昭62−19444号
各公報〉および弾性ポリプロピレン(例えば特開昭61
−179247号公報)などが提案されている.しかし
ながら2これらの高分子重合体は,いずれも低温特性が
不十分であった.また,ポリプロピレンの低温特性を改
良する方法として、プロピレン/エチレン−プロピレン
二段重合法がよく知られているが(例えば,特開昭57
−508[14号公報)、この方法では、柔軟性と実用
性のある引張強さとを兼ね備えた加硫ゴム状重合体を製
造することか困難であった。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a propylene-based elastomer composition. [Prior Art] Thermoplastic elastomers are widely used as energy-saving or resource-saving elastomers, especially as substitutes for vulcanized rubber, in automobile parts, industrial machinery parts, electronic/electrical parts, building materials, etc. Olefinic thermoplastic elastomers (TPO) are generally manufactured by a method of kneading polypropylene and ethylene-propylene-diene rubber (EPDM) in the presence of peroxide (for example, JP-A-61-2177).
Publication No. 47). However, this method has the drawbacks of complicated operations and high manufacturing costs. On the other hand, by directly producing a high molecular weight polymer having properties similar to the mechanical properties of TPO in the polymerization step,
Various attempts have been made to reduce costs.
For example, 2-propylene-hexene copolymer (for example, JP-A-49-53983 and JP-A-62-19444) and elastic polypropylene (for example, JP-A-61
-179247) have been proposed. However, both of these high molecular weight polymers had insufficient low temperature properties. Furthermore, the propylene/ethylene-propylene two-stage polymerization method is well known as a method for improving the low-temperature properties of polypropylene (for example, JP-A-57
-508 [Publication No. 14], it was difficult to produce a vulcanized rubber-like polymer that had both flexibility and practical tensile strength.
[発明が解決しようとする課題]
本発明は、未加硫状態でも実用性のある引張強度を有し
、柔軟性や低温特性が満足でき、表面粘着性が低く、し
かも製造コストが低いプロビボレン系エラストマー組或
物を提供することを目的とするものである。[Problems to be Solved by the Invention] The present invention provides a probibolene-based material that has practical tensile strength even in an unvulcanized state, has satisfactory flexibility and low-temperature properties, has low surface tackiness, and has low manufacturing costs. The object is to provide an elastomer composite.
本発明者らは、前記の目的を達成するために鋭意研究を
重ねた結果,特定のポリプロピレンホモ重合体を用いる
と,架橋させなくても,TOP(部分的に架橋されてい
る)と同様の物性を有するエラストマー組成物が得られ
ることを見出した。本発明は、この知見に基づくもので
ある.[課題を解決するための手段]
すなわち,本発明は、(a)固有粘度が1.2dl/g
以上である沸騰ヘプタン可溶性ポリプロピレン10〜9
0重量%と固有粘度が0.5〜9.0dQ/gである沸
騰ヘプタン不溶性ポリプロピレン90〜10重量%とか
らなるポリプロピレン系重合体10〜95重量%、およ
び
(b)エチレン単位含有量が10〜60モル%で、固有
粘度が0.5〜7.0dl/gであるエチレン−プロピ
レン共重合体、または
(b゜)エチレン単位含有量が10〜60モル%で、ポ
リエン単位含有量が1−10モル%で、固有粘度がO.
S〜7.0dl/gであるエチレンープロピレンーポリ
エン共重合体90〜5重量%からなるプロピレン系エラ
ストマー組戊物に関する.
本発明の組或物において、ボリブロピレン系重合体(a
)は、組戊物の全重量に対して10〜95重量%、好ま
しくは40〜80重量%の量で存在する.ボリブロピレ
ン系重合体(a)の量が10重量%未満になると耐熱性
が著しく低下し、95重量%を超えると耐低温衝撃性が
著しく低下するので好ましくない.
ポリプロピレン系重合体(a)は,(i)固有粘度が1
.2d交/g以上(好ましくは1.5dl/g以上)の
沸騰ヘプタン可溶性ポリプロピレン戊分10〜90重量
%(好ましくは25〜70重量%〉と. (ii)固有
粘度が0.5〜9.Od文/g(好ましくは1.0〜6
.0dJ1/g)の沸騰ヘプタン不溶性ポリプロピレン
戊分90〜IO重量%(好ましくは75〜30重量%)
とからなる。沸騰ヘプタン可溶性ポリプロピレン成分(
i)の固有粘度が1.2dll/g未満であると破断時
応力が低下し,ゴム弾性が損なわれるので好ましくなく
、その含有量が10重量%未満になると低剛性か損なわ
れ、90重量%を超えると十分な機械的強度が得られな
いので好ましくない.沸騰ヘプタン不溶性ポリプロピレ
ン或分(ii)の固有粘度か0.5di/g未満である
と耐衝撃性が著しく低下し、9.0dl/gを超えると
戒形が不可能になる.ボリブロピレン系重合体(a)は
次の性質(i)〜(iv)を有しているものが特に好ま
しい.(i)”C−NMRによるベンタッド分率におい
て,rrrr/l−was−が20%以上である.(百
)示差8量温度計(DSC)にて測定した融解ピーク(
Tm)か150℃以上である.(iff) D S C
にて測定した融解エンタルピー(△H)が1 0 0
Jug以下である.( iv)透過型電子顕微鏡での観
察において、ドメイン構造が観察される.
本発明の組成物においてエチレンープロピレン共重合体
(b)またはエチレンープロピレンージエン共重合体(
b゛)は,組或物の全重量に対して5〜90重量%,好
ましくは20〜60重量%の量で存在する。共重合体(
b)および(b゛)においてエチレン単位の含有量は各
々10〜60モル%(好ましくは20〜50モル%〉で
ある.エチレン単位含有量が10モル%未満になると耐
低温衝撃性が著しく低下し,60モル%を超えると表面
光沢が損なわれるので好ましくない.前記共重合体(b
)および(b′)の固有粘度は0.5〜7.Od文/g
(好ましくは1.0〜3.0dl/g)である.その固
有粘度が0.5du/g未満であると耐低温衝撃性が著
しく低下し、7.0dl/gを超えると表面光沢が損な
われ,耐面衝撃性が損なわれるのて好ましくない。As a result of intensive research to achieve the above object, the present inventors have found that when a specific polypropylene homopolymer is used, the same properties as TOP (partially crosslinked) can be obtained even without crosslinking. It has been found that an elastomer composition having physical properties can be obtained. The present invention is based on this knowledge. [Means for Solving the Problems] That is, the present invention provides (a) an intrinsic viscosity of 1.2 dl/g;
Boiling heptane soluble polypropylene 10 to 9
(b) 10 to 95 weight % of a polypropylene polymer consisting of 0 weight % and 90 to 10 weight % of boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dQ/g, and (b) an ethylene unit content of 10 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl/g, or (b°) an ethylene unit content of 10 to 60 mol% and a polyene unit content of 1 -10 mol%, the intrinsic viscosity is O.
A propylene-based elastomer composite comprising 90 to 5% by weight of an ethylene-propylene-polyene copolymer having a molecular weight of S to 7.0 dl/g. In the composition of the present invention, polypropylene polymer (a
) is present in an amount of 10 to 95% by weight, preferably 40 to 80% by weight, based on the total weight of the composite. If the amount of the polypropylene polymer (a) is less than 10% by weight, the heat resistance will be significantly lowered, and if it exceeds 95% by weight, the low-temperature impact resistance will be significantly lowered, which is not preferred. The polypropylene polymer (a) has (i) an intrinsic viscosity of 1
.. Boiling heptane soluble polypropylene fraction of 2dl/g or more (preferably 1.5dl/g or more) of 10 to 90% by weight (preferably 25 to 70% by weight). (ii) Intrinsic viscosity of 0.5 to 9. Od sentences/g (preferably 1.0-6
.. 0 dJ1/g) of boiling heptane-insoluble polypropylene fraction 90-IO wt% (preferably 75-30 wt%)
It consists of Boiling heptane soluble polypropylene component (
If the intrinsic viscosity of i) is less than 1.2 dll/g, the stress at break will decrease and the rubber elasticity will be impaired, which is undesirable. If the content is less than 10% by weight, the rigidity will be low or impaired, and 90% by weight. Exceeding this is not preferable because sufficient mechanical strength cannot be obtained. If the intrinsic viscosity of the boiling heptane-insoluble polypropylene (ii) is less than 0.5 dl/g, the impact resistance will be significantly reduced, and if it exceeds 9.0 dl/g, it will become impossible to form. Particularly preferred polypropylene polymers (a) have the following properties (i) to (iv). (i) "In the bentad fraction by C-NMR, rrrr/l-was- is 20% or more. (100) The melting peak measured with a differential 8-quantity thermometer (DSC) (
Tm) or 150℃ or higher. (if) DSC
The enthalpy of fusion (△H) measured at 1 0 0
Jug or less. (iv) Domain structure is observed in transmission electron microscopy. In the composition of the present invention, ethylene-propylene copolymer (b) or ethylene-propylene-diene copolymer (b)
b) is present in an amount of 5 to 90% by weight, preferably 20 to 60% by weight, relative to the total weight of the assembly. Copolymer (
In b) and (b), the content of ethylene units is each 10 to 60 mol% (preferably 20 to 50 mol%).When the ethylene unit content is less than 10 mol%, the low-temperature impact resistance is significantly reduced. However, if it exceeds 60 mol%, the surface gloss will be impaired, which is undesirable.
) and (b') have an intrinsic viscosity of 0.5 to 7. Od sentence/g
(preferably 1.0 to 3.0 dl/g). If the intrinsic viscosity is less than 0.5 du/g, the low-temperature impact resistance will be significantly reduced, and if it exceeds 7.0 dl/g, the surface gloss will be impaired and the surface impact resistance will be impaired, which is not preferable.
前記のポリプロピレン系重合体(a)と共重合体(b)
または(b゛)とからなる本発明のエラストマーM1成
物としては、破断伸びが300%以上(好ましくは40
0%以上)であり、破断時応力が1 0 0 Kglc
m”以上(好ましくは1 5 0 Kg/c1以上)で
あり、および/または引張弾性率か8 0 0 0 K
g/cm2以下(好ましくは5000κg/cm”以下
)である組成物が好ましい。The above polypropylene polymer (a) and copolymer (b)
The elastomer M1 composition of the present invention consisting of or (b) has an elongation at break of 300% or more (preferably 40% or more).
0% or more), and the stress at break is 100 Kglc.
m” or more (preferably 150 Kg/c1 or more) and/or tensile modulus of 8000 K
g/cm2 or less (preferably 5000 κg/cm'' or less).
破断伸びが300%未満のものはゴム弾性が損なわれる
ので好ましくなく、破断時応力が100Kg/c12未
満のものはゴム弾性が損なわれるので好ましくなく、更
に引張弾性率が8 0 0 0 Kg/c1を超えるの
は低剛性が損なわれるので好ましくない.
本発明のエラストマー組戊物は例えば、気相多段重合法
,スラリー多段重合法またはブレント法によって調製す
ることができる.以下,それらの調製法について順に説
明する.
