JPH02117905A - Catalytic component for polymerizing alpha-olefin - Google Patents
Catalytic component for polymerizing alpha-olefinInfo
- Publication number
- JPH02117905A JPH02117905A JP27052888A JP27052888A JPH02117905A JP H02117905 A JPH02117905 A JP H02117905A JP 27052888 A JP27052888 A JP 27052888A JP 27052888 A JP27052888 A JP 27052888A JP H02117905 A JPH02117905 A JP H02117905A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polymerization
- compound
- olefin
- solid
- 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
- 239000004711 α-olefin Substances 0.000 title claims abstract description 17
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 8
- 150000002901 organomagnesium compounds Chemical class 0.000 claims abstract description 7
- 150000002900 organolithium compounds Chemical class 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 63
- 239000003054 catalyst Substances 0.000 claims description 29
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 abstract description 26
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 9
- 150000003377 silicon compounds Chemical class 0.000 abstract description 8
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002685 polymerization catalyst Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 150000002681 magnesium compounds Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011949 solid catalyst Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-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
- 238000012661 block copolymerization Methods 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-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
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 2
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 2
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- HLWQPQKVKCQWGG-UHFFFAOYSA-N 3-propyloxiran-2-one Chemical compound CCCC1OC1=O HLWQPQKVKCQWGG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYWDKWWDJJOYEA-UHFFFAOYSA-N CCCC[Mg]OCC Chemical compound CCCC[Mg]OCC RYWDKWWDJJOYEA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 239000001273 butane Substances 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- IWYBVQLPTCMVFO-UHFFFAOYSA-N ethyl 2,2-dichloroacetate Chemical compound CCOC(=O)C(Cl)Cl IWYBVQLPTCMVFO-UHFFFAOYSA-N 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- XSXVXSCMWUJXOS-UHFFFAOYSA-N ethyl 2-ethylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1CC XSXVXSCMWUJXOS-UHFFFAOYSA-N 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】 〔発明の背景〕 技術分野 本発明は、オレフィン重合用触媒に関するものである。[Detailed description of the invention] [Background of the invention] Technical field The present invention relates to an olefin polymerization catalyst.
更に詳しくは、本発明は、特定の固体成分を特定の有機
金属化合物共存下に予備重合に付すことにより得られた
触媒によって、α−オレフィン類の重合体、特にプロピ
レンを主体としたブロック共重合体、を副生成物を少な
く安定した重合条件で工業生産上有ｆ１１に製造するこ
とを可能とするものである。More specifically, the present invention is directed to the production of α-olefin polymers, particularly block copolymers mainly composed of propylene, using a catalyst obtained by subjecting a specific solid component to prepolymerization in the coexistence of a specific organometallic compound. This makes it possible to produce the polymers in an industrially efficient manner with fewer by-products and under stable polymerization conditions.
先行技術
従来、種々のタイプの立体特異性触媒の存在下に、前段
でプロピレンの結晶性単独重合体又は共重合体（以下両
者を総称して単にポリプロピレンということがある）を
製造し、後段で該ポリプロピレンの共存下にプロピレン
と他のａ−オレフィンとを共重合させることによってプ
ロピレンのゴム状共重合体を製造することにより、ポリ
プロピレンの有する優れた剛性を保持しつつ低温時にお
ける耐衝撃性の改良された組成物が得られることが知ら
れている。Prior Art Conventionally, in the presence of various types of stereospecific catalysts, a crystalline homopolymer or copolymer of propylene (hereinafter both may be collectively referred to simply as polypropylene) is produced in the first stage, and then in the second stage. By producing a rubbery copolymer of propylene by copolymerizing propylene and other a-olefins in the coexistence of the polypropylene, it is possible to maintain the excellent rigidity of polypropylene while improving impact resistance at low temperatures. It is known that improved compositions can be obtained.
このようなブロック共重合体を製造する際の触媒として
は、従来三塩化チタン型の触媒が用いられているが、こ
れは触媒活性が低い為に触媒除去工程、すなわち脱触工
程、が必要である（特公昭４３−１．１２３０号、同４
４−１６６６８号、同４４−２０６１２号、同４９−２
４５９３号、特開昭４８−２５７８１号、同５３−３５
７８９号各公報）。Conventionally, titanium trichloride type catalysts have been used as catalysts for producing such block copolymers, but because of their low catalytic activity, a catalyst removal step, that is, a decatalyzing step, is required. Yes (Special Publication No. 43-1.1230, No. 4
No. 4-16668, No. 44-20612, No. 49-2
No. 4593, JP-A-48-25781, JP-A No. 53-35
789 publications).
脱触工程が不要となるまで活性を大きく向上させる方法
として、担持型触媒を用いる方法か近年数多く提案され
ている（特開昭５２−９８０４５号、同５３−８８０４
９号、同５８−８３０１６号各公報）。In recent years, a number of methods using supported catalysts have been proposed as a method to greatly improve the activity to the point where the decatalyzing step becomes unnecessary (JP-A-52-98045, JP-A No. 53-8804).
No. 9 and No. 58-83016).
、このような高活性触媒の開発により、脱触工程が省略
され、副生成物の派生量も減少した。しかし、その反面
、後段の共重合部分の分子量が小さいので、ブロック共
重合体の分子量分布が狭くなって加工時の成型性が悪化
したり、また後段共重合部分の量を増すと、副生成物の
瓜が急増したり、パウダーの付着性が増加し、重合体が
凝集、固着等を起こして運転トラブルとなる等の問題が
あった。With the development of such highly active catalysts, the decatalyzing step has been omitted and the amount of by-products produced has also been reduced. However, on the other hand, since the molecular weight of the copolymerized portion in the later stage is small, the molecular weight distribution of the block copolymer becomes narrow, resulting in poor moldability during processing, and when the amount of the copolymerized portion in the later stage is increased, by-products are generated. There were problems such as a sudden increase in the amount of melted particles, increased adhesion of powder, and agglomeration and sticking of polymers, resulting in operational troubles.
これらの問題を改良する目的として、後段重合開始時に
電子供与性化合物を添加する方法が提案されている（特
開昭５６−１５１７１３号、同６０−５９１３９号、同
６１−６９８２１号、同６１−６９８２２号、同６１−
６９８２３号、同６３−４３９１５号、同６３−１６５
４１７号各公報）。In order to improve these problems, a method has been proposed in which an electron-donating compound is added at the start of the second stage polymerization (JP-A-56-151713, JP-A No. 60-59139, JP-A No. 61-69821, JP-A No. 61-698). No. 69822, 61-
No. 69823, No. 63-43915, No. 63-165
417 publications).
しかしながら、本発明者らの知るところでは、成型加工
性、副生成物、ポリマー付着性を全て満足するには至っ
ていない。However, to the knowledge of the present inventors, molding processability, by-products, and polymer adhesion have not all been satisfied.
〔発明の８！Ｅ要〕
股−旦
本発明は上記の問題点に解決を与えることを目的とし、
固体触媒成分を改良した結果、特定の固体成分を特定の
有機金属化合物を用いて予備重合に付すことにより得ら
れた固体触媒成分の使用によってこの目的を達成しよう
とするものである。[Invention 8! E required] The purpose of the present invention is to provide a solution to the above problems,
As a result of improvements in solid catalyst components, this objective is achieved through the use of solid catalyst components obtained by subjecting specific solid components to prepolymerization using specific organometallic compounds.
すなわち、本発明によるα−オレフィン重合用触媒成分
は、下記の成分（Ａ）および成分（Ｂ）および場合によ
りさらに成分（Ｃ）よりなる固体成分（Ｉ）に成分（Ｉ
Ｉ）の共存下にα−オレフィンを接触させて、このα−
オレフィンを固体成分（Ｉ）１グラムに対して０．０１
〜１００グラム重音させて’Ｉｒ、＞ を二こと、を特
徴とするものである。That is, the catalyst component for α-olefin polymerization according to the present invention is a solid component (I) consisting of the following components (A) and (B), and optionally further component (C);
This α-olefin is brought into contact with the α-olefin in the coexistence of I).
0.01 olefin per gram of solid component (I)
It is characterized by two words: ~100g overtone 'Ir,>.
固体成分（Ｉ）
成分（Ａ）
チタン、マグネシウムおよびハロゲンを必須として含有
する固体成分。Solid component (I) Component (A) A solid component that essentially contains titanium, magnesium, and halogen.
成分（Ｂ）
（但し、Ｒ１は分岐鎖状炭化水素残基を、Ｒ２はＲ１と
同一かもしくは異なる炭化水素残基を、Ｒ３は炭化水素
残基を、ｎは１≦ｎ≦３の数を、それぞれ示す。）
成分（Ｃ）
周期律表第１〜ｍ族金属の有機金属化合物。Component (B) (However, R1 is a branched hydrocarbon residue, R2 is the same or different hydrocarbon residue as R1, R3 is a hydrocarbon residue, and n is the number of 1≦n≦3. , respectively.) Component (C) An organometallic compound of metals from groups 1 to m of the periodic table.
成分（ｎ） 有機マグネシウムあるいは有機リチウム化合物。Component (n) Organomagnesium or organolithium compound.
効果
本発明によるα−オレフィン重合用触媒成分を用いてプ
ロピレンブロック共重合体を製造することにより、高剛
性、高衝撃強度の共重合体を副生成物を少なく得ること
ができる。Effects By producing a propylene block copolymer using the catalyst component for α-olefin polymerization according to the present invention, a copolymer with high rigidity and high impact strength can be obtained with a small amount of by-products.
