JPH0757772B2 - Method for producing ethylene-based polymer - Google Patents
Method for producing ethylene-based polymerInfo
- Publication number
- JPH0757772B2 JPH0757772B2 JP22741588A JP22741588A JPH0757772B2 JP H0757772 B2 JPH0757772 B2 JP H0757772B2 JP 22741588 A JP22741588 A JP 22741588A JP 22741588 A JP22741588 A JP 22741588A JP H0757772 B2 JPH0757772 B2 JP H0757772B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- compound
- mol
- reaction product
- general formula
- 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.)
- Expired - Fee Related
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 51
- 239000005977 Ethylene Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920000642 polymer Polymers 0.000 title claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 41
- -1 Silicon halide compound Chemical class 0.000 claims description 40
- 150000002430 hydrocarbons Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 25
- 150000003623 transition metal compounds Chemical class 0.000 claims description 25
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 17
- 239000007818 Grignard reagent Substances 0.000 claims description 15
- 150000004795 grignard reagents Chemical class 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000003682 vanadium compounds Chemical class 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 150000003755 zirconium compounds Chemical class 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012434 nucleophilic reagent Substances 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 150000004703 alkoxides Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims 1
- 229920005601 base polymer Polymers 0.000 claims 1
- 150000001923 cyclic compounds Chemical class 0.000 claims 1
- 150000002901 organomagnesium compounds Chemical group 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 238000006116 polymerization reaction Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229910002056 binary alloy Inorganic materials 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002002 slurry 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IYTXKIXETAELAV-UHFFFAOYSA-N Nonan-3-one Chemical compound CCCCCCC(=O)CC IYTXKIXETAELAV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- ZKUUVVYMPUDTGJ-UHFFFAOYSA-N methyl 5-hydroxy-4-methoxy-2-nitrobenzoate Chemical compound COC(=O)C1=CC(O)=C(OC)C=C1[N+]([O-])=O ZKUUVVYMPUDTGJ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- VLQZJOLYNOGECD-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O1 VLQZJOLYNOGECD-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-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
- JGEGJYXHCFUMJF-UHFFFAOYSA-N 4-methylpentanal Chemical compound CC(C)CCC=O JGEGJYXHCFUMJF-UHFFFAOYSA-N 0.000 description 1
- OLIBVNMJDNNSKI-UHFFFAOYSA-N CC(C)(C)[Mg] Chemical compound CC(C)(C)[Mg] OLIBVNMJDNNSKI-UHFFFAOYSA-N 0.000 description 1
- ABXKXVWOKXSBNR-UHFFFAOYSA-N CCC[Mg]CCC Chemical compound CCC[Mg]CCC ABXKXVWOKXSBNR-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000003935 benzaldehydes Chemical class 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- SXOZDDAFVJANJP-UHFFFAOYSA-N cyclodecanone Chemical compound O=C1CCCCCCCCC1 SXOZDDAFVJANJP-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LVCMXMSJOUJZFC-UHFFFAOYSA-N diphenyl(silyloxy)silane Chemical compound C=1C=CC=CC=1[SiH](O[SiH3])C1=CC=CC=C1 LVCMXMSJOUJZFC-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- WTJKUFMLQFLJOT-UHFFFAOYSA-N heptadecan-9-one Chemical compound CCCCCCCCC(=O)CCCCCCCC WTJKUFMLQFLJOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-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
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- KMYFNYFIPIGQQZ-UHFFFAOYSA-N magnesium;octane Chemical compound [Mg+2].CCCCCCC[CH2-].CCCCCCC[CH2-] KMYFNYFIPIGQQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecanal Chemical class CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- CDDLDLRMXLVXOP-UHFFFAOYSA-N triethyl(ethylsilyloxy)silane Chemical compound CC[SiH2]O[Si](CC)(CC)CC CDDLDLRMXLVXOP-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は新規な触媒系の存在下にオレフィン類を重合
し、とくには、インフレーション成形、中空成形の如き
成形用途に適した溶融張力（メルトテンション）が大
で、かつ溶融弾性（ダイスウェル比）の大きいオレフィ
ン重合体を優れた触媒効率をもって再現性よく製造する
ことが可能なオレフィン類の重合法に関する。Detailed Description of the Invention (a) Field of Industrial Application The present invention polymerizes olefins in the presence of a novel catalyst system, and in particular, melt tension suitable for molding applications such as inflation molding and blow molding ( The present invention relates to a method for polymerizing olefins which has a high melt tension and a large melt elasticity (die swell ratio) and which can be reproducibly produced with excellent catalytic efficiency.