象杷見旦玉直A
気相多段重合法で用いる触媒系は、例えば、( I )
(D結品性ポリオレフィンと(if)マグネシウム,
チタン、ハロゲン原子および電子供与性化合物からなる
固体触媒成分とからなる固体威分、
(■)有機アルミニウム化合物
(m)アルコキシ基含有芳香族化合物,および(IV)
電子供与性化合物
の組合せからなる.
前記の固体成分(I)は、結晶性ポリオレフイン(i)
1重量部に対して固体触媒或分(ii)をo.oo
s〜30重量部(好ましくは0.02〜10重量部)の
割合で含んでなる.
前記の固体成分(1)は,例えば,固体触媒成分(ii
)と有機アルミニウム化合物と場合により電子供与性化
合物との存在下に、オレフインを予備重合させる方法に
よって調製することができる(予備重合法).
ここで、固体触媒或分0i)は,マグネシウム,チタン
、ハロゲン原子および電子供与性化合物な必須或分とす
るものであり、これはマグネシウム化合物とチタン化合
物と電子供与性化合物とを接触させることによって調製
することができる.マグネシウム化合物としては,例え
ばマグネシウムジクロリトなどのマグネシウムジハライ
ド,酸化マグネシウム,水酸化マグネシウム,ハイドロ
タルサイト,マグネシウムのカルボン酸塩,ジエトキシ
マグネシウムなどのアルコキシマグネシウム、アリロキ
シマグネシウム、アルコキシマグネシウムハライト、ア
リロキシマグネシウムハライト、エチルブチルマグネシ
ウムなどのアルキルマグネシウム、アルキルマグネシウ
ムハライト,あるいは有機マグネシウム化合物と電子供
与体,ハロシラン,アルコキシシラン、シラノール及び
アルミニウム化合物などとの反応物などを挙げることか
てきるが,これらの中でマグネシウムハライド、アルコ
キシマグネシウム、アルキルマグネシウム,アルキルマ
グネシウムハライトか好適である.また,これらのマグ
ネシウム化合物は1種たけで用いてもよいし,2種以上
を組み合せて用いてもよい.
また、チタン化合物としては、例えばテトラメトキシチ
タン,テトラエトキシチタン、テトラーn−ブロボキシ
チタン,テトライソブロボキシチタン、テトラーn−ブ
トキシチタン、テトライソブトキシチタン、テトラシク
ロへキシロキシチタン,テトラフエノキシチタンなどの
テトラアルコキシチタン,四塩化チタン、四臭化チタン
、四ヨウ化チタンなどのテトラハロゲン化チタン、メト
キシチタニウムトリクロリド、エトキシチタニウムトリ
クロリド、ブロボキシチタニウムトリクロリド、n−ブ
トキシチタニウムトリクロリド2エトキシチタニウムト
ソブロくドなどのトリハロゲン化アルコキシチタン,ジ
メトキシチタニウムジクロリド、ジエトキシチタニウム
ジクロリド、ジプロボキシチタニウムジクロリト、ジー
n−ブロボキシチタニウムジクロリド,ジエトキシチタ
ニウムジブロミドなどのジハロゲン化ジアルコキシチタ
ン、トリメトキシチタニウムクロリト,トリエトキシチ
タニウムクロリト,トリブロボキシチタニウムクロリト
,トリーn−ブトキシチタニウムクロリドなどのモノハ
ゴゲン化トリアルコキシチタンなどが挙げられるが,こ
れらの中で高ハロゲン含右チタン化合物、特に四塩化チ
タンが好適である。これらのチタン化合物はそれぞれ単
独で用いてもよいし,2M以上を組み合せて用いてもよ
い。An elongation at break of less than 300% is undesirable because the rubber elasticity is impaired, a stress at break of less than 100 Kg/c12 is undesirable because the rubber elasticity is impaired, and a tensile modulus of elasticity is 8000 Kg/c1. Exceeding this is not preferable because low rigidity will be impaired. The elastomer composite of the present invention can be prepared, for example, by a gas phase multistage polymerization method, a slurry multistage polymerization method, or a Brent method. Below, we will explain their preparation methods in order. The catalyst system used in the gas phase multi-stage polymerization method is, for example, (I)
(D-solidifying polyolefin and (if) magnesium,
a solid component consisting of titanium, a halogen atom, and a solid catalyst component consisting of an electron-donating compound; (■) an organoaluminum compound; (m) an aromatic compound containing an alkoxy group; and (IV)
It consists of a combination of electron-donating compounds. The solid component (I) is crystalline polyolefin (i)
A portion (ii) of the solid catalyst was added to 1 part by weight. oo
s to 30 parts by weight (preferably 0.02 to 10 parts by weight). The solid component (1) is, for example, a solid catalyst component (ii
), an organoaluminum compound, and optionally an electron-donating compound (prepolymerization method). Here, the solid catalyst (0i) includes magnesium, titanium, a halogen atom, and an electron-donating compound, and is produced by bringing the magnesium compound, titanium compound, and electron-donating compound into contact with each other. It can be prepared. Magnesium compounds include, for example, magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylates, alkoxymagnesiums such as diethoxymagnesium, allyloxymagnesium, alkoxymagnesium halites, and aryloxymagnesium halides. Examples include alkylmagnesium halide, alkylmagnesium halide such as roxymagnesium halide and ethylbutylmagnesium, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. Among these, magnesium halides, alkoxymagnesiums, alkylmagnesiums, and alkylmagnesium halites are preferred. Further, these magnesium compounds may be used alone or in combination of two or more. Examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-broboxytitanium, tetraisobroboxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium. Tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide, titanium tetrahalide such as titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, broboxytitanium trichloride, n-butoxytitanium trichloride 2-ethoxytitanium Trihalogenated alkoxytitanium such as tosobrod, dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diproboxytitanium dichloride, di-n-broboxytitanium dichloride, diethoxytitanium dibromide, Examples include monohalogenated trialkoxytitanium such as methoxytitanium chloride, triethoxytitanium chloride, tribroboxytitanium chloride, and tri-n-butoxytitanium chloride. Among these, high halogen-containing titanium compounds, especially quaternary Titanium chloride is preferred. These titanium compounds may be used alone or in combination of 2M or more.
電子供与性化合物は、酸素、窒素2リン、イオウ、ケイ
素などを含有する有機化合物であり,基本的にはプロピ
レンの重合において、規則性を向上することができるも
のである.
このような電子供与性化合物としては、例えばエステル
類、チオエステル類,アミン類、ケトン類,ニトリル類
、ホスフィン類、エーテル類、チオエーテル類,酸無水
物、酸ハライドw42酸アミド類、アルデヒド類,有機
酸類などを挙げることができる.更には,例えば、ジフ
ェニルジメトキシシラン、ジフェニルジエトキシシラン
、ジベンジルジメトキシラン、テトラメトキシシラン、
テトラエトキシシラン,テトラフエノキシシラン,メチ
ルトリメトキシシラン、メチルトリエトキシシラン、メ
チルトリフェノキシシラン、フェニルトリメトキシシラ
ン、ペンジルトリメトキシシランなどの有機ケイ素化合
物、フタル酸一n−ブチル,フタル酸ジイソブチルなど
の芳香族ジカルボン酸エステル,安息香酸、p−メトキ
シ安J!香酸、p一エトキシ安息香酸,トルイル酸など
の芳香族モノカルボン酸の炭素数1〜4のアルキルエス
テル、イソブロビルメチルエーテル、イソブロビルエチ
ルエーテル,t−ブチルメチルエーテル、t−プチルエ
チルエーテル,t−ブチルーn−プロビルエーテル,t
−ブチルーn−プチルエーテル,t−アミルメチルエー
テル,t−アミルエチルエーテルなどの非対称エーテル
、2.2゜−アゾビス(2−エチルプロパン)、2,2
−アゾビス(2−エチルブロバン)、2,2′−アゾビ
ス(2−メチルベンタン),a,a”−アゾビスイソブ
チロニトリル、1.1’−アゾビス(l−シクロヘキサ
ンカルボン酸)、(1−フェニルメチル)一アゾジフエ
ニルメタン,2−フェニルアゾ−2.4−ジメチル−4
ートリキシベンタンニトリルなどのアゾ結合に立体障害
置換基が結合して成るアゾ化合物などが挙げられ、これ
らは1種を用いてもよいし、2種以上を組み合せて用い
てもよい.
具体的には,ジメチルフタレート,ジェチルフタレート
,ジブロビルフタレート、ジイソブチルフタレート,メ
チルエチルフタレート、メチルブロビルフタレート、メ
チルイソブチルフタレート,エチルプロビルフタレート
,エチルイソブチルフタレート,プロビルイソブチルフ
タレートジメチルテレフタレート、ジエチルテレフタレ
ート、ジプロピルテレフタレート,ジイソブチルテレフ
タレート、メチルエチルテレフタレート,メチルブロビ
ルテレフタレート,メチルイソブチルテレフタレート,
エチルプロビルテレフタレート,エチルイソブチルテレ
フタレート、プロビルイソブチルテレフタレート、ジメ
チルイソフタレート、ジエチルイソフタレート、ジプロ
ビルイソフタレート,ジイソブチルイソフタレート、メ
チルエチルイソフタレート、メチルブロビルイソフタレ
ート、メチルイソブチルイソフタレート,エチルプロビ
ルイソフタレート、エチルイソブチルイソフタレート及
びプロビルイソブチルイソフタレートなどの芳香族ジカ
ルボン酸ジエステル、ギ酸メチル、酢酸エチル,酢酸ビ
ニル,酢酸プロビル,酢酸オクチル,酢酸シクロヘキシ
ル,ブロビオン酸エチル,酢酸エチル,吉草酸エチル,
クロロ酢酸メチル、ジクロロ酢酸エチル、メタクリル酸
メチル、クロトン酸エチル,ビバリン酸エチル、マレイ
ン酸ジメチル、シクロヘキサンカルボン酸エチル、安息
香酸エチル、安息香酸ブロビル、安息香酸ブチル、安息
香酸オクチル,安息香酸シクロヘキシル,安怠香酸フエ
ニル,安息香酸ベンジル,トルイル酸エチル,トルイル
酸ア主ル、アニス酸エチル、エトキシ安息香酸エチル,
p−ブトキシ安息香酸エチル、0−クロロ安息香酸エチ
ル及びナフトエ酸エチルなどのモノエステル、γ−バレ
ロラクトン、クマリン、フタリト、炭酸エチレンなどの
炭素数2〜18のエステル角、安息香酸、p−オキシ安
息香酸などの有機酸類、無水コハク酸、無水安息香酸、
無水P−}−ルイル酸などの酸無水物類,アセトン、メ
チルエチルケトン,メチルイソブチルケトン、アセトフ
エノン、ペンゾフエノン、ベンゾキノンなどの炭素数3
〜15のケトン類,アセトアルデヒド,オクチルアルデ
ヒト、ベンズアルデヒド、トルアルデヒド、ナフチルア
ルデヒドなどの炭素数2〜l5のアルデヒド類、アセチ
ルクロリド、ペンジルクロリド,トルイル酸クロリド、
アニス酸クロリトなどの炭素数2〜l5の酸ハライド類
,メチルエーテル、エチルエーテル、イソブロビルエー
テル n−ブチルエーテル,アミルエーテル、テトラヒ
ドロフラン、アニソール、ジフエニルエーテル エチレ
ングリコールブチルエーテルなどの炭素数2〜20のエ
ーテル類,酢酸アミト,安息香酸アミド,トルイル酸ア
ミトなどの酸アミト類、トリブチルアミン、N,N’−
ジメチルビベラジン、トリベンジルアミン、アニリン,
ビリジン、ピコリン、テトラメチルエチレンジアミンな
どのアミン類、アセトニトリル、ペンゾニトリル,トル
ニトリルなどのニトリル類などを挙げることができる.