また、本発明によれば、ゴム状共重合体の＠瓜が多くな
った場合（たとえば３０重量パーセント以上）にも、重
合体粒子の粘着性が少なく、従来問題とされていた運転
上のトラブルを解決することができる。Furthermore, according to the present invention, even when the rubbery copolymer contains a large amount (for example, 30% by weight or more), the stickiness of the polymer particles is small, causing operational problems that were conventionally considered to be a problem. can be solved.
固体成分１
本発明の固体成分Ｉは、特定の成分（Ａ）および成分（
Ｂ）および場合によりさらに成分（Ｃ）よりなるもので
ある。ここで「よりなる」ということは、成分が半水の
もの（すなわち（Ａ）および（Ｂ）または成分（Ａ）、
（Ｂ）および（Ｃ））のみであるということを意味する
ものではなく、成分■の共存下での：ｆ−備重合を経る
ことによる改良効果が損われない限りにおいては、追加
の成分（たとえば、ハロゲン化チタン）を含んでよいこ
とを意味する。Solid component 1 Solid component I of the present invention comprises a specific component (A) and a component (
B) and optionally further comprises component (C). Here, "consisting" means that the component is semi-aqueous (i.e., (A) and (B) or component (A),
This does not mean that (B) and (C)) are the only components, but as long as the improvement effect of the :f-prepolymerization in the coexistence of component (2) is not impaired, additional components ( For example, it means that it may contain titanium halides).
成分（Ａ）および成分（Ｂ）の組み合わせで充分な活性
、嵩密度、立体規則性を有する重合体を得ることができ
るが、これらの物性が不充分な場合にはさらに成分（Ｃ
）を使用することによって改善をみることができる。A polymer having sufficient activity, bulk density, and stereoregularity can be obtained by combining component (A) and component (B), but if these physical properties are insufficient, component (C) may be added.
) can be seen as an improvement.
成分（Ａ）
成分（Ａ）は、チタン、マグネシウムおよびハロゲンを
必須成分として含有する固体成分である。Component (A) Component (A) is a solid component containing titanium, magnesium and halogen as essential components.
ここで「必須成分として含有する」ということは、挙・
示の三成分の外に合目的的な他元素を含だでいてもよい
こと、これらの元素はそれぞれが合目的的な任意の化合
物として存在していてもよいこと、ならびにこれら元素
は相互に結合したものとして存在してもよいこと、を示
すものである。Here, "containing as an essential component" means:
In addition to the three components shown above, other elements may be included for a purpose, each of these elements may exist as any compound for a purpose, and these elements may not interact with each other. This indicates that they may exist in combination.
このような固体成分は公知のものが使用できる。Known solid components can be used as such solid components.
例えば、特開昭５３−４５６８８号、同５４−３８９４
号、同５４−３１０９２号、同５４−３９４８３号、同
５４−９４５９１号、同５４−１１８４８４号、同５４
−１３１５８９号、同５５−７５４１１号、同５５−９
０５１０号、同５５−９０５１１号、同５５−１２７４
０５号、同５５−１４７５０７号、同５５−１５５００
３号、同５６−１８６０９号、同５６−７０００５号、
同５６−７２００１号、同５６−８６９０５号、同５６
−９０８０７号、同５６−
１５５２０６号、同５７−３８０３号、同５７−３４１
０３号、同５７−９２００７号、同５７−１、２１００
３号、同５８−５３０９号、同５８−５３１０号、同５
８−５３１１号、同５８−８７０６、号、同５８−２７
７３２号、同５８−３２６０４号、同５８−３２６０５
号、同５８−６７７０３号、同５８−１１７２０６号、
同５８−１２７７０８号、同５ｇ−１８３７０８号、同
５８−１８３７０９号、同５９−１４９９０５号、同５
９−１４９９０５号各公報等に記載のものが使用される
。For example, JP-A-53-45688, JP-A-54-3894
No. 54-31092, No. 54-39483, No. 54-94591, No. 54-118484, No. 54
-131589, 55-75411, 55-9
No. 0510, No. 55-90511, No. 55-1274
No. 05, No. 55-147507, No. 55-15500
No. 3, No. 56-18609, No. 56-70005,
No. 56-72001, No. 56-86905, No. 56
-90807, 56-155206, 57-3803, 57-341
No. 03, No. 57-92007, No. 57-1, 2100
No. 3, No. 58-5309, No. 58-5310, No. 5
No. 8-5311, No. 58-8706, No. 58-27
No. 732, No. 58-32604, No. 58-32605
No. 58-67703, No. 58-117206,
No. 58-127708, No. 5g-183708, No. 58-183709, No. 59-149905, No. 5
Those described in various publications such as No. 9-149905 are used.
本発明において使用されるマグネシウム源となるマグネ
シウム化合物としては、マグネシウムハライド、ジアル
コキシマグネシウム、アルコキシマグネシウムハライド
、マグネシウムオギシハラ、イド、ジアルキルマグネシ
ウム、酸化マグネシウム、水酸化マグネシウム、マグネ
シウムのカルボン酸塩等があげられる。これらのマグネ
シウム化合物の中でもマグネシウムハライドが好ましい
。Examples of the magnesium compound used as a magnesium source in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium ogishihara, ide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, etc. can give. Among these magnesium compounds, magnesium halide is preferred.
また、チタン源となるチタン化合物は、一般式Ｔｉ（Ｏ
Ｒ）Ｘ（ここでＲ４は炭化水素−ｎ ｎ
残基であり、好ましくは炭素数１〜１０程度のものであ
り、Ｘはハロゲンを示し、ｎはＯ≦ｎ≦４の数を示す。In addition, the titanium compound serving as a titanium source has the general formula Ti(O
R)
）で表わされる化合物があげられる。) can be mentioned.
具体例としては、Ｔ ＩＣ１４、ＴｉＢｒ４、Ｔｉ（Ｏ
Ｃ２Ｈ５）Ｃ１３、Ｔｉ（ＯＣ２Ｈ５）２Ｃ１２、Ｔｉ
（ＯＣ２Ｈ５） ３ＣＩＳＴｉ （０−ｉｃ３Ｈ７）
Ｃ１３、。Specific examples include TIC14, TiBr4, Ti(O
C2H5)C13, Ti(OC2H5)2C12, Ti
(OC2H5) 3CISTi (0-ic3H7)
C13.
Ｔ ｔ （０−ｎ Ｃ４Ｈ９） Ｃ１３、Ｔｉ（０−ｎ
Ｃ４Ｈ９）２Ｃ１２、Ｔｉ（ＯＣ２Ｈ５）Ｂｒ３、Ｔｉ
（ＯＣ２Ｈ５）（ＯＣ４Ｈ９）２ＣＩ５Ｔｌ（０−ｎＣ
４Ｈ９）３ＣＩＳＴｉ（０−Ｃ６Ｈ５）Ｃ１３、Ｔｉ（
Ｏ−１Ｃ４Ｈ９）２Ｃ１２、Ｔ ｉ （ＯＣ５Ｈ１，）
Ｃｌ ３、Ｔｉ（ＯＣ６Ｈ１３）Ｃ１３、Ｔｌ（ＯＣ
２Ｈ５）４、Ｔｔ （ＯｎＣ３Ｈ７）４、Ｔｌ（０−ｎ
Ｃ４Ｈ９）４、Ｔ ｉ （０−ｉ Ｃ４Ｈ９） ４、Ｔ
ｉ （０−ｎＣ６Ｈ１３） ４、Ｔｌ（０−ｎＣ８Ｈ１
７）４、
Ｔｉ〔０ＣＨ２ＣＨ（Ｃ２Ｈ５）Ｃ４Ｈ９〕４等かある
。T t (0-n C4H9) C13, Ti(0-n
C4H9)2C12, Ti(OC2H5)Br3, Ti
(OC2H5) (OC4H9)2CI5Tl (0-nC
4H9)3CISTi(0-C6H5)C13,Ti(
O-1C4H9)2C12, T i (OC5H1,)
Cl3, Ti(OC6H13) C13, Tl(OC
2H5)4, Tt (OnC3H7)4, Tl(0-n
C4H9) 4, T i (0-i C4H9) 4, T
i (0-nC6H13) 4, Tl(0-nC8H1
7) 4, Ti[0CH2CH(C2H5)C4H9]4 etc.
また、ＴｉＸ’（ここでＸ′はハロゲンを示す）に後述
する電子供与体を反応させた分子化合物を用いることも
できる。具体例としては、ＴｌＣ１４ａＣＨ３ＣＯＣ２
Ｈ５、ＴｉＣｌ４・ＣＨ３ＣＯ２Ｃ２Ｈ５、Ｔ ＩＣＩ
４・Ｃ６Ｈ５ＮＯ２、Ｔ ＩＣｌ ４・ＣＨ３ＣＯＣ
１、Ｔ Ｉ Ｃ１４・Ｃ６Ｈ３ＣＯＣ１１Ｔ１Ｃ１４・
Ｃ６Ｈ５Ｃ０，ＣＩ、Ｔ ｉＣ］ ４・Ｃ６Ｈ５Ｃ０２
Ｃ２Ｈ５、Ｔ ｉＣＩ ４・ＣＩＣＯＣ２Ｈ５、Ｔ Ｉ
Ｃｌ ４・Ｃ４Ｈ４０等があげられる。Furthermore, a molecular compound obtained by reacting TiX' (where X' represents a halogen) with an electron donor described later can also be used. As a specific example, TlC14aCH3COC2
H5, TiCl4・CH3CO2C2H5, T ICI
4・C6H5NO2, T ICl 4・CH3COC
1, T I C14・C6H3COC11T1C14・
C6H5C0, CI, T iC] 4・C6H5C02
C2H5, T iCI 4・CICOC2H5, T I
Examples include Cl4.C4H40.