なお、本発明において重合という語は、単独重合のみな
らず共重合を含めた意味で用い、同様に重合体という語
は、単独重合体のみならず共重合体を含めた意味で用い
る。In the present invention, the term “polymerization” is used to include not only homopolymerization but also copolymerization, and similarly, the term “polymer” is used to include not only homopolymer but also copolymer.
（ロ） 従来の技術 本発明者らは、先にエチレン系重合体の各種用途分野、
特に押出成形および中空成形などの溶融成形の分野に適
したポリエチレンの製造方法として、特願昭60−77963
号および特願昭62−146065号を提案した。(B) Conventional Technology The inventors of the present invention have previously described various fields of use of ethylene polymers,
Particularly, as a method for producing polyethylene suitable for the field of melt molding such as extrusion molding and blow molding, Japanese Patent Application No. 60-77963
And Japanese Patent Application No. 62-146065.
しかし、これらの方法では触媒活性は比較的高いが、得
られるエチレン系重合体の溶融張力および溶融弾性に劣
り、その結果特に中空成形の分野においては成形時にド
ローダウンの現象が起こり易かったり、複雑な形状に成
形するときには金型形状に適合し難い等、その改善が強
く要望されている。However, in these methods, the catalytic activity is relatively high, but the melt tension and melt elasticity of the resulting ethylene polymer are inferior, and as a result, the phenomenon of drawdown easily occurs during molding, especially in the field of hollow molding, and it is complicated. There is a strong demand for improvement such that it is difficult to conform to the shape of the mold when it is molded into a different shape.
（ハ） 発明が解決しようとする問題点 オレフィン重合体は、種々の成形方法により成形され、
多方面の用途に供されている。これら成形方法や用途に
応じて、オレフィン重合体に要求される特性も異なって
くる。例えばインフレーションフィルムを高速で成形し
ようとする場合、バブルのゆれがなく、安定して高速成
形を行なうためには、オレフィン重合体として分子量の
割には溶融張力の大きいものを選択しなければならな
い。同様の特性が中空成形、とくに大型容器の中空成形
におけるたれ下りを防止するために必要である。大型容
器の中空成形においてはまた、複雑な形状に成形すると
きには、溶融弾性がある程度大きい方が金型形状に適合
し易く、良好な形成品が得られることが多い。(C) Problems to be Solved by the Invention The olefin polymer is molded by various molding methods,
It is used for various purposes. The properties required of the olefin polymer also differ depending on these molding methods and applications. For example, when an inflation film is to be formed at a high speed, it is necessary to select an olefin polymer having a large melt tension relative to its molecular weight in order to perform stable high speed formation without bubble fluctuation. Similar properties are required to prevent sagging in blow molding, especially in large containers. In the hollow molding of a large-sized container, when molding into a complicated shape, it is easy to conform to the shape of the mold if the melt elasticity is large to some extent, and a good molded product is often obtained.
本発明者らは、触媒活性が高く、かつ溶融張力および溶
融弾性が大きいポリオレフィン、特にエチレン系重合体
を容易に得ることが可能な触媒系について鋭意検討を行
った結果、特定の触媒成分〔Ｃ〕と有機アルミニウム化
合物〔Ｄ〕との組合わせを満足する触媒を用いることに
より、前記従来技術の欠点が改善できることを発見し
た。The present inventors have conducted diligent studies on a catalyst system which has a high catalytic activity and a large melt tension and melt elasticity, particularly an ethylene-based polymer. As a result, the specific catalyst component [C It was discovered that the drawbacks of the prior art can be improved by using a catalyst satisfying the combination of the above] and the organoaluminum compound [D].