これらの中で、エステル類、エーテル類、ケトン類及び
酸無水物が好ましく、特に,フタル酸ジーn−ブチル、
フタル酸ジイソブチルなどの芳香族ジカルボン酸ジエス
テル,安息香酸、p−メトシキ安怠香酸,P一エトキシ
安息香酸,トルイル酸などの芳香族モノカルボン酸の炭
素数1〜4のアルキルエステルなどが好適である.芳香
族ジカルボン酸ジエステルは,.触媒活性及び活性持続
性を向上させるので特に好ましい.
前記の固体触媒成分(ii)の調製は、公知の方法(特
開昭53−43094号公報,特開昭55−13510
2号公報、特開昭55−1コ5l03号公報、特開昭s
a−taaoa号公報)で行なうことができる.例えば
(1)マグネシウム化合物又はマグネシウム化合物と電
子供与体との錯化合物を,電子供与体及び所望に応じて
用いられる粉砕助剤などの存在下に粉砕して,チタン化
合物と反応させる方法,(2)還元能を有しないマグネ
シウム化合物の液状物と液状チタン化合物とを,電子供
与体の存在下において反応させて.固体状のチタン複合
体を析出させる方法、(3)前記(1)又は(2)で得
られたものにチタン化合物を反応させる方法,(4〉前
記(1)または(2)で得られたものに、さらに電子供
与体及びチタン化合物を反応させる方法、(5)マグネ
シウム化合物又はマグネシウム化合物と電子供与体との
錯化合物を、電子供与体、チタン化合物及び所望に応じ
て用いられる粉砕助材などの存在下で粉砕したのち,ハ
ロゲン又はハロゲン化合物で処理する方法、(6)前記
(1)〜(4)で得られた化合物をハロゲン又はハロゲ
ン化合物で処理する方法.などによって調製することが
てきる.
さらに,これらの方法以外の方法(特開昭56−166
205号公報,特開昭57−63309号公報、特開昭
57−190004号公報、特開昭57−300407
号公報、特開昭58−47003号公報)によっても,
前記固体触媒或分(ii)を調製することかできる.
また、周期表n〜■族に属する元素の酸化物、例えば、
酸化ケイ素,酸化マグネシウム、酸化アルミニウムなど
の酸化物又は周期表■〜■族に属する元素の酸化物の少
なくとも1種を含む複合酸化物,例えば、シリカアルミ
ナなどに前記マグネシウム化合物を担持させた固形物と
電子供与体とチタン化合物とを,溶媒中で、0〜200
″C、好ましくは10〜150℃の範囲の温度によて2
分〜24時間接触させることにより固体触媒成分(11
)を調製することができる.
また,固体触媒戒分(ii)の調製に当たり、溶媒とし
てマグネシウム化合物、電子供与体及びチタン化合物に
対して不活性な有機溶媒,例えば、ヘキサン、ヘプタン
などの脂肪族炭化水素、ベンゼン2 トルエンなどの芳
香族炭化水素、あるいは炭素数l〜l2の飽和又は不飽
和の脂肪族,脂環式及び芳香族炭化水素のモノ及びポリ
ハロゲン化合物などのハロゲン化炭化水素などを使用す
ることができる.
このようにして調製された固体触媒戊分(ii)の組成
は,通常マグネシウム/チタン原子比が2〜100、ハ
ロゲン/チタン原子比が5〜200,・α子供与体/チ
タンモル比が0.1−10の範囲にある。Electron-donating compounds are organic compounds containing oxygen, nitrogen, diphosphorus, sulfur, silicon, etc., and basically can improve the regularity in propylene polymerization. Examples of such electron-donating compounds include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, and organic Examples include acids. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxylane, tetramethoxysilane,
Organosilicon compounds such as tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, pendyltrimethoxysilane, mono-n-butyl phthalate, phthalic acid Aromatic dicarboxylic acid esters such as diisobutyl, benzoic acid, p-methoxyben J! C1-4 alkyl esters of aromatic monocarboxylic acids such as aromatic acid, p-ethoxybenzoic acid, toluic acid, isobrobyl methyl ether, isobrobyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl n-propyl ether, t
-Asymmetric ethers such as butyl-n-butyl ether, t-amylmethyl ether, t-amyl ethyl ether, 2.2°-azobis(2-ethylpropane), 2,2
-Azobis(2-ethylbroban), 2,2'-azobis(2-methylbentane), a,a''-azobisisobutyronitrile, 1,1'-azobis(l-cyclohexanecarboxylic acid), (1 -phenylmethyl)-1azodiphenylmethane, 2-phenylazo-2,4-dimethyl-4
Examples include azo compounds in which a sterically hindered substituent is bonded to an azo bond, such as -trixybentanenitrile, and these may be used alone or in combination of two or more. Specifically, dimethyl phthalate, jetyl phthalate, dibrobyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl brobyl phthalate, methyl isobutyl phthalate, ethyl probyl phthalate, ethyl isobutyl phthalate, probyl isobutyl phthalate dimethyl terephthalate, diethyl Terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl brobyl terephthalate, methyl isobutyl terephthalate,
Ethylpropyl terephthalate, ethyl isobutyl terephthalate, probyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, diprobyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl brobyl isophthalate, methyl isobutyl isophthalate, ethyl probyl Aromatic dicarboxylic acid diesters such as isophthalate, ethyl isobutyl isophthalate and probyl isobutyl isophthalate, methyl formate, ethyl acetate, vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl blobionate, ethyl acetate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl bivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, brovyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Phenyl laxate, benzyl benzoate, ethyl toluate, alkyl toluate, ethyl anisate, ethyl ethoxybenzoate,
Monoesters such as ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, ester angles having 2 to 18 carbon atoms such as γ-valerolactone, coumarin, phthalite, ethylene carbonate, benzoic acid, p-oxy Organic acids such as benzoic acid, succinic anhydride, benzoic anhydride,
Acid anhydrides such as P-}-ruyl anhydride, 3 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, benzoquinone, etc.
~15 ketones, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthylaldehyde, acetyl chloride, pendyl chloride, toluic acid chloride,
Acid halides with 2 to 15 carbon atoms such as anisyl chloride, methyl ether, ethyl ether, isobrobyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethers with 2 to 20 carbon atoms such as ethylene glycol butyl ether Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N,N'-
Dimethylbiverazine, tribenzylamine, aniline,
Examples include amines such as pyridine, picoline, and tetramethylethylenediamine, and nitriles such as acetonitrile, penzonitrile, and tolnitrile. Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl phthalate,
Suitable examples include diesters of aromatic dicarboxylic acids such as diisobutyl phthalate, alkyl esters of aromatic monocarboxylic acids having 1 to 4 carbon atoms such as benzoic acid, p-methoxybenzoic acid, P-ethoxybenzoic acid, and toluic acid. be. Aromatic dicarboxylic acid diesters are. It is particularly preferred because it improves catalyst activity and activity sustainability. The above-mentioned solid catalyst component (ii) can be prepared by a known method (JP-A-53-43094, JP-A-55-13510).
Publication No. 2, JP-A-55-1-5103, JP-A-S
a-taaoa publication). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a grinding aid used as desired, and reacting it with a titanium compound; ) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor. A method of precipitating a solid titanium composite, (3) A method of reacting a titanium compound with the material obtained in (1) or (2) above, (4) A method of reacting a titanium compound with the material obtained in (1) or (2) above. (5) A method of reacting a magnesium compound or a complex compound of a magnesium compound and an electron donor with an electron donor, a titanium compound, and a grinding aid used as desired. (6) A method in which the compound obtained in (1) to (4) above is treated with a halogen or a halogen compound. In addition, methods other than these methods (Japanese Unexamined Patent Publication No. 56-166
205, JP 57-63309, JP 57-190004, JP 57-300407
According to Japanese Patent Application Laid-open No. 58-47003),
The solid catalyst part (ii) can be prepared. In addition, oxides of elements belonging to groups n to ■ of the periodic table, for example,
A composite oxide containing at least one oxide of an oxide such as silicon oxide, magnesium oxide, or aluminum oxide or an oxide of an element belonging to groups ■ to ■ of the periodic table, such as a solid material in which the magnesium compound is supported on silica alumina, etc. , an electron donor, and a titanium compound in a solvent at a concentration of 0 to 200
2°C, preferably at a temperature in the range of 10-150°C.
The solid catalyst component (11
) can be prepared. In addition, in preparing the solid catalyst component (ii), an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, benzene, toluene, etc. Aromatic hydrocarbons or halogenated hydrocarbons such as mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used. The composition of the solid catalyst fraction (ii) prepared in this way is usually a magnesium/titanium atomic ratio of 2 to 100, a halogen/titanium atomic ratio of 5 to 200, and an α-child donor/titanium molar ratio of 0. It is in the range of 1-10.
こうして得られた固体触媒戒分(it)と、有機アルミ
ニウム化合物と場合により電子供与性化合物との存在下
に、オレフィンを予it合させることによって、前記の
固体戊分(I)を調製することかできる。The above-mentioned solid catalyst component (I) is prepared by preliminarily combining the solid catalyst component (IT) thus obtained with an olefin in the presence of an organoaluminum compound and optionally an electron-donating compound. I can do it.
ここで用いる有機アルミニウム化合物としては、一般式
AfLR3pXz−p( 1 )
(式中のR1は炭素数1〜10のアルキル基,Xは塩素
、臭素などのハロゲン原子、pは1〜3の数である)
で表される化合物を挙げることができる.このようなア
ルミニウム化合物としては、例えば、トリメチルアルミ
ニウム,トソエチルアルミニウム,トリイソブロビルア
ルミニウム,トリイソブチルアルミニウム,トリオクチ
ルアルミニウムなどのトリアルキルアルミニウム,ジエ
チルアルミニウムモノクロリド,ジイソプロビルアルミ
ニウムモノクロリド、ジインブチルアルミニウムモノク
ロリド,ジオクチルアルミニウムモノクロリトなどのジ
アルキルアルミニウムモノハライド、エチルアルミニウ
ムセスキクロリドなどのアルキルアルミニウムセスキハ
ライトなどを好適に使用することができる.これらのア
ルミニウム化合物は1種を用いてもよいし、2種以上を
組み合せて用いてもよい.