これらのチタン化合物の中でも好ましいものは、Ｔ１Ｃ
ｌ Ｔｉ （ＯＥｔ） Ｔｉ （ＯＢｕ） ４
．４ゝ ４ゝ
Ｔｉ （ＯＢｕ）ＣＩ３等である。Among these titanium compounds, preferred are T1C
l Ti (OEt) Ti (OBu) 4
．． 4ゝ4ゝTi (OBu)CI3 etc.
ハロゲン源は、上述のマグネシウムおよび（または）チ
タンのハロゲン化合物から供給されるのが普通であるが
、アルミニウムのハロゲン化物やケイ素のハロゲン化物
、リンのハロゲン化物といった公知のハロゲン化剤から
供給することもできる。The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but may also be supplied from known halogenating agents such as aluminum halides, silicon halides, and phosphorous halides. You can also do it.
触媒成分中に含まれるハロゲンはフッ素、塩素、臭素、
ヨウ素又はこれらの混合物であってよく、特に塩素が好
ましい。Halogens contained in catalyst components include fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred.
本発明に用いる固体成分は、上記必須成分の他に５ｉＣ
１４、ＣＨ３ＳｉＣｌ３、メチルハイドロジエンポリシ
ロキサン等のケーｒ索化合物、Ａ１（ＯＩＣ３Ｈ７）３
、Ａｌ０１３、ＡｌＢｒ Ａｌ（ＯＣ２Ｈ５）３．
３ゝ
ＡＩ （ＯＣＨ３） ２Ｃ１等のアルミニウム化合物
、Ｂ（ＯＣ６Ｈ５）３′：９“のホウ素化合物等の他成
分の使用も可能であり、これらがケイ素、アルミニウム
及びホウ素等の成分として固体成分中に残存することは
差支えない。In addition to the above essential components, the solid components used in the present invention include 5iC
14, CH3SiCl3, Kerr's compound such as methylhydrodiene polysiloxane, A1(OIC3H7)3
, Al013, AlBr Al(OC2H5)3. It is also possible to use other components such as aluminum compounds such as 3ゝAI (OCH3) 2C1, and boron compounds such as B(OC6H5)3':9'', which are incorporated into the solid component as components such as silicon, aluminum and boron. There is no problem with it remaining.
更に、この固体成分を製造する場合に、電子供与体を所
謂内部ドナーとして使用して製造することもできる。Furthermore, when producing this solid component, it is also possible to use electron donors as so-called internal donors.
この固体成分の製造に利用できる電子供与体（内部ドナ
ー）としては、アルコール類、フェノール類、ケトン類
、アルデヒド類、カルボン酸類、有機酸又は無機酸類の
エステル類、エーテル類、酸アミド類、酸無水物類のよ
うな含酸素電子供与体、アンモニア、アミン、ニトリル
、イソシアネートのような含窒素電子供与体などを例示
することができる。Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid Examples include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.
より具体的には、（イ）メタノール、エタノール、プロ
パツール、ペンタノール、ヘキサノール、オクタツール
、ドデカノール、オクタデシルアルコール、ベンジルア
ルコール、フェニルエチルアルコール、クミルアルコー
ル、イソプロピルベンジルアルコールなどの炭素数１な
いし１８のアルコール類、（ロ）フェノール、クレゾー
ル、キシレノール、エチルフェノール、プロピルフェノ
ール、クミルフェノール、ノニルフェノール、ナフトー
ルなどのアルキル基を有してよい炭素数６ないし２５の
フェノール類、（ハ）アセトン、メチルエチルケトン、
メチルイソブチルケトン、アセトフェノン、ベンゾフェ
ノンなどの炭素数３ないし１５のケトン類、（ニ）アセ
トアルデヒド、プロピオンアルデヒド、オクチルアルデ
ヒド、ベンズアルデヒド、トルアルデヒド、ナフトアル
デヒ １ドなどの炭素数２ないし１５のアルデヒド
類、（ホ）ギ酸メチル、酢酸メチル、酢酸エチル、酢酸
ビニル、酢酸エチルセロソルブ、酢酸プロピル、 。More specifically, (a) methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol and the like having 1 to 18 carbon atoms; alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone ,
Ketones having 3 to 15 carbon atoms, such as methyl isobutyl ketone, acetophenone, and benzophenone; ) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, ethyl acetate cellosolve, propyl acetate, .
酢酸オクチル、酢酸シクロヘキンル、プロピオン酸エチ
ル、酪酸メチル、吉草酸エチル、ステアリン酸エチル、
クロル酢酸メチル、ジクロル酢酸エチル、メタクリル酸
メチル、クロトン酸エチル、シクロヘキサンカルボン酸
エチル、安息香酸メチル、安息香酸エチル、安息香酸エ
チルセロソルブ、安息香酸プロピル、安息香酸ブチル、
安息香酸オクチル、安息香酸シクロヘキンル、安息香酸
フェニル、安已香酸ベンジル、トルイル酸メチル、トル
イル酸エチル、トルイル酸アミル、エチル安息香酸エチ
ル、アニス酸メチル、アニス酸エチル、エトキシ安息香
酸エチル、フタル酸ジエチル、フタル酸ジブチル、フタ
ル酸ジヘブチル、γ−ブチロラクトン、α−バレロラク
トン、クマリン、フタリド、炭酸エチレンなどの炭素数
２ないし２゜の有機酸エステル類、（へ）ケイ酸エチル
、ケイ酸ブチル、フェニルトリエトキンシラン、ジフェ
ニルジメトキシシラン、第三ブチルメチルジメトキシシ
ランなどのケイ酸エステルまたはシランのようなケイ素
化合物類、（ト）アセチルクロリド、ベンゾイルクロリ
ド、トルイル酸クロリド、アニス酸クロリド、塩化フタ
ロイル、イソ塩化フタロイルなどの炭素数２ないし１５
の酸ハライド類、（チ）メチルエーテル、エチルエーテ
ル、イソプロピルエーテル、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、ジフェニル
エーテルなどの炭素数２ないし２０のエーテル類、（す
）酢酸アミド、安息香酸アミド、トルイル酸アミドなど
の酸アミド類、（ヌ）メチルアミン、エチルアミン、ジ
エチルアミン、トリブチルアミン、ピペリジン、トリベ
ンジルアミン、アニリン、ピリジン、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、（ル）アセト
ニトリル、ベンゾニトリル、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。これら電子供与体は
、２８以上用いることができる。これらの中で好ましい
のは有機酸エステル、酸ハライドおよびケイ素化合物で
あり、特に好ましいのは酢酸エチルセロソルブ、フタル
酸エステル、フタル酸ハライドおよび有機アルコキシケ
イ素である。Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, ethyl cellosolve benzoate, propyl benzoate, butyl benzoate,
Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, phthalate Diethyl acid, dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, organic acid esters with carbon atoms of 2 to 2° such as ethylene carbonate, (he)ethyl silicate, butyl silicate , silicon compounds such as silicic acid esters or silanes such as phenyltriethquinsilane, diphenyldimethoxysilane, tert-butylmethyldimethoxysilane, (t)acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, phthaloyl chloride, 2 to 15 carbon atoms such as phthaloyl isochloride
acid halides, (th) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, (th) acetic acid amide, benzoic acid amide, toluic acid Acid amides such as amide, amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, (l)acetonitrile, benzonitrile, tolnitrile, etc. Nitriles, etc. can be mentioned. 28 or more of these electron donors can be used. Preferred among these are organic acid esters, acid halides, and silicon compounds, and particularly preferred are ethyl cellosolve acetate, phthalic acid esters, phthalic acid halides, and organic alkoxy silicones.
上記各成分の使用量は、本発明の効果が認められるかぎ
り任意のものでありうるが、−前約には、次の範囲内が
好ましい。The amount of each of the above components to be used may be arbitrary as long as the effects of the present invention are observed, but it is preferably within the following range.
チタン化合物の使用量は、使用するマグネシウム化合物
の使用量に対してモル比でｌＸｌ０’〜１０００の範囲
内がよく、好ましくは０，０１〜１０の範囲内である。The amount of the titanium compound to be used is preferably in the range of 1X10' to 1000, preferably in the range of 0.01 to 10, in terms of molar ratio to the amount of the magnesium compound used.
ハロゲン源としてそのための化合物を使用する場合は、
その使用量はチタン化合物および（または）マグネシウ
ム化合物がハロゲンを含む、含まないにかかわらず、使
用するマグネシウムの使用量に対してモル比でＩ×１０
−２〜１０００の範囲内がよく、好ましくは０．１〜１
００の範囲内である。前記の任意成分としてのケイ素、
アルミニウムおよびホウ素化合物の使用量は、上記のマ
グネシウム化合物の使用量に対してモル比でｌＸｌ０’
〜１００の範囲内がよく、好ましくは０．０１〜１の範
囲内である。When using such compounds as halogen sources,
The amount used is I x 10 in molar ratio to the amount of magnesium used, regardless of whether the titanium compound and/or magnesium compound contains halogen or not.
-2 to 1000, preferably 0.1 to 1
It is within the range of 00. silicon as an optional component of the above;
The amounts of aluminum and boron compounds to be used are lXl0' in molar ratio to the amount of magnesium compound used above.
It is preferably within the range of 100 to 100, preferably 0.01 to 1.
電子供与件化合物の使用量は、上記のマグネシウム化合
物の使用量に対してモル比でｌＸｌ０’〜１０の範囲内
がよく、好ましくは０．０１〜５の範囲内である。The amount of the electron donating compound to be used is preferably in the range of lXl0' to 10, preferably in the range of 0.01 to 5, in terms of molar ratio to the amount of the magnesium compound used.