（ニ） 問題点を解決するための手段 本発明者らは、上述の問題点を特願昭60−77963号およ
び特願昭62−146065号を基礎とし、触媒の調製法と重合
体の諸物性との関連を鋭意追求し本発明を完成した。(D) Means for Solving Problems Based on the above-mentioned problems based on Japanese Patent Application No. 60-77963 and Japanese Patent Application No. 62-146065, the present inventors have prepared a catalyst preparation method and various polymers. The present invention has been completed by earnestly pursuing the relationship with physical properties.
即ち、本発明者らは、 下記〔Ｉ〕〜〔III〕の成分 〔Ｉ〕ヒドロポリシロキサンとグリニヤール試薬との反
応で得られる反応生成物〔Ａ〕、または反応生成物
〔Ａ〕にさらにアルコール、アルデヒドおよびケトンよ
り選ばれる少くとも一種類以上の親核的試薬を反応させ
て得られる反応生成物〔Ｂ〕 〔II〕遷移金属化合物 〔III〕ハロゲン化ケイ素化合物、および／またはハロ
ゲン化有機アルミニウム化合物 を接触させて得られる触媒成分〔Ｃ〕と有機アルミニウ
ム化合物〔Ｄ〕を用いて、エチレンまたはエチレンと他
のα−オレフィンを重合、もしくは共重合する方法にお
いて、成分〔II〕として、（１）一般式Ti（OR7）LX4-L
（R7はC1〜C12の炭化水素基、Ｘはハロゲン原子、かつ
０≦ｌ≦４）で表わされるチタン化合物、（２）一般式
VO（OR8）mX3-m（R8はC1〜C12の炭化水素基、Ｘはハロ
ゲン原子、かつ０≦ｍ≦３）またはVX4（Ｘはハロゲン
原子）で表わされるバナジウム化合物、および（３）一
般式Zr（OR9）nX4-n（R9はC1〜C12の炭化水素基、Ｘは
ハロゲン原子、かつ０≦ｎ≦４）で表わされるジルコニ
ウム化合物の混合物あるいはこれらのこれらを特定の順
序で添加することにより、高い触媒活性を保持し、か
つ、溶融張力および溶融弾性のいずれをも増大せしめる
ことを見い出したものである。That is, the present inventors have found that the reaction product [A] obtained by the reaction of the following components [I] to [III] [I] hydropolysiloxane with a Grignard reagent, or the reaction product [A] with an alcohol Reaction product [B] [II] transition metal compound [III] silicon halide compound, and / or organoaluminum halide obtained by reacting at least one or more nucleophilic reagents selected from aldehydes, aldehydes and ketones. In the method of polymerizing or copolymerizing ethylene or ethylene with another α-olefin using the catalyst component [C] obtained by contacting the compound and the organoaluminum compound [D], the component [II] is ) General formula Ti (OR 7 ) L X 4-L
(R 7 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ l ≦ 4), a titanium compound represented by the formula (2).
Vanadium compound represented by VO (OR 8 ) m X 3-m (R 8 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ m ≦ 3) or VX 4 (X is a halogen atom) And (3) a mixture of zirconium compounds represented by the general formula Zr (OR 9 ) n X 4-n (R 9 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ n ≦ 4) Alternatively, it has been found that by adding these in a specific order, it is possible to maintain high catalytic activity and increase both melt tension and melt elasticity.
本発明の生成物〔Ａ〕の製造に使用されるヒドロポリシ
ロキサンは一般式 （R1はC1〜C12の炭化水素基又はアルコキシ基、あるい
はフェノキシ基、ａは0,1,または２、ｂは1,2,または３
で、かつａ＋ｂ≦３）で表わされる構造単位をもつ鎖状
または環状の含ケイ素化合物である。ヒドロポリシロキ
サンの重合度は特に限定する必要はないが液状低重合物
から25℃における粘度が100,000センチストークスにい
たる種々の重合度のグリース状ないしはワックス状のも
のまで使用できる。また完全に固体状のものであっても
よい。ヒドロポリシロキサンの末端構造は特に大きな影
響を及ぼさず不活性基、例えばトリアルキルシリル基で
封鎖されていてもさしつかえない。The hydropolysiloxane used in the production of the product [A] of the present invention has the general formula (R 1 is a C 1 -C 12 hydrocarbon group, an alkoxy group, or a phenoxy group, a is 0, 1, or 2, b is 1, 2, or 3
And a chain-like or cyclic silicon-containing compound having a structural unit represented by a + b ≦ 3). The degree of polymerization of the hydropolysiloxane is not particularly limited, but it is possible to use from a liquid low polymer to a grease-like or wax-like one having various degrees of polymerization having a viscosity at 25 ° C. of 100,000 centistokes. It may be completely solid. The terminal structure of the hydropolysiloxane does not have a great influence and may be blocked with an inert group such as a trialkylsilyl group.