更に,場合により存在させることのできる電子供与性化
合物としては,前記固体触媒或分(ii)に関連して説
明した化合物を用いることができる.固体威分(I)の
調製方法において,オレフインとして,例えばエチレン
.プロピレン、ブテンーl、4−メチルベンテンーエな
どの炭素数2〜10のα−オレフインを用い.a常30
〜80℃,好ましくは55〜70℃の範囲の温度におい
て,予備重合を行ない,好ましくは融点100℃以上の
結晶性ポリオレフインを形成させる.この際、触媒系の
アルミニウム/チタン原子比は通常0.1〜Zoo、好
ましくは0.5〜5の範囲で選ばれ、また電子供与性化
合物/チタンモル比はO〜50,好ましくは0.1〜2
の範囲で選ばれる.
前記の固体成分(I)は,粒径の揃った結晶性ポリプロ
ピレンやポリエチレンなどの結晶性パウダーに前記固体
触媒成分(ii)と有機アルミニウム化合物と電子供与
性化合物(融点100℃以上のもの)とを分散させる方
法(分散法)によって調製することもできる.
更に、前記の予備重合法と分散法とを組合せて固体成分
(I)を調製することもできる.気相多段重合法に用い
る触媒系は,前記のとおり、固体威分(1)と有機アル
ミニウム化合物(II)とアルコキシ基含有芳香族化合
!!m (m)と電子供与性化合物(117)とを接触
させて調製するが、有機アルミニウム化合物(■)及び
電子供与性化合物(IV)としては、前記で説明した化
合物を各々用いることかできる.
また、アルコキシ基含有芳香族化合物(m)は,例えば
,一般式
[式中のRlは炭素数1〜20のアルキル基,R2は炭
素数i〜10の炭化水素基,水酸基またはニトロ基,m
はl〜6の整数,nは0〜(6一m)の整数である.]
で表される化合物であり,具体的には、例えばm−メト
キシトルエン、0−メトキシフェノール、m−メトキシ
フェノール、2−メトキシ−4−メチルフェノール、ビ
ニルアニソール,p一(l−プロベニル)アニソール,
p−アリルアニソール、1.3−ビス(p−メトキシフ
ェニル)−1−ベンテン,5−アリルー2−メトキシフ
ェノール、4−アリルー2−メトキシフェノール,4−
ヒトロキシー3−メトキシベンジルアルコール、メトキ
シベンジルアルコール,ニトロアニソール,ニトロフェ
ネトールなどのモノアルコキシ化合物、0−ジメトキシ
ベンゼン、m−ジメトキシベンゼン、p−ジメトキシベ
ンゼン,3,4−ジメトキシトルエン2 2,6−ジメ
トキシフェノール、1−アリル−3.4−ジメトキシベ
ンゼンなどのジアルコキシ化合物及びl,3.5−トリ
メトキシベンゼン、5−アリルーl,2,3−トリメト
キシベンゼン、5−アリルー1,2.4−一トソメトキ
シベンゼン、l,2.3−トリメトキシー5−(1−ブ
ロベニル)ベンゼン、l,2.4−トリメトキシー5−
(1−プロベニル)ベンゼン,1,2.3−トリメトキ
シベンゼン、1,2.4−トリメトキシベンゼンなどの
トリアルコキシ化合物などが挙げられるが、これらの中
でジアルコキシ化合物及びトリアルコキシ化合物が好適
である.これらのアルコキシ基含有芳香族化合物は,そ
れぞれ単独で用いてもよいし、2種以上を組み合せて用
いてもよい.前記の触媒系において、固体成分(I)は
、チタン原子換算で反応容al見当り0.0005〜1
モルの量で使用する.また,アルコキシ基含有芳香族化
合物(m)の使用量は、固体成分(1)中のチタン原子
1モルに対して、0.01〜500モル、好ましくは1
〜300モルである.この使用量が0.01モル未満に
なると生威ボリマーの物性が低下し、500モルを超え
ると触媒活性が低下するので好ましくない,この触媒系
においてアルミニウムとチタンとの原子比は1:1〜3
000 (好ましくは1:40〜800)である.この
原子比の範囲外になると十分な触媒活性が得られない.
更に,アルコキシ基含有芳香族化合物(m)と電子供与
性化合物(19)とのモル比は、1:0.01〜l00
(好ましくは1:0.2〜100)である.
気相多段重合法では、最初の重合(第1段重合〉はプロ
ピレンの単独重合である.分子量調節は公知の手段(例
えば水素濃度のmt!j>によって行なうことができる
.重合温度は、一般に40〜90℃(好ましくは60〜
75℃)であり、重合圧力は10〜45κg/c鳳2(
好ましくは20〜3 0 Kg/cm”) .そして重
合時間は5分〜10時間である.
第2回から最終回の重合(第n段重合〉は,エチレンー
プロピレン共重合またはエチレン−プロピレンーポリエ
ン共重合である.
共重合体に用いることのできる非共役ポリエンとしては
、例えば,ジシクロベンタジエン、トリシクロベンタジ
エン、5−メチル−2,5−ノルボルナジエン、5−メ
チレンー2−ノルボルネン、5−エチリデン−2一ノル
ボルネン,5−イソブロピリデンー2−ノルボルネン、
5−イソブロベニルー2−ノルボルネン,5−(1−ブ
テニン)−2一ノルボルネン,シクロオクタジエン、ビ
ニルシクロヘキセン、1,5.9−シクロドデカトリエ
ン,6−メチル−4.7,8.9−テトラヒドロインデ
ン、2−2゜−ジシクロベンテニル,トランス−1.2
−ジビニルシクロブタン、1.4−へキサジエン,4−
メチル−1.4−へキサジエン、1.6−オクタジエン
、1.7一才クタシエン、l,8−ノナジエン、1.9
−デカジエン、3.6−ジメチル−1.7−オクタジェ
ン、4.5−ジメチル−1.7−オクタジェン、1,4
.7−オクタトリエン、5−メチルー1.8一ノナジエ
ン、ノルボルナジエン2ビニルノルボルネン等を挙げる
ことができる.これらの非共役ポリエンのうち、特にジ
シクロベンタジェン,5−エチリデン−2−ノルボルネ
ン,1.7−オクタジエンか好ましい.
各々の重合段階において、分子量調節は,公知の手段(
例えば水素濃度の調節)によって行なうことかできる.
エチレン−プロピレン共重合体の場合に,エチレン単位
含有量のrll!iは,仕込みガス組戒により行なうこ
とができる.またエチレンープロピレンーポリエン共重
合体の場合にも、ポリエン単位含有量調節は、ポリエン
化合物の仕込量により行なうことができる.重合温度は
20〜90℃(好ましくは40〜50℃〉であり,重合
圧力は5 〜3 0 Kg/cm” (好ましくは10
〜20Kg/cm”) .そして重合時間は5分〜10
時間である.
スラリー多段重合法
スラリー多段重合法においては、例えば、以下の2種類
の触媒系のいずれかを用いることができる.すなわち、
(1)(イ〉マグネシウム,チタン、ハロゲン原子およ
び電子供与体を必須威分とする固体戚分と、(ロ)アル
コキシ基含有芳香族化合物と、(ハ)有機アルミニウム
化合物との組合せから成る触媒系、または
(2)(A)前記の(イ)固体威分と(ロ)アルコキシ
基含有芳香族化合物とを、(ハ)有槻アルミニウム化合
物の存在下または不存在下に反応させて得られる固体触
媒或分、および
(B)有機アルくニウム化合物の組合せから威る触媒系
である.
まず、前記(1)の触媒系について説明すると、固体成
分(イ)はマグネシウム.チタン、ハロゲン原子および
電子供与体を必llI成分とするものであり、マグネシ
ウム化合物とチタン化合物と電子供与体とを接触させる
ことにより調製することができる.
また、この固体威分(イ)の調製に当たり,溶媒として
マグネシウム化合物、電子供与体およびチタン化合物に
対して不活性な*機溶媒、例えば,脂肪族炭化水素(ヘ
キサン,ヘブタンなど)、芳香族炭化水素〈ベンゼン、
トルエンなど)、あるいはハロゲン化炭化水素(炭素数
l〜l2の飽和または不飽和の脂肪族,脂環式および芳
香族炭化水素のモノ及びポリハロゲン化合物など)を単
独でまた2種以上を組み合せて使用することができる.
触媒系(1)の固体成分(イ)を調製する際に用いるマ
グネシウム化合物、チタン化合物および電子供与性化合
物は,各々,前記の気相多段重合法の触媒系に関連して
述べた各化合物と同じものであることができる.これら
の化合物から,公知の方法(例えば気相多段重合法で述
べた方法)で固体戊分(イ)を調製することができる.
こうして得られた固体戊分(イ)と接触させるアルコキ
シ基含イ1芳香族化合物(ロ>siよび有機アルミニウ
ム化合物(ハ)としても,前記気相多段重合法の触媒系
に関連して述べた各化合物を用いることができる.
触媒系(1)を4lJI&する各成分の使用量について
は,固体或分(イ)は,通常チタン原子に換算して反応
容積if当たり、0.0005〜1モルで使用し,アル
コキシ基含有芳香族化合物(ロ)は,固体威分(イ)の
チタン原子に対するモル比が,通常0.01〜50o(
好ましくは1〜300)になる割合で用いられる.この
モル比が0.01未満になると生成ボリマーの物性が低
下し,500を超えると触媒活性が低下するので好まし
くない.また2有機アルミニウム化合物(ハ)は,アル
ミニウム/チタン原子比が通常l〜3000(好ましく
は40〜8oo)になるような量で使用する.この量が
前記範囲を逸脱すると触媒活性が不十分となる.
次に,前記の触媒系(2)について説明すると、この触
媒系(2)における固体触媒成分(A)は,前記触媒系
(1)の固体成分(イ)とアルコキシ基含有芳香族化合
物(ロ)とを、前記の有機アルミニウム化合物(ハ)の
存在下または不存在下に反応させることによって調製す
ることができる.この調製には、一般に炭化水素系溶媒
(例えば、前記触媒系(1)の調製に用いる炭化水素系
溶媒)を用いる.
反応温度は、通常0−150℃(好ましくは10〜50
℃)であり,この温度が0℃未満になると反応が十分に
進行せず,150℃を超えると副反応が起こり,活性が
低下する.
反応時間は、反応温度によって変化するが,通常は1分
間〜20時間、好ましくは10〜60分間である.
有機アルミニウム化合物(ハ)の存在下で固体触媒成分
(A)を調製する場合に、このアルミニウム化合物(ハ
)の濃度は,通常0.05〜100ミリモル/J1(好
ましくは1〜10ミリモル/l)である.この濃度が0
.05ミリモル/文未渦になると、有機アルミニウム化
合物(ハ)を存在させて反応を行なう効果が十分に得ら
れず、100ミリモル/文を超えると固体成分(イ)中
のチタンの還元が進行して、触媒活性か低下する.
一方,有機アルミニウム化合物(ハ)の不存在下で、固
体成分(イ)とアルコキシ基含有芳香族化合物(ロ)と
を反応させて固体触媒成分(A)を調製する場合に,ア
ルコキシ基含有化合物(ロ)は、固体戊分(イ)中のチ
タン原子に対するモル比が、通常0.1〜200(好ま
しくは、1〜50)になるような割合で用いられ,また
,その化合物(ロ)の濃度は、通常0.01〜10ミリ
モル/l(好ましくは0.1〜2ミリモル/l)の範囲
で選ばれる.チタン原子に対するモル比が前記範囲を逸
脱すると所望の活性を有する触媒が得られにくい.また
濃度が0.01ミリモル/交未満では容積効率が低くて
実用的でないし、10ミリモル/lを超えると過反応か
起こりやすく、触媒活性が低下する.