成分（Ａ）は、上述のチタン源、マグネシウム源および
ハロゲン源、更には必要により電子供与体等の他成分を
用いて、例えば以下の様な製造法により製造される。Component (A) is produced, for example, by the following production method using the above titanium source, magnesium source and halogen source, and further, if necessary, other components such as an electron donor.
（イ） ハロゲン化マグネシウムと必要に応じて電子供
与体とチタン含有化合物とを接触させる方法。(a) A method of bringing magnesium halide and, if necessary, an electron donor and a titanium-containing compound into contact.
（ロ） アルミナ又はマグネシアをハロゲン化リン化合
物で処理し、それにハロゲン化マグネシウム、電子供与
体、チタンハロゲン含有化合物を接触させる方法。(b) A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide, an electron donor, and a titanium/halogen-containing compound.
（ハ） ハロゲン化マグネシウムとチタンテトラアルコ
キシドおよび特定のポリマーケイ素化合物を接触させて
得られる固体成分に、チタンハロゲン化合物およびまた
はケイ素のハロゲン化合物を接触させる方法。(c) A method of contacting a titanium halogen compound and/or a silicon halogen compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound.
このポリマーケイ素化合物としては、下式で示されるも
のが適当である。As this polymer silicon compound, those represented by the following formula are suitable.
■
（ここで、Ｒは炭素数１〜１０程度の炭化水素残基、ｎ
はこのポリマーケイ素化合物の粘度が１〜１００センチ
スト一クス程度となるような重合度を示す）
これらのうちでは、メチルハイドロジエンポリシロキサ
ン、１． ３． ５． ７−チトラメチルシクロテトラ
シロキサン、１，３，５，７．９−ペンタメチルシクロ
ペンクンロキサン、エチルハイドロジエンポリシロキサ
ン、フェニルハイドロジエンポリシロキサン、シクロへ
キシルハイドロジエンポリシロキサン、等が好ましい。(Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
indicates a degree of polymerization such that the viscosity of the polymeric silicon compound is about 1 to 100 centistics) Among these, methylhydrodiene polysiloxane, 1. 3. 5. Preferred are 7-titramethylcyclotetrasiloxane, 1,3,5,7.9-pentamethylcyclopenchunroxane, ethylhydrodiene polysiloxane, phenylhydrodiene polysiloxane, cyclohexylhydrodiene polysiloxane, and the like.
（ニ） マグネシウム化合物をチタンテトラアルコキシ
ドおよび電子供与体で溶解させて、ハロゲン化剤または
チタンハロゲン化合物で析出させた固体成分に、チタン
化合物を接触させる方法。(d) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound.
（ホ） グリニヤール試薬等の有機マグネシウム化合物
をハロゲン化剤、還元剤等と作用させた後、これに必要
に応じて電子供与体とチタン化合物とを接触させる方法
。(e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the compound as necessary.
（へ） アルコキシマグネシウム化合物にハロゲン化剤
および／またはチタン化合物を電子供与体の（ｊ在もし
くは不存在下に接触させる方法。(f) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.
成分（Ｂ）
（但しに１は分岐鎖状炭化水素残基を、Ｒ−はＲ１と同
一かもしくは異なる炭化水素残基を、Ｒ３は炭化水素残
基を、ｎは１≦ｎ≦３の数を、それぞれ示す）で表わさ
れるケイ素化合物である。Component (B) (where 1 is a branched hydrocarbon residue, R- is the same or different hydrocarbon residue as R1, R3 is a hydrocarbon residue, and n is a number of 1≦n≦3) It is a silicon compound represented by (respectively shown).
ここで、Ｒ１はケイ素原子に隣接する炭素原子から分岐
しているものが好ましい。その場合の分岐基は、アルキ
ル基、シクロアルキル基またはアリール基（たとえば、
フェニル基またはメチル置換フェニル基）であることか
好ましい。さらに好ましいＲ１は、ケイ素原子に隣接す
る炭素原子、すなわちα−位炭素原子、か２級または′
う級の炭素原子であるものである。とりわけ、ケイ素片
ｒに結合している炭素原子が３級のものが好ましい。Here, R1 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example,
phenyl group or methyl-substituted phenyl group). More preferably, R1 is a carbon atom adjacent to a silicon atom, that is, an α-position carbon atom, a secondary or
It is a class carbon atom. Particularly preferred is one in which the carbon atom bonded to the silicon piece r is tertiary.
Ｒ１の炭素数は通常３〜２０、好ましくは４〜１０、で
ある。The number of carbon atoms in R1 is usually 3 to 20, preferably 4 to 10.
Ｒ″″は、炭素数１〜２０、好ましくは１〜１０、の分
岐あるいは直鎖状の脂肪族炭化水素基であることがふつ
うである。Ｒ３は脂肪族炭化水素基、好ましくは炭素数
１〜４の鎖状脂肪族炭化水素基、であることがふつうで
ある。R″″ is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R3 is usually an aliphatic hydrocarbon group, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms.
成分（Ｂ）のケイ素化合物の具体例は、下記の通りであ
る。Specific examples of the silicon compound of component (B) are as follows.
（ＣＨ） Ｃ３ｔ （ＣＨ）（ＯＣＨ３） ２．（Ｃ
Ｈ） Ｃ３ｉ （ＣＨ（ＣＨ））（ＯＣＨ３） ２．
（ＣＨ３）３Ｃ８ｉ（ＣＨ３）（ＯＣ２Ｈ５）２、（Ｃ
Ｈ） Ｃ３ｉ （ＣＨ） （ＯＣＨ３） ２．（ＣＨ
３）（Ｃ２Ｈ５）ＣＨ８ｉ（ＣＨ３）（ＯＣＨ３）２、
（（ＣＨ３）２ＣＨＣＨ２）２Ｓｉ（ＯＣＨ３）２、（
Ｃ２Ｈ５）（ＣＨ３）２Ｃ８ｉ（ＣＨ３）（ＯＣＨ３）
２、（Ｃ２Ｈ５）（ＣＨ３）２Ｃ８ｉ（ＣＨ３）（ＯＣ
２Ｈ５）２、（ＣＨ） Ｃ５ｒ （ＯＣＨ３） ３、
（ＣＨ３）３Ｃ８ｌ（ＯＣ２Ｈ５）３、（Ｃ２Ｈ５）３
Ｃ８１（ＯＣ２Ｈ５）３・（ＣＨ３）（Ｃ２Ｈ５）ＣＨ
８１（ＯＣＨ３）、（ＣＨ） （ＣＨ） ｃｓｉ （
ＯＣＨ３） ３．（ＣＨ）（ＣＨ） Ｃ８ｉ （ＯＣ
２Ｈ５）３．成分（Ｃ）
成分（Ｃ）は、周期律表第Ｉ〜ＩＩＩ族金属の１機金属
化合物である。金属としては、リチウム、ナトリウム、
カリウム、マグネシウム、亜鉛およびアルミニウムが代
表的である。これらの金属に直結して有機金属化合物を
形成すべき有機基は、アルキル基（炭素数１〜１０程度
）およびフェニルないし低級アルキル置換フェニル基か
代表的である。これらの金属の原子価はその少なくとも
−はこのようなａ機Ｌ（で充足されなければならないが
、残、りの原子価は他の基、たとえばアルコキシ括（炭
素数１〜１０程度）、ハロゲン原子等によって充足され
ていてもよい。(CH) C3t (CH) (OCH3) 2. (C
H) C3i (CH(CH))(OCH3) 2.
(CH3)3C8i(CH3)(OC2H5)2, (C
H) C3i (CH) (OCH3) 2. (CH
3) (C2H5)CH8i (CH3) (OCH3)2,
((CH3)2CHCH2)2Si(OCH3)2, (
C2H5)(CH3)2C8i(CH3)(OCH3)
2, (C2H5) (CH3)2C8i (CH3) (OC
2H5)2, (CH) C5r (OCH3) 3,
(CH3)3C8l (OC2H5)3, (C2H5)3
C81(OC2H5)3・(CH3)(C2H5)CH
81 (OCH3), (CH) (CH) csi (
OCH3) 3. (CH) (CH) C8i (OC
2H5)3. Component (C) Component (C) is a single metal compound of metals from groups I to III of the periodic table. Metals include lithium, sodium,
Potassium, magnesium, zinc and aluminum are representative. Typical organic groups to be directly bonded to these metals to form organometallic compounds are alkyl groups (about 1 to 10 carbon atoms) and phenyl to lower alkyl-substituted phenyl groups. At least one of the valences of these metals must be satisfied by such a group, but the remaining valences must be satisfied by other groups, such as alkoxy groups (about 1 to 10 carbon atoms), halogens, etc. It may be filled with atoms, etc.
このような有機金属化合物としては、具体的には、メチ
ルリチウム、ｎ−ブチルリチウム、第三ブチルリチウム
などの有機リチウム化合物、ジエチル亜鉛、ジローブチ
ル亜鉛などの有機亜鉛化合物、ジブチルマグネシウム、
ブチルエチルマグネシウム、ブチルマグネシウムプロミ
ドなどの有機マグネシウム化合物、トリメチルアルミニ
ウム、トリエチルアルミニウム、トリｎ−ブチルアルミ
ニウム、トリイソブチルアルミニウム、ジエチルアルミ
ニウムクロリド、エチルアルミニウムセスキクロリド、
ジエチルアルミニウムクロリドなどの有機アルミニウム
化合物か例示される。このうち、有機アルミニウム化合
物が好ましい。Specifically, such organometallic compounds include organolithium compounds such as methyllithium, n-butyllithium, and tert-butyllithium; organozinc compounds such as diethylzinc and dibutylzinc; dibutylmagnesium;
Organomagnesium compounds such as butyl ethylmagnesium, butylmagnesium bromide, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride,
Examples include organoaluminum compounds such as diethylaluminum chloride. Among these, organic aluminum compounds are preferred.