本発明において通常用いられているヒドロポリシロキサ
ンはテトラメチルジシロキサン、テトラエチルジシロキ
サン、ジフェニルジシロキサン、トリメチルシクロトリ
シロキサン、テトラメチルシクロテトラシロキサン、メ
チルヒドロポリシロキサン、フェニルヒドロポリシロキ
サン、エトオキシヒドロポリシロキサン、シクロオクチ
ルヒドロポリシロキサン、クロルフェニルヒドロポリシ
ロキサン等が挙げられる。The hydropolysiloxanes usually used in the present invention are tetramethyldisiloxane, tetraethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, etoxyhydropolysiloxane. Examples thereof include siloxane, cyclooctylhydropolysiloxane, chlorophenylhydropolysiloxane, and the like.
本発明において使用されるグリニヤール試薬は含ハロゲ
ン有機化合物と金属マグネシウムとの反応で得られるも
のであって、 一般式 （MgR2 2）ｐ・（MgR2X）ｑ （R2はC1〜C12の炭化水素基、Ｘはハロゲン原子、ま
た、ｐおよびｑは０〜１の数を表わし、ｐ＋ｑ＝１） で示される化合物、およびそのエーテル錯化合物、又は
それらの混合物である。例えばｐ＝0,q＝１の場合は、
いわゆる狭義のグリニヤール試薬であってMgR2Xであ
る。ｐ＝1,q＝０の場合はMgR2 2で示されるジヒドロカル
ビルマグネシウムである。このほか、p,qが中間の種々
の値をとった場合は（MgR2 2）ｐ・（MgR2X）ｑで示され
る有機ハロゲン化マグネシウムである。さらに、これら
のすべてについて、そのエーテル錯化合物又はこれらの
混合物等のいずれであってもよい。さらには又、粘度調
整剤として他の有機金属化合物を少量含むものであって
も何らさしつかえない。The Grignard reagent used in the present invention is obtained by reacting a halogen-containing organic compound with metallic magnesium, and has the general formula (MgR 2 2 ) p · (MgR 2 X) q (R 2 is C 1 to C 12 hydrocarbon groups, X is a halogen atom, p and q are numbers of 0 to 1, and p + q = 1), a compound thereof, an ether complex compound thereof, or a mixture thereof. For example, when p = 0 and q = 1,
It is a so-called Grignard reagent in a narrow sense and is MgR 2 X. For p = 1, q = 0 is a dihydrocarbyl magnesium represented by MgR 2 2. In addition, when p and q take various intermediate values, it is an organic magnesium halide represented by (MgR 2 2 ) p · (MgR 2 X) q . Further, all of them may be the ether complex compound or a mixture thereof. Furthermore, it does not matter even if it contains a small amount of other organometallic compound as a viscosity modifier.
上記グリニヤール試薬は公知の方法で、ジエチルエーテ
ル、ジブチルエーテル、テトラヒドロフラン等のエーテ
ル系溶媒中、またはヘプタン、オクタン、ベンゼン、ト
ルエン等の炭化水素系溶媒中で、適当量のエーテル、ア
ミン等の錯化剤の存在下において容易に合成される。The Grignard reagent is a known method, in an ether solvent such as diethyl ether, dibutyl ether or tetrahydrofuran, or in a hydrocarbon solvent such as heptane, octane, benzene or toluene, a suitable amount of ether, amine or the like is complexed. Easily synthesized in the presence of the agent.