触媒系(2)における有機アルミニウム化合物(B)と
しては,前記の気相多段法の触媒に関して例示した有機
アルミニウム化合物を用いることができる.
触媒系(2)における各成分の使用量については,固体
触媒−威分(A)は、チタン原子に換算して、反応容8
!ll当たり、通常0.0005〜1ミリモル/lの範
囲になるような量で用い、そして有機アルミニウム化合
物(B)は、アルミニウム/チタン原子比が,通常1〜
3000 (好ましくは40〜800〉の範囲になるよ
うな量で用いられる.この原子比が前記範囲を逸脱する
と触媒活性が不十分になる.
本発明のスラリー多段重合法における重合順序および重
合段数は特に制限されず、任意に選ぶことができる.例
えば,第1段および第3段の重合でプロピレン単独重合
を行ない,第2段および第4段の重合でエチレン−プロ
ピレン共重合またはエチレン−プロピレンーポリエン重
合を行なうことができる.重合段数(nの数)は前記気
相多段法と同様に、所望の生戊物を得るために最適な段
数を選べばよく、重合形式としては.iti続重合法ま
たは非連続重合法のいずれも用いることかできる.
プロピレン単独重合の場合,重合温度は通常0〜200
℃(好ましくは60〜100℃)の範囲,そしてプロピ
レン圧は、通常1〜5 0 Kg/cm”の範囲で選ば
れる.また、エチレン−プロピレン共重合またはエチレ
ンープロピレンーポリエン共重合の場合には,重合温度
は通常0〜200゜C(好ましくは40〜80℃)の範
囲、そしてオレフィン圧は通常1〜5 0 Kg/cs
”の範囲で選ばれる.
前記重合においては、いずれも反応時間は5分〜10時
間程度で十分であり,また重合体の分子量の調節は公知
の手段、例えば重合器中の水素濃度を調製することによ
り行なうことができる.エチレンープロピレン共重合体
の場合のエチレン単位含有.ia節は、仕込ガス組成に
より行なうことができ、そしてエチレン−プロピレンー
ポリエン共重合体の場合のポリエン単位含有量の調節は
,仕込み量により行なうことができる.ポリエンモノマ
ーとしては前記気相多段法で述べたポリエンモノマーを
用いることかできる.
zb之上圭
本発明のエラストマー組成物は、ポリプロピレンホモ重
合体(a)とエチレンープロピレン共重合体(b)また
はエチレン−プロピレンーポリエン共重合体(b”)と
を公知の方法(例えば、ドライブレンドまたは混線)に
より,ブレンドにすることにより調製することができる
.プロピレンホ七重合体(a)は、前記の気相多段、ま
たはスラリー多段重合法において第1段重合により得る
ことができ、また、エチレン−プロピレン共重合体(b
)またはエチレンープロピレンーポリエン共重合体(b
゛)は、各々公知の方法で得ることかできる.本発明に
おいては、重合後の後処理は常法により行なうことがで
きる.すなわち,気相多段重合法においては、重合後2
重合器から導出されるボリマー粉体に,この中に含まれ
る未反応才レフィンなどを除くために、窒素気流などを
通過させてもよい。また、所望に応じて押出機よりベレ
ット化してもよくその際、触媒を完全に失活させるため
に、少量の水、アルコールなどを添加することもできる
。また,スラリー多段重合法においては,重合後,重合
器から導出させるボリマーから完全にモノマーを分離し
たのち,ベレット化することができる.
軟質ポリプロピレン重合体組戊物は、通常用いられてい
る成形方法より種々の成形品とし、多様な用途に供する
ことができる。The organoaluminum compound used here has the general formula AfLR3pXz-p(1) (in the formula, R1 is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom such as chlorine or bromine, and p is a number of 1 to 3). The following compounds can be mentioned. Examples of such aluminum compounds include trialkylaluminum such as trimethylaluminum, tosoethylaluminum, triisobrobylaluminum, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisoprobylaluminium monochloride, and diimbutylaluminum. Monochloride, dialkylaluminum monohalides such as dioctylaluminum monochloride, and alkylaluminum sesquihalites such as ethylaluminum sesquichloride can be suitably used. These aluminum compounds may be used alone or in combination of two or more. Furthermore, as the electron-donating compound that may be present if necessary, the compounds described in connection with the solid catalyst (ii) can be used. In the method for preparing solid olefin (I), for example, ethylene. Using an α-olefin having 2 to 10 carbon atoms such as propylene, butene-1, and 4-methylbentenene. a regular 30
Prepolymerization is carried out at a temperature in the range of -80°C, preferably 55-70°C, to form a crystalline polyolefin preferably having a melting point of 100°C or higher. At this time, the aluminum/titanium atomic ratio of the catalyst system is usually selected in the range of 0.1 to Zoo, preferably 0.5 to 5, and the electron donating compound/titanium molar ratio is selected in the range of O to 50, preferably 0.1. ~2
Selected within the range. The solid component (I) is prepared by adding the solid catalyst component (ii), an organoaluminum compound, and an electron-donating compound (having a melting point of 100°C or higher) to a crystalline powder such as crystalline polypropylene or polyethylene with a uniform particle size. It can also be prepared by dispersing (dispersion method). Furthermore, the solid component (I) can also be prepared by combining the prepolymerization method and the dispersion method described above. As mentioned above, the catalyst system used in the gas phase multi-stage polymerization method is the solid component (1), the organoaluminum compound (II), and the alkoxy group-containing aromatic compound! ! It is prepared by bringing m (m) into contact with the electron-donating compound (117), and the compounds explained above can be used as the organoaluminum compound (■) and the electron-donating compound (IV), respectively. Further, the alkoxy group-containing aromatic compound (m) can be prepared by, for example, the general formula [wherein Rl is an alkyl group having 1 to 20 carbon atoms, R2 is a hydrocarbon group having i to 10 carbon atoms, a hydroxyl group or a nitro group, m
is an integer from 1 to 6, and n is an integer from 0 to (61m). ] Specifically, for example, m-methoxytoluene, 0-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p-(l-probenyl)anisole ,
p-allylanisole, 1,3-bis(p-methoxyphenyl)-1-bentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-
Monoalkoxy compounds such as hydroxyloxy 3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenethole, 0-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene 2 2,6- Dialkoxy compounds such as dimethoxyphenol, 1-allyl-3,4-dimethoxybenzene and l,3,5-trimethoxybenzene, 5-allyl l,2,3-trimethoxybenzene, 5-allyl 1,2.4 -monosomethoxybenzene, l,2,3-trimethoxy5-(1-brobenyl)benzene, l,2,4-trimethoxy5-
Examples include trialkoxy compounds such as (1-probenyl)benzene, 1,2.3-trimethoxybenzene, and 1,2.4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferred. It is. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more. In the above catalyst system, the solid component (I) has an apparent reaction volume al of 0.0005 to 1 in terms of titanium atoms.
Use in molar quantities. Further, the amount of the alkoxy group-containing aromatic compound (m) to be used is 0.01 to 500 mol, preferably 1 mol to 1 mol of titanium atom in the solid component (1).
~300 moles. If the amount used is less than 0.01 mol, the physical properties of the biopolymer will deteriorate, and if it exceeds 500 mol, the catalytic activity will decrease, which is not preferable.In this catalyst system, the atomic ratio of aluminum and titanium is 1:1 to 3
000 (preferably 1:40-800). If the atomic ratio falls outside of this range, sufficient catalytic activity will not be obtained.
Furthermore, the molar ratio of the alkoxy group-containing aromatic compound (m) and the electron donating compound (19) is 1:0.01 to 100
(preferably 1:0.2-100). In the gas phase multistage polymerization method, the first polymerization (first stage polymerization) is homopolymerization of propylene. Molecular weight adjustment can be performed by known means (for example, by adjusting the hydrogen concentration mt!j>. The polymerization temperature is generally 40~90℃ (preferably 60~
75°C), and the polymerization pressure was 10 to 45 κg/c Otori 2 (
The polymerization time is preferably 20 to 30 Kg/cm") and the polymerization time is 5 minutes to 10 hours. The second to final polymerization (nth stage polymerization) consists of ethylene-propylene copolymerization or ethylene-propylene copolymerization. This is polyene copolymerization. Examples of non-conjugated polyenes that can be used in the copolymer include dicyclobentadiene, tricyclobentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, and 5-methyl-2,5-norbornadiene. -ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
5-isobrobenyl-2-norbornene, 5-(1-butenine)-2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5.9-cyclododecatriene, 6-methyl-4.7,8.9-tetrahydroindene , 2-2°-dicyclobentenyl, trans-1.2
-divinylcyclobutane, 1,4-hexadiene, 4-
Methyl-1,4-hexadiene, 1,6-octadiene, 1.7 1 year old ctadiene, 1,8-nonadiene, 1.9
-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 1,4
.. Examples include 7-octatriene, 5-methyl-1.8-nonadiene, norbornadiene, 2-vinylnorbornene, and the like. Among these non-conjugated polyenes, dicyclobentadiene, 5-ethylidene-2-norbornene, and 1,7-octadiene are particularly preferred. At each polymerization step, molecular weight adjustment is carried out by known means (
This can be done, for example, by adjusting the hydrogen concentration.
In the case of ethylene-propylene copolymer, the ethylene unit content rll! i can be done according to the preparatory gas regulations. Also in the case of ethylene-propylene-polyene copolymers, the polyene unit content can be adjusted by adjusting the amount of the polyene compound charged. The polymerization temperature is 20 to 90°C (preferably 40 to 50°C), and the polymerization pressure is 5 to 30 Kg/cm" (preferably 10
〜20Kg/cm'') .The polymerization time is 5 minutes to 10 minutes.
It's time. Slurry multistage polymerization method In the slurry multistage polymerization method, for example, either of the following two types of catalyst systems can be used. That is, from the combination of (1) (a) a solid component containing magnesium, titanium, a halogen atom, and an electron donor as essential components, (b) an aromatic compound containing an alkoxy group, and (c) an organoaluminum compound. or (2) (A) by reacting the above (a) solid component and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an Aritsuki aluminum compound. This is a catalyst system that is effective due to the combination of the obtained solid catalyst and (B) an organic alkunium compound. First, to explain the catalyst system of (1) above, the solid component (A) is composed of magnesium, titanium, and halogen. It must contain atoms and an electron donor as components, and can be prepared by bringing a magnesium compound, a titanium compound, and an electron donor into contact. Mechanical solvents that are inert to magnesium compounds, electron donors, and titanium compounds, such as aliphatic hydrocarbons (hexane, hebutane, etc.), aromatic hydrocarbons (benzene,
toluene, etc.), or halogenated hydrocarbons (mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms, etc.) alone or in combination of two or more. It can be used. The magnesium compound, titanium compound, and electron-donating compound used in preparing the solid component (a) of the catalyst system (1) are each of the compounds described in connection with the catalyst system for the gas phase multistage polymerization method. It can be the same thing. From these compounds, solid bokan (a) can be prepared by known methods (for example, the method described in the gas phase multi-stage polymerization method).