成分■
成分■は、有機リチウムあるいは有機マグネシウム化合
物である。リチウムおよびマグネシウムに結合すべき基
については、成分（Ｃ）について上記したところがあて
はまる。Ingredient ■ Ingredient ■ is an organolithium or organomagnesium compound. Regarding the groups to be bonded to lithium and magnesium, what has been said above for component (C) applies.
このような有機金属化合物としては、具体的には、メチ
ルリチウム、ｎ−ブチルリチウム、第ニブチルリチウム
、第三ブチルリチウム、ジエチルマグネシウム、ジロー
ブチルマグネシウム、モロ−ヘキシルマグネシウム、ブ
チルエチルマグネシウム、ヘキシルエチルマグネシウム
、ブチルマグネシウムプロミド、第三ブチルマグネシウ
ムプロミド、ｎ−ブチルマグネシウムエトキシドなどが
例示される。Specifically, such organometallic compounds include methyllithium, n-butyllithium, nibutyllithium, tert-butyllithium, diethylmagnesium, dibutylmagnesium, moro-hexylmagnesium, butylethylmagnesium, hexylethyl Examples include magnesium, butylmagnesium bromide, tert-butylmagnesium bromide, and n-butylmagnesium ethoxide.
予備重合
固体成分（Ｉ）および成分（■）にα−オレフィンを接
触させて、このα−オレフィンを固体成分（Ｉ）Ｉｇあ
たり、０．０１〜１００ｇ重合させることにより、本発
明のα−オレフィン重合用触媒成分を得る。この重合、
すなわち予備重合、に使用するα−オレフィンとしては
、エチレン、プロピレン、１−ブテン、１−ヘキセン、
１−オクテン、ブタジェン、１．４−ヘキサジエン、１
゜５〜へキサジエン、４−メチルペンテン−１，３−メ
チルブテン−１、スチレン、ｐ−メチルスチレン、ジビ
ニルベンゼン等が用いられる。また、これらのオレフィ
ンを、複数個段階的に、あるいは共存で使用してもよい
。予（ｉｉ！重合時の温度は任意であるが、好ましくは
一２０℃から７０℃、さらに好ましくは０℃から５０℃
、である。The α-olefin of the present invention is produced by bringing an α-olefin into contact with prepolymerized solid component (I) and component (■), and polymerizing 0.01 to 100 g of this α-olefin per Ig of solid component (I). A catalyst component for polymerization is obtained. This polymerization,
That is, the α-olefins used for prepolymerization include ethylene, propylene, 1-butene, 1-hexene,
1-octene, butadiene, 1,4-hexadiene, 1
5-hexadiene, 4-methylpentene-1,3-methylbutene-1, styrene, p-methylstyrene, divinylbenzene, etc. are used. Further, a plurality of these olefins may be used in stages or in combination. Pre(ii! The temperature during polymerization is arbitrary, but preferably from -20°C to 70°C, more preferably from 0°C to 50°C.
, is.
固体成分（Ｉ）と成分（ＩＩ）の量比は任意であるが、
好ましくは固体成分（Ｉ）中のチタン１モルに対して成
分（ＩＩ）を０．０１〜１００倍モル、さらに好ましく
は、０，１〜１０倍モル、使用する。Although the quantitative ratio of solid component (I) and component (II) is arbitrary,
Preferably, component (II) is used in an amount of 0.01 to 100 times, more preferably 0.1 to 10 times, mole per mole of titanium in solid component (I).
予備重合は、−前約に不活性溶媒中で行なうが、液状上
ツマー中あるいはガス状モノマー中で行なうことも可能
である。また、分子量制御のために水素を共存すること
も可能である。The prepolymerization is first carried out in an inert solvent, but it is also possible to carry out the prepolymerization in liquid supernatants or in gaseous monomers. Further, it is also possible to coexist hydrogen in order to control the molecular weight.
触媒成分の利用／オレフィンの重合
触媒の形成
前記の本発明による固体触媒成分は、これを重合活性化
剤であるＨ機アルミニウム化合物と組み合わせることに
より、有用なα−オレフィン重合用触媒を与える。Utilization of Catalyst Component/Formation of Olefin Polymerization Catalyst The solid catalyst component according to the present invention described above can be combined with an H-organic aluminum compound as a polymerization activator to provide a useful catalyst for α-olefin polymerization.
有機アルミニウム化合物としては、チーグラー・ナツタ
型触媒に使用されるものとして公知のもの、たとえば、
トリメチルアルミニウム、トリエチルアルミニウム、ト
リイソブチルアルミニウム、ジエチルアルミニウムクロ
リド、エチルアルミニウムセスキクロリド、ジエチルア
ルミニウムヒドリド、ジエチルアルミニウムエトキシド
、メチルアルモキサン等が用いられる。また、これらの
うちの２種類以上を組み合わせて使用することも可能で
ある。Examples of organoaluminum compounds include those known for use in Ziegler-Natsuta type catalysts, such as:
Trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, methylalumoxane, etc. are used. It is also possible to use two or more of these in combination.
オレフィン重合
このような触媒はａ−オレフィンの重合に広く利用する
ことができるが、本発明による触媒成分の利点を特に享
受することができるのはプロピレンのブロック共重合で
ある。Olefin Polymerization Although such catalysts can be widely used for the polymerization of a-olefins, it is the block copolymerization of propylene that can particularly benefit from the catalyst components according to the invention.
プロピレンのブロック共重合は公知であって、重合工程
は、少なくとも前段重合および後段重合の二段階よりな
る。Block copolymerization of propylene is known, and the polymerization process consists of at least two stages: first-stage polymerization and second-stage polymerization.
（前段重合）
前段重合は、プロピレン単独あるいはプロピレン／エチ
レン混合物を前記触媒を何する重合系に供給して、−段
あるいは多段に重合させて、プロピレン単独重合体また
はエチレン含量７重量％以下、好ましくは０．５重皿９
６以下のプロピレン／エチレン共重合体を全重合ｍの３
０〜９５重二％、好ましくは５０〜９０重二％、に相当
する量形成させる工程である。(First-stage polymerization) In the first-stage polymerization, propylene alone or a propylene/ethylene mixture is supplied to a polymerization system using the above-mentioned catalyst, and is polymerized in one stage or in multiple stages to produce a propylene homopolymer or an ethylene content of 7% by weight or less, preferably. is 0.5 heavy plate 9
Total polymerization of propylene/ethylene copolymer of 6 or less m3
This is a step of forming an amount corresponding to 0 to 95%, preferably 50 to 90%.
前段重合でプロピレン・エチレン共重合体中のエチレン
含量が７重量％を越えると、最終共重合体の嵩密度が低
下し、低結晶性重合体の副生量が大幅に増大する。また
、重合割合が上記範囲の下限未満では、やはり低結晶性
重合体の副生量が増加する。一方、重合割合が上記範囲
の上限を越えると、ブロック共重合体の目的である耐衝
撃強度の向上効果が現われなくなると共に、本発明の触
媒成分固有の効果であるスパイラルフローの改良効果も
現われなくなる。If the ethylene content in the propylene/ethylene copolymer exceeds 7% by weight in the first stage polymerization, the bulk density of the final copolymer will decrease and the amount of by-product of low crystallinity polymer will increase significantly. Moreover, if the polymerization ratio is less than the lower limit of the above range, the amount of by-product of the low crystalline polymer will increase. On the other hand, if the polymerization ratio exceeds the upper limit of the above range, the effect of improving impact strength, which is the purpose of the block copolymer, will not appear, and the effect of improving spiral flow, which is an effect unique to the catalyst component of the present invention, will also not appear. .
前段重合の重合温度は３０〜９５°Ｃ１好ましくは５０
〜８５℃、程度であり、重合圧力は通常１〜５０ｋｇ／
ｃｄＧの範囲である。前段重合においては、水素などの
分子量調節剤を用いてＭ Ｆ Ｒを制御して、最終共重
合体の溶融流動性を高めておくのが好ましい。The polymerization temperature in the first stage polymerization is 30 to 95°C, preferably 50°C.
~85℃, and the polymerization pressure is usually 1~50kg/
cdG range. In the first-stage polymerization, it is preferable to control M FR using a molecular weight regulator such as hydrogen to enhance the melt fluidity of the final copolymer.
（後段重合）
後段重合は、前段重合に引きつづいて、プロピレン／エ
チレン混合物をさらに導入してエチレン倉ユが２０〜１
０（］重量％、好ましくは３０〜１００重二９６、更に
好ましくは３０〜７０重量％、のプロピレン／エチレン
共重合体を一段又は多段で得る工程である。この上程で
は、全重合体量の５〜７０重量％、好ましくは１０〜５
０重量％、にト（」当する量を形成することが望ましい
。(Second-stage polymerization) In the second-stage polymerization, following the first-stage polymerization, a propylene/ethylene mixture is further introduced until the ethylene capacity is 20 to 1.
This is a process for obtaining a propylene/ethylene copolymer of 0% by weight, preferably 30 to 100% by weight, more preferably 30 to 70% by weight, in one or multiple stages. 5-70% by weight, preferably 10-5
It is desirable to form an amount equivalent to 0% by weight.