一般式MgR2Xの具体例としては、メチルマグネシウムク
ロライド、エチルマグネシウムクロライド、エチルマグ
ネシウムブロマイド、ｎ−プロピルマグネシウムクロラ
イド、ｎ−プロピルマグネシウムクロライド、ｎ−ブチ
ルマグネシウムクロライド、tert−ブチルマグネシウム
クロライド、ｎ−オクチルマグネシウムクロライド、フ
ェニルマグネシウムクロライド、等が挙げられる。Specific examples of the general formula MgR 2 X include methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, n-propyl magnesium chloride, n-propyl magnesium chloride, n-butyl magnesium chloride, tert-butyl magnesium chloride, n-octyl. Magnesium chloride, phenyl magnesium chloride and the like can be mentioned.
また、一般式MgR2 2の具体例としては、ジエチルマグネ
シウム、ジ−ｎ−プロピルマグネシウム、ｎ−ブチルエ
チルマグネシウム、ジ−ｎ−ブチルマグネシウム、ジ−
tert−ブチルマグネシウム、ジ−ｎ−オクチルマグネシ
ウム、ジフェニルマグネシウム等が挙げられる。Specific examples of the general formula MgR 2 2, diethyl magnesium, di -n- propyl magnesium, n- butyl ethyl magnesium, di -n- butyl magnesium, di -
Examples include tert-butyl magnesium, di-n-octyl magnesium, diphenyl magnesium and the like.
ヒドロポリシロキサンとグリニヤール試薬とを反応させ
る方法としては次のような方法がとられる。適当な溶媒
中で合成したグリニヤール試薬に対し、攪拌しながらヒ
ドロポリシロキサンを少しずつ添加し（逆にヒドロポリ
シロキサンにグリニヤール試薬を添加してもよい。）、
全量添加後加熱して所定時間反応させる。あるいはグリ
ニヤール試薬を合成するときと同じように適当な溶媒中
に金属マグネシウムを分散させ、攪拌しながら有機ハロ
ゲン化合物とヒドロポリシロキサンの混合物を所定の温
度で滴下した後、所定時間反応させても良い。この反応
は室温で激しい発熱を伴って進行するがその反応を完結
するために20〜100℃特に30〜80℃で１〜５時間加熱す
ることが好ましい。100℃以上ではSi−Ｈ結合が分解し
好ましくない。ヒドロポリシロキサンとグリニヤール試
薬との仕込みは、mol比でMgR2:Siとして1:1〜20、特に
1:1〜５が好ましい。As a method for reacting the hydropolysiloxane with the Grignard reagent, the following method is used. Hydropolysiloxane is added little by little to the Grignard reagent synthesized in an appropriate solvent while stirring (conversely, the Grignard reagent may be added to the hydropolysiloxane).
After adding the whole amount, heat and react for a predetermined time. Alternatively, as in the case of synthesizing a Grignard reagent, metallic magnesium may be dispersed in a suitable solvent, and a mixture of an organic halogen compound and hydropolysiloxane may be added dropwise at a predetermined temperature with stirring and then reacted for a predetermined time. . This reaction proceeds at room temperature with intense heat generation, but in order to complete the reaction, it is preferable to heat at 20 to 100 ° C, particularly 30 to 80 ° C for 1 to 5 hours. Above 100 ° C, the Si-H bond is decomposed, which is not preferable. The hydropolysiloxane and the Grignard reagent were charged at a molar ratio of MgR 2 : Si of 1: 1 to 20, particularly
1: 1-5 is preferable.
反応生成物〔Ａ〕を得る反応は、ヒドロポリシロキサン
としてメチルヒドロポリシロキサンを用いた場合、次の
ように進行することが知られている（特公昭52−13232
号）。It is known that the reaction to obtain the reaction product [A] proceeds as follows when methylhydropolysiloxane is used as the hydropolysiloxane (Japanese Patent Publication No. 52-13232).
issue).
反応生成物〔Ａ〕はテトラヒドロフラン中で合成したグ
リニヤール試薬を使用した場合には溶液で得られ、ジエ
チルエーテル等の鎖状のエーテル化合物を使用した場合
には、懸濁状で得られる。 The reaction product [A] is obtained as a solution when the Grignard reagent synthesized in tetrahydrofuran is used, and as a suspension when a chain ether compound such as diethyl ether is used.