An alkoxy group-containing aromatic compound (b) and an organoaluminum compound (c), which are brought into contact with the solid fraction (b) thus obtained, are also used as described in connection with the catalyst system of the gas phase multistage polymerization method. Each compound can be used. Regarding the amount of each component used to make 4 lJI of the catalyst system (1), the solid fraction (a) is usually 0.0005 to 1 mol per reaction volume if in terms of titanium atoms. In the alkoxy group-containing aromatic compound (b), the molar ratio of the solid component (a) to the titanium atoms is usually 0.01 to 50o(
It is preferably used at a ratio of 1 to 300). If this molar ratio is less than 0.01, the physical properties of the produced polymer will deteriorate, and if it exceeds 500, the catalytic activity will decrease, which is not preferable. Further, the organic aluminum compound (c) is used in such an amount that the aluminum/titanium atomic ratio is usually 1 to 3000 (preferably 40 to 8oo). If this amount exceeds the above range, the catalyst activity will be insufficient. Next, to explain the catalyst system (2), the solid catalyst component (A) in this catalyst system (2) is composed of the solid component (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (RO). ) in the presence or absence of the organoaluminum compound (c). For this preparation, a hydrocarbon solvent (for example, the hydrocarbon solvent used in the preparation of the catalyst system (1)) is generally used. The reaction temperature is usually 0-150°C (preferably 10-50°C).
℃), and if this temperature is below 0℃, the reaction will not proceed sufficiently, and if it exceeds 150℃, side reactions will occur and the activity will decrease. The reaction time varies depending on the reaction temperature, but is usually 1 minute to 20 hours, preferably 10 to 60 minutes. When preparing the solid catalyst component (A) in the presence of the organoaluminum compound (c), the concentration of the aluminum compound (c) is usually 0.05 to 100 mmol/J1 (preferably 1 to 10 mmol/l). ). This concentration is 0
.. When the amount is less than 0.5 mmol/liter, the effect of the reaction in the presence of the organoaluminum compound (c) cannot be sufficiently obtained, and when it exceeds 100 mmol/liter, the reduction of titanium in the solid component (a) progresses. As a result, the catalytic activity decreases. On the other hand, when preparing the solid catalyst component (A) by reacting the solid component (A) with the alkoxy group-containing aromatic compound (B) in the absence of the organoaluminum compound (C), the alkoxy group-containing compound (B) is used in such a proportion that the molar ratio to the titanium atoms in the solid fraction (A) is usually 0.1 to 200 (preferably 1 to 50), and the compound (B) The concentration is usually selected in the range of 0.01 to 10 mmol/l (preferably 0.1 to 2 mmol/l). If the molar ratio to titanium atoms is outside the above range, it will be difficult to obtain a catalyst with the desired activity. Further, if the concentration is less than 0.01 mmol/l, the volumetric efficiency is low and it is not practical, and if it exceeds 10 mmol/l, overreaction tends to occur and the catalytic activity decreases. As the organoaluminum compound (B) in the catalyst system (2), the organoaluminum compounds exemplified in connection with the catalyst for the gas phase multi-stage method described above can be used. Regarding the amount of each component used in the catalyst system (2), the solid catalyst (A) has a reaction volume of 8 in terms of titanium atoms.
! The organoaluminum compound (B) is usually used in an amount in the range of 0.0005 to 1 mmol/l, and the organoaluminum compound (B) has an aluminum/titanium atomic ratio of usually 1 to 1 mmol/l.
3000 (preferably in the range of 40 to 800). If this atomic ratio deviates from the above range, the catalyst activity will be insufficient. The polymerization order and number of polymerization stages in the slurry multistage polymerization method of the present invention are as follows: It is not particularly limited and can be selected arbitrarily.For example, propylene homopolymerization is carried out in the first and third stage polymerization, and ethylene-propylene copolymerization or ethylene-propylene copolymerization is carried out in the second and fourth stage polymerization. Polyene polymerization can be carried out.The number of polymerization stages (the number of n) can be selected as the optimal number to obtain the desired green material, as in the gas phase multistage method. Either legal or discontinuous polymerization methods can be used. In the case of propylene homopolymerization, the polymerization temperature is usually 0 to 200 ℃.
°C (preferably 60 to 100 °C), and the propylene pressure is usually selected within the range of 1 to 50 Kg/cm. The polymerization temperature is usually in the range of 0 to 200°C (preferably 40 to 80°C), and the olefin pressure is usually in the range of 1 to 50 Kg/cs.
In each of the above polymerizations, a reaction time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, such as adjusting the hydrogen concentration in the polymerization vessel. In the case of ethylene-propylene copolymers, the ethylene unit content.IA can be determined by the feed gas composition, and in the case of ethylene-propylene-polyene copolymers, the polyene unit content. Adjustment can be made by changing the amount of charge. As the polyene monomer, the polyene monomer described in the gas phase multi-stage method can be used. and an ethylene-propylene copolymer (b) or an ethylene-propylene-polyene copolymer (b'') by a known method (for example, dry blending or cross-mixing). The propylene heptapolymer (a) can be obtained by the first stage polymerization in the gas phase multi-stage or slurry multi-stage polymerization method, and can also be obtained by the ethylene-propylene copolymer (b).
) or ethylene-propylene-polyene copolymer (b
゛) can be obtained by each known method. In the present invention, post-treatment after polymerization can be carried out by conventional methods. That is, in the gas phase multi-stage polymerization method, 2
A stream of nitrogen or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove unreacted olefins contained therein. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added in order to completely deactivate the catalyst. In addition, in the slurry multistage polymerization method, after polymerization, the monomer can be completely separated from the polymer that is discharged from the polymerization vessel and then pelletized. The soft polypropylene polymer assembly can be made into various molded products using commonly used molding methods and used for a variety of purposes.
射出戒形による場合には、軟質であるという特性や良好
な塗装性、戒形性、耐傷付性または耐低温衝撃性により
,自動車外装部品に好適に用いられる.具体的にはバン
パー、モール、塗装用マツトガート,サイトシールド、
スポイラー等である.
中空成形のよる場合には、良好な戊形性を利用して、従
来のプロプロピレンでは偏肉しがちであった部分、たと
えばダクトの蛇四等に好適てある.また,深絞り用材料
としても好適である.押出成形による場合には、良好な
耐衝撃性または耐熱性を利用して、エンジンのアンダー
カバー用シート等に用いられる.また、良好なソフトな
感触を利用して,自動車内装部品に好適に用いられる.
例えば,天井材やトランクルーム内張、インナーパネル
表皮材等である.また加工性や絶縁性を利用しての弱電
部品分野における絶縁シートや,耐熱性、耐候性または
耐摩耗性を利用しての電線ケーブル分野におけるフレキ
シブルコートやブースターケーブル等にも.さらには土
木や建材分野では防水シート止木材または目地材として
の用途もある。When molded by injection molding, it is suitable for use in automobile exterior parts due to its soft properties, good paintability, moldability, scratch resistance, and low-temperature impact resistance. Specifically, bumpers, moldings, paint guards, sight shields,
Spoilers etc. In the case of blow molding, it takes advantage of its good formability and is suitable for parts where conventional propylene tends to have uneven thickness, such as duct snakes. It is also suitable as a material for deep drawing. When made by extrusion molding, it is used for engine undercover sheets, etc., due to its good impact resistance and heat resistance. Also, due to its good soft feel, it is suitable for use in automobile interior parts.
Examples include ceiling materials, trunk linings, and inner panel skin materials. It can also be used as insulating sheets in the field of light electrical parts by taking advantage of its workability and insulation properties, as well as flexible coats and booster cables in the field of electric wires and cables by taking advantage of its heat resistance, weather resistance, and abrasion resistance. Furthermore, in the fields of civil engineering and building materials, it is also used as a lumber for waterproof sheets or as a joint material.
たの樹脂との積層体とすれば2種々多様な目的を満足さ
せることのできるシートを得ることができる。By making a laminate with other resins, it is possible to obtain a sheet that can satisfy a variety of purposes.
[実施例]
次に,実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない.
笈連1」二二東樵羞
(1)固体触媒戊分(11)の調製
十分に窒素置換した内容a 5 0 0 m lのガラ
ス製三ツ口フラスコに、精製ヘプタン20mu、fJi
g (OEt)t 4gおよびフタル酸ジーn−ブチル
l.2gを加え.系内を90℃に保ち,かきまぜなから
TiCl44mlを滴下した後,更にT I C l4
1 1 1 malを追加投入して、110℃に昇湿し
た.110℃で2時間反応させた後、80℃の精製ヘプ
タンで洗浄した.得られた固相部にTiC文.i15m
lを加え、110℃でさらに2時間反応させた.反応終
了後、生成物を精製ヘプタン100mlで数回洗浄して
、固体触媒成分(it)とした。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples. (1) Preparation of solid catalyst (11) In a 500 ml glass three-necked flask, add 20 mu of purified heptane, fJi
g (OEt)t 4g and di-n-butyl phthalate l. Add 2g. After keeping the inside of the system at 90°C and adding 44 ml of TiCl dropwise without stirring,
1 1 1 mal was added and the humidity was raised to 110°C. After reacting at 110°C for 2 hours, it was washed with purified heptane at 80°C. A TiC pattern was added to the obtained solid phase part. i15m
1 was added, and the reaction was continued at 110°C for an additional 2 hours. After the reaction was completed, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component (it).
(2)固体成分(I)の調製
十分に窒素置換した内容a2.5文のガラス製耐圧三ツ
口フラスコに精製ヘプタン1.7文、AIEtzO.0
7モル、ジフェニルジメトキシシラン(DPDMS)0
.05ミリモルおよび前記(1)の固体触媒威分120
gを加えた。系内な30℃に保ち,攪拌しなからプロピ
レンを連続的に供給し、内圧を0.5Kg/c−に保っ
た.この反応:l1時間粛統した後精製ヘプタン11で
5回洗浄し.固体或分(I)を得た.
(3)気相第1段重合
ポリプロピレンパウダー20gを含む51のステンレス
製耐圧オートクレープに、AIEt! 3ミリモル、1
−アリル−3.4−ジメトキシベンゼン(ADMB)0
.15ミリモル、ジフェニルジメトキシシラン(DPD
MS)0.23ミリモルおよび前記(2)の固体成分(
1)100mg(Ti原子に換算して0.06ミリモル
)を含むヘブタン溶液20njLを加えた.系内な5分
間排気後、全圧が2 8 Kg/cm”になるまでプロ
ピレンガスを供給しながら70゜Cで1.7時間気相重
合を行なった.
(4)気相第2段重合
前記(3)の反応が終了した後、系内な脱圧し,排気し
た後、水素ガス0 . 5 Kg/cm”、エチレンー
プロピレン混合ガス(モル比1/4)を1 0 Kg/
cm”まで供給し、50℃で1.4時間気相重合を行な
った.