後段重合では、他のコモノマーを共存させても良い。例
えば、１−ブテン、１−ペンテン、１−ヘキセン等のα
−オレフィンを用いることができる。In the latter stage polymerization, other comonomers may be present together. For example, α of 1-butene, 1-pentene, 1-hexene, etc.
-Olefins can be used.
後段重合の重合７？Ｌ度は、３０〜９０°Ｃ１好ましく
は５０〜８０℃、程度である。重合圧力は、１〜５０ｋ
ｇ／ｃｊＧの範囲が通常用いられる。Post-stage polymerization 7? The L degree is about 30 to 90°C, preferably 50 to 80°C. Polymerization pressure is 1 to 50k
A range of g/cjG is commonly used.
前段重合から後段重合に移る際に、プロピレンガスまた
はプロピレン／エチレン混合ガスと水素ガスをパージし
て次の工程に移ることか好ましい。When moving from the first-stage polymerization to the second-stage polymerization, it is preferable to purge the propylene gas or propylene/ethylene mixed gas and hydrogen gas before moving on to the next step.
また、必要に応じて触媒、特に有機アルミニウム化合物
、を追加することもできる。Further, a catalyst, especially an organoaluminum compound, can be added as necessary.
後段重合で分子量調節剤は、目的に応して用いても用い
なくても良い。A molecular weight regulator may or may not be used in the post-polymerization depending on the purpose.
（重合様式）
このようなプロピレンブロック共重合体の製造法は、回
分式、連続式、半回分式のいずれのｈ−法によっても実
施可能である。この際、ヘプタン等の不活性炭化水素溶
媒中で重合を行なう方法、使用する（Ｉ１量体自身を媒
質として重合を行なう方法、媒質を使用せずにガス状の
単量体中で重合を行なう方法、さらには、これらを組み
合わせて重合を行なう方法がある。(Polymerization mode) Such a method for producing a propylene block copolymer can be carried out by any h-method, such as a batch method, a continuous method, or a semi-batch method. At this time, a method is used in which polymerization is carried out in an inert hydrocarbon solvent such as heptane (a method in which polymerization is carried out using the I monomer itself as a medium, and a method in which polymerization is carried out in a gaseous monomer without using a medium). There are also methods for carrying out polymerization by combining these methods.
また、後段重合工程で生成すべきゴムの分子量を高分子
量化する目的で、後段重合中に、電子供与性化合物やＨ
機金属化ご物を添加することも可能である。In addition, in order to increase the molecular weight of the rubber to be produced in the later polymerization process, electron-donating compounds and H
It is also possible to add metallization.
実験例
実施ド１１１
〔固体成分（Ｉ）の製造〕
充分に窒素置換したフラスコに脱水および脱酸素したｎ
−へブタン２００ ミリリットルを導べし、次いでＭｇ
Ｃｌ ２を０．４モル、
ｒｔ （０−ｎＣ４Ｈ９） ４を〔〕、８モル導入し９
５℃で２時間反応させた。反応終了後、４０℃に温度を
下げ、次いでメチルヒドロポリシロギサン（２０センチ
ストークスのもの）を４８ミリリツトル導入し、３時間
反応させた。生成した固体成分をローへブタンで洗ｉ”
ｐＬだ。Experimental Example No. 111 [Production of solid component (I)] Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- introduce 200 ml of hebutane, then Mg
0.4 mol of Cl 2 and 8 mol of rt (0-nC4H9) 4 were introduced and 9
The reaction was carried out at 5°C for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 48 milliliters of methylhydropolysiloxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 3 hours. Wash the generated solid components with raw butane.
It's pL.
ついで充分に窒素置換したフラスコに上記と同様にｌ’
ｉ’ｉ製したｎ−へブタンを５０ミリリツトル導入し、
上記で合成した固体成分をＭｇ原子換算で０．２４モル
導入した。ついでｎ−へブタン２５ミリリゾトルにＳ
ｉ Ｃｌ ４ｏ、 ４モルを混合して３０℃、１０分間
でフラスコへ導入し、７０°Ｃて３時間反応させた。反
応終了後、ｎ−へブタンで洗浄した。次いてｎ−へブタ
ンを２５ミリリットルにフタル酸クロライド０．０２４
モルを混合して、７０℃／３０分間でフラスコ・＼導入
し、９０℃で１時間反応させた。Then, in the same manner as above, add l' to a flask that has been sufficiently purged with nitrogen.
Introducing 50 milliliters of n-hebutane produced by i'i,
0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then add S to 25 millilizotol of n-hebutane.
4 moles of iCl4O were mixed and introduced into a flask at 30°C for 10 minutes, followed by reaction at 70°C for 3 hours. After the reaction was completed, it was washed with n-hebutane. Next, add 25 ml of n-hebutane to 0.024 ml of phthalic acid chloride.
The moles were mixed, introduced into the flask at 70°C for 30 minutes, and reacted at 90°C for 1 hour.
反応終了後、ｎ−へブタンで洗浄した。次いでＳ ｓ
Ｃｌ ４ ２０ミリリツトルを導入して８０ ’Ｃで６
時間反応させた。反応終了後、ｎ−へブタンで充分に洗
浄した。このもの（成分（Ａ））のチタン含量は、１，
２１重量パーセントであった。After the reaction was completed, it was washed with n-hebutane. Then S s
Introducing 20ml of Cl4 and heating at 80'C
Allowed time to react. After the reaction was completed, it was thoroughly washed with n-hebutane. The titanium content of this material (component (A)) is 1,
It was 21% by weight.
充分に窒素置換したフラスコに充分に精製したｎ−へブ
タンを５０ミリリツトル導入し、次いで上記で得た成分
を５グラム導入し、次いで（ＣＨ３） ３Ｃ３ｉ （Ｃ
Ｈ３）（ＯＣＨ３） ２（成分（Ｂ））を１．６ミリリ
ツトル導入し、次いでＴｉＣｌ４０．５２ミリリツトル
、更にトリエチルアルミニウム（成分（Ｃ））３．０グ
ラムをそれぞれ導入し、３０℃で２時間接触させた。50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, then 5 grams of the component obtained above was introduced, and then (CH3) 3C3i (C
1.6 ml of H3)(OCH3) 2 (component (B)) was introduced, then 0.52 ml of TiCl and 3.0 g of triethylaluminum (component (C)) were introduced, and the mixture was contacted at 30°C for 2 hours. I let it happen.
接触終了後、ｎ−へブタンで充分洗浄して、固体成分（
Ｉ）とした。固体成分（Ｉ）中のチタン含量は、３．６
４重量パーセントであった。After the contact is complete, wash thoroughly with n-hebutane to remove the solid components (
I). The titanium content in solid component (I) is 3.6
It was 4% by weight.
充分に窒素置換した内容積１．５リツトルの攪拌式オー
トクレーブに、脱水および脱酸素したｎ−へブタン４０
０ｍ１を導入し、系内を１５℃に冷却した後、成分（Ｉ
Ｉ）としてｎ−ブチルリチウム０．４ｇおよび上記固体
成分（Ｉ）を４ｇ導入し、プロピレンを８ ｇ ／ Ｈ
ｒで０．５時間フィードして予備重合を行なった。プロ
ピレンフィード終了後、１０分間残圧重合を行なった。In a stirred autoclave with an internal volume of 1.5 liters that was sufficiently purged with nitrogen, 40% of dehydrated and deoxygenated n-hebutane was added.
After introducing 0 ml of component (I) and cooling the system to 15°C, the component (I
0.4 g of n-butyllithium and 4 g of the above solid component (I) were introduced as I), and propylene was introduced at a rate of 8 g/H.
Prepolymerization was carried out by feeding at r for 0.5 hours. After the end of propylene feeding, residual pressure polymerization was carried out for 10 minutes.
終了後、ローへブタンで２回洗浄して、目的の重合用触
媒成分を得た。この重合用触媒成分４グラム上には、ポ
リマーが３，７２グラムあり、従って本発明重合用触媒
成分が７．７２グラム得られた。After completion, the mixture was washed twice with rhohebutane to obtain the desired polymerization catalyst component. On 4 grams of this polymerization catalyst component, there were 3.72 grams of polymer, so 7.72 grams of the polymerization catalyst component of the present invention were obtained.
内容積１．５リツトルの攪拌式オートクレーブ内をプロ
ピレンで充分置換した後、充分に脱水および脱酸素した
ｎ−へブタン５００ミリリツトル導入し、さらに上記重
合用触媒成分を２０ミリグラム（３９，４ミリグラムポ
リマー含む）、トリエチルアルミニウム５０ミリグラム
をプロピレン雰囲気下に導入した。After sufficiently purging the inside of a stirred autoclave with an internal volume of 1.5 liters with propylene, 500 ml of n-hebutane that had been sufficiently dehydrated and deoxygenated was introduced, and 20 mg (39.4 mg polymer) of the above polymerization catalyst component was added. ), 50 milligrams of triethylaluminum were introduced under a propylene atmosphere.
前段重合は、水素２７０ミリリツトル導入した後、温度
を７５℃にしてプロピレンを０．９１７グラム／分の定
速で導入した。３時間後、プロピレンの導入を停止し、
重合を７５℃で継続した。In the first stage polymerization, after introducing 270 milliliters of hydrogen, the temperature was raised to 75° C. and propylene was introduced at a constant rate of 0.917 g/min. After 3 hours, the introduction of propylene was stopped and
Polymerization was continued at 75°C.