メルトインデックス(MI)が0.1g/10分のプロ
ビレンエラストマ−550gが得られた。このエラスト
マーは、ポリプロピレンホモ重合体65重量%とエチレ
ン−プロピレン共重合体35重量%とからなり,ホモ重
合体は,固有粘度が1.95dl/gの沸騰ヘプタン可
溶分(HSP分)35重量%と固有粘度が4.78dl
/gの沸騰ヘプタン不溶分(HIP分)65重量%とか
らなり, !3C−NMRによるベンタッド分率におい
てr r r r / 1 − m m m mが34
.5%.DSCにて測定した融解ピーク温度(Tm)が
158℃、DSCにて測定した融解エンタルピー(△H
)が62.6J/g,そして透過型電子顕微鏡での観察
においてドメイン構造が観察された.一方,共重合体の
エチレン単位含有量は31モル%であり,固有粘度は4
.81d見/gであった.
所定の割合のHSP部が得られるようにADMB/DP
DMSを変えたこと以外は、実施
例lと同様に行なった.
実施例5〜7並びに比較例2
HSP部の固有粘度が所定の値になるように,水素濃度
を変えたこと以外は、実施例lと同様に行なった.
威分<a>と成分(b)または(b゛)との成分比が所
定の割合になるように第2段重合時間を変えたこと以外
は、実施例lと同様に行なった.実施例10:ブレンド
法
実施例lの触媒を用いて合威したプロピレンホ七重合体
とEPゴムを溶融ブレンドした.(1)気相法によるプ
ロピレンホモ重合ボリブロピレンパウダー20gを含む
5iのステンレス製耐圧オートクレープに,AIEt3
3ミリモル、1−アリル−3,4−ジメトキシベンゼン
(ADMB)0.15ミリモル、ジフエニルシメトキシ
シラン(DPDMS)0.23ミリモルおよび前記実施
例l(2)の固体成分(I)100mg(Ti原子に換
算して0.06ミリモル)を含むヘブタン溶液20mJ
lを加えた.系内を5分間排気後,全圧が2 8 Kg
/c■2になるまでプロピレンガスを供給しなから70
’Cで1.7時間気相重合を行なった.
(2)プロピレンホ七重合体とEPゴムとの溶融ブレン
ド
前記(1)で得られたプロピレンホ七重合体13gとエ
チレンープロピレン共重合体ゴム(日本合威ゴム社製:
商品名EPO2P)7gとを内容a3 0 m lのラ
ボブラストミル中で195℃において2時間溶融混練し
た(回転数70r p m ) *メルトインデックス
が0.5g/10分の二ラストマー20gが得られた.
このエラストマーは,固有粘度が1.95d文/gのH
SP(沸騰ヘプタン可溶分)35重量%と固有粘度が4
.78d見/gのHIP(沸騰ヘプタン不溶分)65重
量%とからなるポリプロピレンホモ重合体65重量%と
、エチレン単位含有量が73.1モル%で固有粘度か1
.37d文/gのエチレン−プロピレン共重合体35重
量%とからなる.
得られた混線物のプレス成形結果を第1表に示す.
g迦艷(Lユ
実施例10に記載の操作を繰返すが、但し,エチレンプ
ロピレンゴムとして、エチレン単位含有量が71.3モ
ル%で固有粘度が1.97d交/gのもの(日本合成ゴ
ム社製:商品名EPO7P)を用いた.
笈凰真ユ6
(1)気相第1段重合
ボリブロピレンパウダー20gを含む5皇のステンレス
製耐圧オートクレープに、AIEt32ミリモル,ジフ
ェニルジメトキシシラン(DPDMS)0.5ミリモル
、並びに前記実施例(1)および(2)の固体戊分(I
)17mg(Ti原子に換算して0.0lミリモル)を
含むヘプタン溶液20mJLを加えた.系内な5分間排
気後、全圧か3 1 Kg/cm”になるまてプロピレ
ンガスを供給しながら70℃で1.7時間気相重合を行
なった.
(2)気相第2段重合
前記(1)の反応が終了した後,系内を脱圧し,窒素ガ
スを常圧まで供給し、続いてジシクロベンタジエン3.
8ml <30Zリモル)を添加し、排気した後、エチ
レンープロピレン混合ガス(モル比2/3)を10κg
/cm”まて供給し550℃で1.4時間気相重合を行
なった.
メルトインデックス(Ml)がo.Ig/10分の軟質
プロピレン540gが得られた.この軟質プロピレンは
、ボリブロピレンホモ重合体65瓜量%とエチレン−プ
ロピレン共重合体35ffiffi%とからなり、ホモ
重合体は、固有粘度が1.95di/gの沸騰ヘプタン
可溶分(HSP分)35重量%と固有粘度が4.78d
見/gの沸羞ヘブタン不溶分(HIP分)65重量%と
からなり.”C−NMRによるベンタット分率において
r r r r / 1−mmmmが34.5%,DS
Cにて測定した融解ピーク温度(Tm)が158℃、D
SCにて測定した融解エンタルピー(△H)が62.6
J/g,そして透過型電子顕微鏡での観察においてドメ
イン構造が観察された.一方2共重合体のエチレン単位
含有量は31モル%、ポリエン単位含有量は35重量%
であり、そして固有粘度は4.79dl/gであった.
前記の各実施例および比較例の結果を第1表に示す.評
価は以下の方法によって行なった.工互且里亙
示差熱量分析計(Perkin−Elmer社製のDS
C−7)により、融解ピーク温度(Tm :すなわち,
融解ピークの頂点の温度)をJIS−7121に準拠し
て測定した.また、融解エンタルピー(ΔH:すなわち
、結晶融解時に吸収される総熱エネルギ!)はJ I
S−K7 1 22に準拠して測定した.過 電子顕微
鏡観 (TEM)
測定用試料の作成は.Rub.染色法及び超薄切片法に
より実施した.透過型電子顕微鏡(日本電子社@:JE
M−100CKrl型)をfff イ、加速電圧100
KV及び倍率1000〜60oooの条件下にてa察し
た.
’3C−NMRによるポリプロピレン立体規則 測定法
測定機器としては、日本電子社製のJNM−FX−20
0(”C核共鳴周波!5 0 . 1 MHz)を用い
た.測定条件は以下のとおりである.測定モード:プロ
トン完全デッカプリング法バルス@:6.9μs (4
5” )
パルス繰り返し時間=3s
積算回数: ioooo回
溶媒: l,2.4−トリクロロベンゼン/重ベンゼン
(90/10容量%)
試料濃度: 250mg/2.5mJl溶媒測定温度:
l30℃
前記の測定条件下で、メチル基の立体規則性によるケミ
カルシフトの違いによりベンッタド分率を測定する。(2) Preparation of solid component (I) In a pressure-resistant three-necked glass flask with contents a 2.5 g, which had been sufficiently purged with nitrogen, 1.7 g of purified heptane, AIEtzO. 0
7 mol, diphenyldimethoxysilane (DPDMS) 0
.. 05 mmol and the solid catalyst content of (1) above 120
g was added. The system was maintained at 30°C, propylene was continuously supplied without stirring, and the internal pressure was maintained at 0.5 kg/c-. The reaction was incubated for 1 hour and then washed 5 times with purified heptane 11. A solid fraction (I) was obtained. (3) Into 51 stainless steel pressure-resistant autoclaves containing 20 g of gas-phase first-stage polymerized polypropylene powder, AIEt! 3 mmol, 1
-Allyl-3,4-dimethoxybenzene (ADMB) 0
.. 15 mmol, diphenyldimethoxysilane (DPD
MS) 0.23 mmol and the solid component (2) above (
1) 20 njL of hebutane solution containing 100 mg (0.06 mmol in terms of Ti atoms) was added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70°C for 1.7 hours while supplying propylene gas until the total pressure reached 28 Kg/cm. (4) Gas phase second stage polymerization After the reaction in (3) was completed, the system was depressurized and exhausted, and then hydrogen gas was added at 0.5 Kg/cm" and ethylene-propylene mixed gas (molar ratio 1/4) was added at 10 Kg/cm".
cm'' and gas phase polymerization was carried out at 50°C for 1.4 hours. 550 g of propylene elastomer with a melt index (MI) of 0.1 g/10 minutes was obtained. The homopolymer is composed of 65% by weight of a copolymer and 35% by weight of an ethylene-propylene copolymer. 78dl
/g of boiling heptane insoluble content (HIP content) 65% by weight, ! In the bentad fraction by 3C-NMR, r r r r / 1 - m m m m is 34
.. 5%. The melting peak temperature (Tm) measured by DSC was 158°C, and the enthalpy of melting (△H) measured by DSC was 158°C.
) was 62.6 J/g, and a domain structure was observed in transmission electron microscopy. On the other hand, the ethylene unit content of the copolymer is 31 mol%, and the intrinsic viscosity is 4.
.. It was 81d/g. ADMB/DP so that a predetermined proportion of HSP parts can be obtained.
The same procedure as in Example 1 was carried out except that the DMS was changed. Examples 5 to 7 and Comparative Example 2 The same procedure as in Example 1 was carried out except that the hydrogen concentration was changed so that the intrinsic viscosity of the HSP part became a predetermined value. The same procedure as in Example 1 was carried out, except that the second stage polymerization time was changed so that the ratio of component <a> to component (b) or (b) was a predetermined ratio. Example 10: Blending method The propylene heptapolymer synthesized using the catalyst of Example 1 and EP rubber were melt-blended. (1) Propylene homopolymerization by gas phase method In a 5i stainless steel pressure-resistant autoclave containing 20 g of polypropylene powder, AIEt
3 mmol, 0.15 mmol of 1-allyl-3,4-dimethoxybenzene (ADMB), 0.23 mmol of diphenylcimethoxysilane (DPDMS) and 100 mg of the solid component (I) of Example 1(2) above (Ti 20 mJ of hebutane solution containing 0.06 mmol (calculated as atoms)
Added l. After evacuating the system for 5 minutes, the total pressure was 28 kg.
70 without supplying propylene gas until /c■2.
Gas phase polymerization was carried out at 'C for 1.7 hours. (2) Melt blending of propylene heptapolymer and EP rubber 13 g of the propylene heptapolymer obtained in (1) above and ethylene-propylene copolymer rubber (manufactured by Nippon Goui Rubber Co., Ltd.:
(trade name: EPO2P) was melt-kneaded for 2 hours at 195°C in a lab blast mill with a content of 30 ml (rotation speed: 70 rpm). *20 g of bilastomer with a melt index of 0.5 g/10 minutes was obtained. Ta.
This elastomer has an intrinsic viscosity of 1.95 db/g.
SP (boiling heptane soluble content) 35% by weight and intrinsic viscosity 4
.. 65% by weight of a polypropylene homopolymer consisting of 65% by weight of HIP (insoluble matter in boiling heptane) of 78 d/g and an ethylene unit content of 73.1 mol% with an intrinsic viscosity of 1
.. It consists of 35% by weight of ethylene-propylene copolymer of 37dm/g. Table 1 shows the results of press molding of the resulting mixed wire. Repeat the operation described in Example 10, but use ethylene propylene rubber with an ethylene unit content of 71.3 mol% and an intrinsic viscosity of 1.97 d/g (Japan Synthetic Rubber). Co., Ltd. (trade name: EPO7P). (1) In a pressure-resistant stainless steel autoclave containing 20 g of gas-phase first-stage polymerized polypropylene powder, 32 mmol of AIEt and diphenyldimethoxysilane (DPDMS) were used. ) 0.5 mmol as well as the solid fraction (I) of Examples (1) and (2) above.
20 mJL of heptane solution containing 17 mg (0.0 l mmol in terms of Ti atoms) was added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70°C for 1.7 hours while supplying propylene gas until the total pressure reached 31 Kg/cm. (2) Gas phase second stage polymerization After the reaction in (1) is completed, the pressure in the system is depressurized, nitrogen gas is supplied to normal pressure, and then dicyclobentadiene 3.
After adding 8 ml <30
/cm” and gas phase polymerization was carried out at 550°C for 1.4 hours. 540 g of soft propylene with a melt index (Ml) of o.Ig/10 minutes was obtained. The homopolymer is composed of 65% by weight of a homopolymer and 35% by weight of an ethylene-propylene copolymer. 4.78d
It consists of 65% by weight of boiling hebutane insoluble content (HIP content) per gram. "The bentat fraction by C-NMR is r r r r / 1-mmmm 34.5%, DS
The melting peak temperature (Tm) measured at C was 158°C, D
Melting enthalpy (△H) measured by SC is 62.6
J/g, and a domain structure was observed in transmission electron microscopy. On the other hand, the ethylene unit content of the 2 copolymer is 31 mol%, and the polyene unit content is 35% by weight.
and the intrinsic viscosity was 4.79 dl/g. The results of each of the above examples and comparative examples are shown in Table 1. The evaluation was performed using the following method. Industrial differential calorimeter (DS manufactured by Perkin-Elmer)
C-7), the melting peak temperature (Tm: i.e.,
The temperature at the top of the melting peak) was measured in accordance with JIS-7121. Also, the enthalpy of fusion (ΔH: that is, the total thermal energy absorbed during crystal melting!) is J I
Measured in accordance with S-K7 1 22. How to prepare a sample for electron microscopy (TEM) measurement. Rub. It was performed using the staining method and ultrathin section method. Transmission electron microscope (JEOL@:JE
M-100CKrl type) fff a, acceleration voltage 100
A was observed under the conditions of KV and magnification of 1000 to 60ooo. Polypropylene stereoregularity by '3C-NMR Measurement method: JNM-FX-20 manufactured by JEOL Ltd.
0 ("C nuclear resonance frequency! 50.1 MHz).The measurement conditions are as follows.Measurement mode: Proton complete decoupling method Pulse @: 6.9 μs (4
5”) Pulse repetition time = 3s Integration number: ioooo times Solvent: l,2.4-trichlorobenzene/heavybenzene (90/10% by volume) Sample concentration: 250mg/2.5mJl Solvent measurement temperature:
130°C Under the above measurement conditions, the bentad fraction is measured based on the difference in chemical shift due to the stereoregularity of the methyl group.
詳しくは.22.5 〜19.5ppyymli城に現
われるm m m m〜m r r mの各ピークの面
積強度比からベンタット分率を計算する.
なお,各雰囲気メチル基のケミカルシフトはテトラメチ
ルシラン(TMS)を標準物質とした場合に、以下のと
おりである.
mmmm − 21.86ppm
mmmr − 21.62ppm
mmrr − 21.08ppm
mmrm+rrmr − 20.89ppmrrr
r − 20.36ppmmrr
m − 19.97ppmメルト
フローレート Ml)
測定条件として、試験温度・230℃及び試験荷重2.
16Kgfを用い,JIS−K7210に準拠して測定
した.
北皇薯奎
試験片としてJIS2号型ダンベル(厚さlm m .
プレス成形品)を用い、試験速度5 0 m m/ m
i n及び試験温度23゜Cの条件下でJIS−K7
113に準拠して測定した.
アイゾット 撃
試験片として、JISZ号のA切欠き《厚さ3mm、プ
レス成形品)を用い、試験温度−20”Cの条件下で、
JIS−K7110に準拠して測定した.
ショア硬 D(デュロメーターD硬さ)試験片として,
厚さ3mm板(プレス成形品)を用い,試験温度23℃
の条件下で.JIS−K7215に準拠して測定した.
[以下、余白]
[発明の効果]For more information. Calculate the bentat fraction from the area intensity ratio of each peak of m m m m to m r r m appearing in the 22.5 to 19.5 ppyymli castle. The chemical shifts of methyl groups in each atmosphere are as follows when tetramethylsilane (TMS) is used as a standard substance. mmmm - 21.86ppm
mmmr - 21.62ppm
mmrr - 21.08ppm
mmrm+rrmr - 20.89ppmrrr
r - 20.36ppmmrr
m - 19.97 ppm melt flow rate Ml) The measurement conditions were a test temperature of 230°C and a test load of 2.
It was measured using 16Kgf in accordance with JIS-K7210. A JIS No. 2 dumbbell (thickness lm m.
(press molded product) at a test speed of 50 mm/m
JIS-K7 under the conditions of i.n. and test temperature of 23°C.
Measured in accordance with 113. Using JISZ No. A notch (thickness 3 mm, press molded product) as an Izod impact test piece, under the test temperature of -20"C,
Measured in accordance with JIS-K7110. As a Shore hardness D (durometer D hardness) test piece,
Using a 3mm thick plate (press molded product), test temperature 23℃
Under the conditions of. Measured in accordance with JIS-K7215. [Hereinafter in the margin] [Effects of the invention]
Claims (3)
ヘプタン可溶性ポリプロピレン10〜90重量%と固有
粘度が0.5〜9.0dl/gである沸騰ヘプタン不溶
性ポリプロピレン90〜10重量%とからなるポリプロ
ピレン系重合体10〜95重量%、および (b)エチレン単位含有量が10〜60モル%で、固有
粘度が0.5〜7.0dl/gであるエチレン−プロピ
レン共重合体90〜5重量% からなるプロピレン系エラストマー組成物。(1) (a) 10-90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl/g or more and 90-10% by weight of boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5-9.0 dl/g. and (b) an ethylene-propylene copolymer 90 having an ethylene unit content of 10 to 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl/g. -5% by weight of a propylene-based elastomer composition.
ヘプタン可溶性ポリプロピレン10〜90重量%と固有
粘度が0.5〜9.0dl/gである沸騰ヘプタン不溶
性ポリプロピレン90〜10重量%とからなるポリプロ
ピレン系重合体10〜95重量%、および (b)エチレン単位含有量が10〜60モル%で、ポリ
エン単位含有量が1〜10モル%で、固有粘度が0.5
〜7.0dl/gであるエチレン−プロピレン−ポリエ
ン共重合体90〜5重量% からなるプロピレン系エラストマー組成物。(2) (a) 10-90% by weight of boiling heptane-soluble polypropylene with an intrinsic viscosity of 1.2 dl/g or more and 90-10% by weight of boiling heptane-insoluble polypropylene with an intrinsic viscosity of 0.5-9.0 dl/g and (b) an ethylene unit content of 10 to 60 mol%, a polyene unit content of 1 to 10 mol%, and an intrinsic viscosity of 0.5.
A propylene-based elastomer composition comprising 90 to 5% by weight of an ethylene-propylene-polyene copolymer having a concentration of ~7.0 dl/g.
00Kg/cm^2以上であり、そして引張弾性率が8
000Kg/cm^2以下である、請求項1または2の
いずれかに記載のプロピレン系エラストマー組成物。(3) Elongation at break is 300% or more and stress at break is 1
00Kg/cm^2 or more, and the tensile modulus is 8
The propylene-based elastomer composition according to claim 1 or 2, which has a tensile strength of 000 Kg/cm^2 or less.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30857389A JP2804554B2 (en) | 1989-11-28 | 1989-11-28 | Propylene elastomer composition |
PCT/JP1990/001216 WO1991008259A1 (en) | 1989-11-28 | 1990-09-21 | Flexible polypropylene resin, propylene elastomer composition, and production of olefin polymer |
DE69032786T DE69032786T2 (en) | 1989-11-28 | 1990-09-21 | FLEXIBLE POLYPROPYLENE RESIN, POLYPROPYLENE ELASTOMER MIXTURE AND PRODUCTION OF OLEFIN POLYMERS |
EP98103661A EP0850990A1 (en) | 1989-11-28 | 1990-09-21 | Flexible polypropylene resins, propylene based elastomer compositions and process for production of olefin polymers |
EP90913734A EP0455813B1 (en) | 1989-11-28 | 1990-09-21 | Flexible polypropylene resin, propylene elastomer composition, and production of olefin polymer |
US08/991,536 US6001933A (en) | 1989-11-28 | 1997-12-16 | Flexible polypropylene resins, propylene based elastomer compositions and process for production of olefin polymers |
US09/352,361 US6156846A (en) | 1989-11-28 | 1999-07-13 | Flexible polypropylene resins, propylene bases elastomer compositions and process for production of olefin polymers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30857389A JP2804554B2 (en) | 1989-11-28 | 1989-11-28 | Propylene elastomer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03168234A true JPH03168234A (en) | 1991-07-22 |
JP2804554B2 JP2804554B2 (en) | 1998-09-30 |
Family
ID=17982656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30857389A Expired - Fee Related JP2804554B2 (en) | 1989-11-28 | 1989-11-28 | Propylene elastomer composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2804554B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0606618A3 (en) * | 1992-12-25 | 1994-10-19 | Idemitsu Petrochemical Co | A polyolefinic resin and a resin composition comprising said resin. |
JP2002060561A (en) * | 2000-06-05 | 2002-02-26 | Idemitsu Petrochem Co Ltd | Covering material for protecting wire |
JP2006240520A (en) * | 2005-03-04 | 2006-09-14 | Sumitomo Chemical Co Ltd | Vehicular undercover |
JP2012219118A (en) * | 2011-04-05 | 2012-11-12 | Sumitomo Chemical Co Ltd | Extruded molding |
WO2023233697A1 (en) * | 2022-06-03 | 2023-12-07 | 住友電気工業株式会社 | Resin composition and power cable |
-
1989
- 1989-11-28 JP JP30857389A patent/JP2804554B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0606618A3 (en) * | 1992-12-25 | 1994-10-19 | Idemitsu Petrochemical Co | A polyolefinic resin and a resin composition comprising said resin. |
JP2002060561A (en) * | 2000-06-05 | 2002-02-26 | Idemitsu Petrochem Co Ltd | Covering material for protecting wire |
JP2006240520A (en) * | 2005-03-04 | 2006-09-14 | Sumitomo Chemical Co Ltd | Vehicular undercover |
JP4715238B2 (en) * | 2005-03-04 | 2011-07-06 | 住友化学株式会社 | Automotive undercover |
JP2012219118A (en) * | 2011-04-05 | 2012-11-12 | Sumitomo Chemical Co Ltd | Extruded molding |
WO2023233697A1 (en) * | 2022-06-03 | 2023-12-07 | 住友電気工業株式会社 | Resin composition and power cable |
JP7405311B1 (en) * | 2022-06-03 | 2023-12-26 | 住友電気工業株式会社 | Resin compositions and power cables |
Also Published As
Publication number | Publication date |
---|---|
JP2804554B2 (en) | 1998-09-30 |
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