圧力が２ｋｇｃｄゲージとなった時点で中間サンプルと
して１／１０サンプリングした。さらに気相部を０ 、
２ ｋｇ ／ ｃｊゲージまでパージした後、プロピレ
ンを０．１３３グラム／分およびエチレンを０．２００
グラム／分、それぞれ定速で６５℃下１．５時間導入し
た。When the pressure reached 2 kg CD gauge, 1/10 sample was taken as an intermediate sample. Furthermore, the gas phase part is set to 0,
0.133 g/min of propylene and 0.200 g/min of ethylene after purging to 2 kg/cj gauge
gram/min, respectively, at a constant rate of 65° C. for 1.5 hours.
重合終了後、気相部をパージし、スラリーをか過、乾燥
して、１６２．２グラムのポリマーを得た。一方、濾液
を乾燥することにより、副生低結晶性重合体３．３７グ
ラムを得た。生成ポリマーのＭＦＲは５，５２グラム／
１０分であり、嵩密度は０．４６４ｇ／ｃｃであった。After the polymerization was completed, the gas phase was purged, and the slurry was filtered and dried to obtain 162.2 grams of polymer. On the other hand, by drying the filtrate, 3.37 g of a by-product low crystalline polymer was obtained. The MFR of the produced polymer is 5,52 grams/
10 minutes, and the bulk density was 0.464 g/cc.
また、中間サンプルを乾燥することで得られたポリマー
のＭＦＲは、１８．９グラム／１０分であった。粉体ポ
リマーの安息角は３２．７度であった。この重合の収率
は、９２００ｇポリマー／ｇ−固体触媒である。Furthermore, the MFR of the polymer obtained by drying the intermediate sample was 18.9 grams/10 minutes. The angle of repose of the powder polymer was 32.7 degrees. The yield of this polymerization is 9200 g polymer/g solid catalyst.
実施例２
〔重合用触媒成分の製造〕
実施例１で使用した成分（ＩＩＩ）のｎ−ブチルリチウ
ムの瓜を０．２４グラムにかえる以外は全て実施例１と
同様にして操作を行なった。得られた重合用触媒成分４
グラム上にポリマーが４．１２グラムあり、従って本発
明触媒成分が８．１２グラム得られた。Example 2 [Manufacture of catalyst component for polymerization] All operations were carried out in the same manner as in Example 1 except that the amount of n-butyllithium melon used in Example 1 as component (III) was changed to 0.24 g. Obtained polymerization catalyst component 4
There were 4.12 grams of polymer per gram, thus yielding 8.12 grams of the catalyst component of the present invention.
重合用触媒を変える以外は全て実施例１と同一条件で重
合を行なった。結果は、表１に示す通りであった。Polymerization was carried out under the same conditions as in Example 1 except that the polymerization catalyst was changed. The results were as shown in Table 1.
実施例３
実施例２で得られた重合用触媒成分１７ミリグラム（３
４，５ミリグラムポリマー含’＃）、トリエチルアルミ
ニウム１２５ミリグラムおよび水素を２００ミリリツト
ルとする以外は全て、実施例１と同一条件で重合を行な
った。結果は、表−１に示すに示す通りであった。Example 3 17 milligrams of the polymerization catalyst component obtained in Example 2 (3
Polymerization was carried out under the same conditions as in Example 1, except that the amount of polymer was 4.5 mg, 125 mg of triethylaluminum, and 200 ml of hydrogen. The results were as shown in Table-1.
比較例１
〔重合用触媒成分の製造〕
実施例１で得られた固体成分（Ｉ）４グラムを用い、成
分（ＩＩ）のかわりにトリエチルアルミニウム０．６グ
ラム使用する以外は全て実施例１と同一条件で予備重合
を行なった。得られた重合用触媒成分４グラム上にはポ
リマーが４．２グラムあり、従って本発明触媒成分が８
．２グラム得られた。Comparative Example 1 [Manufacture of catalyst component for polymerization] All procedures were carried out as in Example 1 except that 4 grams of solid component (I) obtained in Example 1 was used and 0.6 grams of triethylaluminum was used instead of component (II). Prepolymerization was carried out under the same conditions. There are 4.2 grams of polymer on 4 grams of the polymerization catalyst component obtained, and therefore 8 grams of the catalyst component of the present invention.
．． 2 grams were obtained.
（プロピレンの共重合〕
上記重合用触媒成分１７ミリグラム（３４，９ミリグラ
ムポリマー含ａ）、トリエチルアルミニウム１２５ミリ
グラムおよび水素を２００ミリリットルとする以外は全
て実施例１と同一条件で重合を行なった。結果は、表−
１に示す通りであった。(Copolymerization of propylene) Polymerization was carried out under the same conditions as in Example 1, except that 17 mg of the above polymerization catalyst component (34.9 mg polymer included a), 125 mg of triethylaluminum, and 200 ml of hydrogen were used.Results is table-
It was as shown in 1.
実施例４．５．６．７および比較例２
〔重合用触媒成分の製造〕
実施例−１の固体成分−Ｉを４ｇ用い、成分■として表
−２に示す化合物を用いる以外は全て実施例１と同一条
件で予備重合を行なった。結果は、表−２に示す通りで
あった。Example 4.5.6.7 and Comparative Example 2 [Manufacture of catalyst component for polymerization] All examples were the same except that 4 g of solid component-I of Example-1 was used and the compound shown in Table-2 was used as component (2). Prepolymerization was carried out under the same conditions as in Example 1. The results were as shown in Table-2.
実施例〕と同一条件で重合を行なった。結果は、表−３
に示す通りであった。Polymerization was carried out under the same conditions as in Example]. The results are shown in Table 3.
It was as shown in
実施例８
〔固体成分Ｉの製造〕
充分に窒素置換したフラスコに脱水および脱酸素したｎ
−へブタン２００ミリリツトルを導入し、次いでＭｇＣ
ｌ２を０．４モル、
Ｔ Ｌ （０−ｎ Ｃ４Ｈ９） ４を０，８モル導入
し、９５℃で２時間反応させた。反応終了後、４０℃に
温度を下げ、次いでメチルヒドロポリシロキサン（２０
センチストークスのもの）を４８ミリリツトル導入し、
３時間反応させた。生成した固体成分をｎ−ヘプタンで
洗浄した。Example 8 [Production of solid component I] Dehydrated and deoxidized n was placed in a flask that was sufficiently purged with nitrogen.
- 200 ml of hebutane is introduced, then MgC
0.4 mol of 12 and 0.8 mol of T L (0-n C4H9) 4 were introduced, and the mixture was reacted at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and then methylhydropolysiloxane (20°C
Introduced 48 milliliters of centistokes),
The reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-heptane.
次いで充分に窒素置換したフラスコに上記と同様に精製
したｎ−へブタンを５０ミリリツトル導入し、上記で合
成した固体成分をＭｇ原子換算で０．２４モル導入した
。ついでｎ−へブタン２５ミリリツトルにＳ Ｌ Ｃ１
４０，４モルを混合して３０℃、３０分間でフラスコへ
導入し、７０℃で３時間反応させた。反応終了後、ｎ−
へブタンで洗浄した。Next, 50 milliliters of n-hebutane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, add 25 ml of n-hebutane to S L C1.
40.4 moles were mixed and introduced into a flask at 30°C for 30 minutes, followed by reaction at 70°C for 3 hours. After the reaction is complete, n-
Washed with hebutane.
次いでトルエン２５ミリリツトルにジフェニルメタノー
ル０．５５ｇを溶解させ、これを５０℃／３０分でフラ
スコに導入して、９０℃で３時間反応させた。反応終了
後、ｎ−へブタンで洗浄した。次いでＴ ｔ Ｃｌ ４
２５ ｍｌを追加して、９０℃で２時間反応させた。上
澄みを除去した後、さらにＴｉＣｌ４を２５ｍ１追加し
て、９０℃で２時間反応させた。反応終了後、ｎ−へブ
タンで洗浄した。洗浄終了後、２−エトキシエチルアセ
テート０．１４ｍ１ （ＩｍＭ）を追加して、９０℃で
２時間反応させた。反応終了後、ヘプタンで洗浄した。Next, 0.55 g of diphenylmethanol was dissolved in 25 ml of toluene, and this was introduced into the flask at 50° C. for 30 minutes, and reacted at 90° C. for 3 hours. After the reaction was completed, it was washed with n-hebutane. Then T t Cl 4
25 ml was added and reacted at 90°C for 2 hours. After removing the supernatant, 25 ml of TiCl4 was added and reacted at 90°C for 2 hours. After the reaction was completed, it was washed with n-hebutane. After the washing was completed, 0.14 ml (ImM) of 2-ethoxyethyl acetate was added and reacted at 90°C for 2 hours. After the reaction was completed, it was washed with heptane.
次いで、ＴｉＣｌ４を０．４３ミリリツトル、（ＣＨ）
Ｃ８ｉ （ＣＨ３）（ＯＣＨ３） ２を１．０６ミ
リリツトル、次いでトリエチルアルミニウム２．４グラ
ムを３０℃条件下に導入して、２時間反応を行なった。Then, add 0.43 ml of TiCl4, (CH)
1.06 ml of C8i (CH3)(OCH3) 2 and then 2.4 g of triethylaluminum were introduced at 30°C, and a reaction was carried out for 2 hours.
反応終了後、ヘプタン洗浄を行なって、目的の固体成分
（Ｉ）を得た。固体成分（Ｉ）中のチタン含量は、４．
３６重量％であった。After the reaction was completed, washing with heptane was performed to obtain the target solid component (I). The titanium content in solid component (I) is 4.
It was 36% by weight.
上記固体成分４ｇを用いる以外は全て実施例１と同一条
件で予備重合を実施した。得られた重合用触媒成分４グ
ラム上にはポリマーが４．ＯＯグラムあり、全体で８．
０グラム回収された。Prepolymerization was carried out under the same conditions as in Example 1 except that 4 g of the above solid component was used. On 4 grams of the polymerization catalyst component obtained, 4.0 g of polymer was placed. OOgram included, total 8.
0 grams recovered.
上記の重合用触媒成分を用いる以外は全て実施例、１と
同一条件で重合を実施した。結果は、表−３に示す通り
であった。Polymerization was carried out under the same conditions as in Example 1 except for using the above polymerization catalyst component. The results were as shown in Table-3.
実施例９
〔固体成分（Ｉ）の製造〕
充分に窒素置換したフラスコに脱水および脱酸素したｎ
−へブタン２００ミリリツトルを導入し、次いでＭｇＣ
１つを０．４モル、
Ｔ ｌ（０−ｎ Ｃ４Ｈ９） ４を０．８モル導入し、
９５℃で２時間反応させた。反応終了後、４０℃に温度
を下げ、次いでメチルヒドロボリンロキサン（２０セン
チストークスのもの）を４８ミリリツトル導入し、３時
間反応させた。生成した固体成分をｎ−へブタンで洗浄
した。Example 9 [Production of solid component (I)] Dehydrated and deoxidized n was placed in a flask that was sufficiently purged with nitrogen.
- 200 ml of hebutane is introduced, then MgC
Introducing 0.4 mol of 1 and 0.8 mol of Tl(0-n C4H9)4,
The reaction was carried out at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 48 milliliters of methylhydroborinoxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane.
ついで充分に窒素置換したフラスコに上記と同様に精製
したローへブタンを５０ミリリットル導人し、上記で合
成した固体成分をＭ ｇ原子換算で０．２４モル導入し
た。Next, 50 ml of rhohebutane purified in the same manner as above was introduced into a flask which had been sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms.
次いでＳ ＩＣｌ ４ ０− ９６モルを１５℃で一括
でフィードして、１５℃で２時間反応させた。Next, 0-96 mol of SICl4 was fed all at once at 15°C, and the mixture was reacted at 15°C for 2 hours.
次いで全体を９０℃に昇温させて、さらに２時間反応さ
せた。反応終了後、ｎ−へブタンで洗浄した。次いで第
三ブチルメチルジメトキシシランを０．０６モルフィー
ドし、１５℃ １時間反応させた。反応終了後ｎ−へブ
タン洗浄を行なって、固体成分（Ｉ）を得た。この固体
成分中には、チタンが４．８８重量％、第三ブチルメチ
ルジメトキシシランが１５．４重量％含まれていた。Then, the temperature of the whole was raised to 90°C, and the reaction was continued for an additional 2 hours. After the reaction was completed, it was washed with n-hebutane. Next, 0.06 mol of tert-butylmethyldimethoxysilane was fed, and the mixture was reacted at 15°C for 1 hour. After completion of the reaction, washing with n-hebutane was performed to obtain solid component (I). This solid component contained 4.88% by weight of titanium and 15.4% by weight of tert-butylmethyldimethoxysilane.
充分に窒素置換した内容積１．５リツトルの攪拌式オー
トクレーブに、脱水および脱酸素した「】−へブタン４
００ｍ１を導入し、系内を１５°Ｃに冷却した後、成分
（ＩＩ）としてｎ−ブチルリチウム０．８ｇ、上記固体
成分（Ｉ）を１２グラム導入し、プロピレンを１６グラ
ム／Ｈｒて０． ５時間フィードして、予備重合を行な
った。プロピレンフィード終了後、１０分間桟正単合を
行なった。In a stirred autoclave with an internal volume of 1.5 liters that was sufficiently purged with nitrogen, dehydrated and deoxygenated
After cooling the system to 15°C, 0.8 g of n-butyllithium as component (II) and 12 g of the above solid component (I) were introduced, and propylene was added at 16 g/Hr to 0.0 ml. Preliminary polymerization was carried out by feeding for 5 hours. After the propylene feed was completed, straight monomerization was carried out for 10 minutes.
終了後、ｎ−へブタンで２回洗浄して、目的の重合用触
媒成分を得た。この重合用触媒成分１２グラム上には、
７．２グラムのポリマーがあり、全体で１９．２グラム
回収された。After completion, the reaction mixture was washed twice with n-hebutane to obtain the desired polymerization catalyst component. On 12 grams of this polymerization catalyst component,
There were 7.2 grams of polymer, with a total of 19.2 grams recovered.
上記重合用触媒成分を２５ミリグラム（４０ミリグラム
ポリマー含有）、トリエチルアルミニウム１２５ミリグ
ラムおよび水素を２００ミリリツトル導入する以外は全
て実施例１と同一条件で重合を行なった。結果は、表−
３に示す通りであった。Polymerization was carried out under the same conditions as in Example 1, except that 25 milligrams of the above polymerization catalyst component (containing 40 milligrams of polymer), 125 milligrams of triethylaluminum, and 200 milliliters of hydrogen were introduced. The results are shown in table-
It was as shown in 3.
これらの表でＥＰＲ部の推定Ｍ Ｆ Ｒは、次式により
求めｔ二ものである。In these tables, the estimated MFR of the EPR section is calculated using the following equation.
ＥＰＲ推定ＭＦＲ−
Ａは生成ポリマー瓜、ａｌは前段重合量（フィードモノ
マー量、溶剤溶解量、および気相部残存量から推定）、
ａ２は後段重合量（推定）、ＭＦＲ−Ｐは生成ポリマー
のＭＦＲ，ＭＦＲ−１は前段終了後の中間サンプルの〜
ＩＦＲ１をそれぞれ示す。EPR estimated MFR-A is the produced polymer, al is the amount of polymerization in the previous stage (estimated from the amount of feed monomer, the amount of solvent dissolved, and the amount remaining in the gas phase),
a2 is the amount of post-stage polymerization (estimated), MFR-P is the MFR of the produced polymer, and MFR-1 is ~ of the intermediate sample after the completion of the first stage.
IFR1 is shown respectively.
／ ／ ／/ / /
第１図は、チーグラー触媒に関する本発明の技術内容の
理解を助けるためのものである。
出願人代理人 佐 藤 −雄FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts. Applicant's agent Mr. Sato
Claims (1)
りさらに成分（Ｃ）よりなる固体成分（ I ）に成分（
II）の共存下にα−オレフィンを接触させて、このα−
オレフィンを固体成分（ I ）１グラムに対して０．０
１〜１００グラム重合させて得たことを特徴とする、α
−オレフィン重合用触媒成分。 ￥固体成分（ I ）￥ ￥成分（Ａ）￥ チタン、マグネシウムおよびハロゲンを必須として含有
する固体成分。 ￥成分（Ｂ）￥ Ｒ＾１Ｒ＾２＿３＿−＿ｎＳｉ（ＯＲ＾３）＿ｎ（但し
、Ｒ＾１は分岐鎖状炭化水素残基を、Ｒ＾２はＲ＾１と
同一かもしくは異なる炭化水素残基を、Ｒ＾３は炭化水
素残基を、ｎは１≦ｎ≦３の数を、それぞれ示す。） で表わされるケイ素化合物。 ￥成分（Ｃ）￥ 周期律表第 I 〜III族金属の有機金属化合物。 ￥成分（II）￥ 有機マグネシウムあるいは有機リチウム化合物。[Scope of Claims] 1. A solid component (I) consisting of the following components (A) and (B) and optionally further component (C) is added to the component (I).
II), the α-olefin is brought into contact with the α-olefin, and the α-olefin is
0.0 olefin per gram of solid component (I)
α, characterized by being obtained by polymerizing 1 to 100 grams
- Catalyst component for olefin polymerization. ￥Solid component (I)￥￥Component (A)￥ A solid component that essentially contains titanium, magnesium, and halogen. ¥Component (B)¥ R^1R^2_3_-_nSi(OR^3)_n (where, R^1 is a branched hydrocarbon residue, and R^2 is a hydrocarbon residue that is the same as or different from R^1. group, R^3 represents a hydrocarbon residue, and n represents a number of 1≦n≦3. ¥Component (C)¥ Organometallic compound of metals from groups I to III of the periodic table. ￥Component (II)￥ Organomagnesium or organolithium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63270528A JP2656573B2 (en) | 1988-10-26 | 1988-10-26 | Catalyst component for α-olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63270528A JP2656573B2 (en) | 1988-10-26 | 1988-10-26 | Catalyst component for α-olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02117905A true JPH02117905A (en) | 1990-05-02 |
| JP2656573B2 JP2656573B2 (en) | 1997-09-24 |
Family
ID=17487475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63270528A Expired - Lifetime JP2656573B2 (en) | 1988-10-26 | 1988-10-26 | Catalyst component for α-olefin polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2656573B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7238758B2 (en) | 2002-08-19 | 2007-07-03 | Ube Industries, Ltd. | Catalysts for polymerization or copolymerization of α-olefins, catalyst components thereof, and processes for polymerization of α-olefins with the catalysts |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01165608A (en) * | 1987-12-22 | 1989-06-29 | Tosoh Corp | Improved production of stereoregular polyolefin |
-
1988
- 1988-10-26 JP JP63270528A patent/JP2656573B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01165608A (en) * | 1987-12-22 | 1989-06-29 | Tosoh Corp | Improved production of stereoregular polyolefin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7238758B2 (en) | 2002-08-19 | 2007-07-03 | Ube Industries, Ltd. | Catalysts for polymerization or copolymerization of α-olefins, catalyst components thereof, and processes for polymerization of α-olefins with the catalysts |
| EP3020738A2 (en) | 2002-08-19 | 2016-05-18 | Toho Titanium Co., Ltd. | Catalyst and catalyst component thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2656573B2 (en) | 1997-09-24 |
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