本発明の反応生成物〔Ｂ〕を得るために使用される親核
的試薬は一般式R6OH（R6はC1〜C13の炭化水素基）で示
されるアルコールである。The nucleophilic reagent used to obtain the reaction product [B] of the present invention is an alcohol represented by the general formula R 6 OH (R 6 is a C 1 to C 13 hydrocarbon group).
さらに一般式R3COR4（R3,R4はそれぞれ水素原子またはC
1〜C17の炭化水素基を表わし、相互に同じでも異なって
いてもよい）、および一般式 （R5はC3〜C17の２価の炭化水素基）で示されるアルデ
ヒド、またはケトンが使用できる。Further, the general formula R 3 COR 4 (R 3 and R 4 are hydrogen atoms or C
1 to C 17 hydrocarbon group, which may be the same or different from each other), and a general formula An aldehyde or a ketone represented by (R 5 is a C 3 -C 17 divalent hydrocarbon group) can be used.
アルコールの具体例としては、メタノール、エタノー
ル、ｎ−プロパノール、イソプロパノール、ｎ−ブタノ
ール、sec−ブタノール、２−エチルブタノール、ｎ−
ヘプタノール、ｎ−オクタノール、２−エチルヘキサノ
ール、ｎ−デカノール、ステアリルアルコール、シクロ
ヘキサノール、ベンジルアルコール、フェノール、クレ
ゾール等が挙げられる。Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, 2-ethylbutanol, n-.
Examples thereof include heptanol, n-octanol, 2-ethylhexanol, n-decanol, stearyl alcohol, cyclohexanol, benzyl alcohol, phenol and cresol.
アルデヒドの具体例としては、ホルムアルデヒド、アセ
トアルデヒド、ｎ−プロピルアルデヒド、ｎ−ブチルア
ルデヒド、イソブチルアルデヒド、ｎ−バレルアルデヒ
ド、トリメチルアセトアルデヒド、イソヘキサアルデヒ
ド、ｎ−オクチルアルデヒド、２−エチルヘキサアルデ
ヒド、ｎ−デカアルデヒド、トリデカアルデヒド、ステ
アルアルデヒド、ベンズアルデヒド、等が挙げられる。Specific examples of the aldehyde include formaldehyde, acetaldehyde, n-propylaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, trimethylacetaldehyde, isohexaldehyde, n-octylaldehyde, 2-ethylhexaldehyde, n-deca. Aldehydes, tridecaaldehydes, stearaldehydes, benzaldehydes and the like can be mentioned.
ケトンの具体例としては、アセトン、メチルエチルケト
ン、ジエチルケトン、メチルイソブチルケトン、ジ−ｎ
−ブチルケトン、ジ−ｎ−オクチルケトン、エチルヘキ
シルケトン、ベンゾフェノン、シクロブタノン、シクロ
ヘキサノン、シクロデカノン等が挙げられる。Specific examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di-n.
-Butyl ketone, di-n-octyl ketone, ethylhexyl ketone, benzophenone, cyclobutanone, cyclohexanone, cyclodecanone and the like can be mentioned.
これら親核的試薬は単独または２種類以上の混合物で、
反応生成物〔Ａ〕との反応に使用される。These nucleophiles may be used alone or as a mixture of two or more kinds,
Used in the reaction with the reaction product [A].
本発明に使用される反応生成物〔Ｂ〕を得るための反応
は、反応生成物〔Ａ〕に親核的試薬を攪拌下に滴下する
ことによって行われる。The reaction for obtaining the reaction product [B] used in the present invention is carried out by dropwise adding a nucleophilic reagent to the reaction product [A] with stirring.
反応は発熱を伴って室温で進行する。滴下終了後、反応
を完結するため、30〜100℃で１〜５時間反応させるこ
とが好ましい。この反応は所望の不活性炭化水素溶媒を
あらかじめ反応生成物〔Ａ〕に添加し、希釈した状態で
行うこともできる。The reaction proceeds exothermically at room temperature. After completion of the dropping, the reaction is preferably completed at 30 to 100 ° C. for 1 to 5 hours in order to complete the reaction. This reaction can be carried out in a state where the desired inert hydrocarbon solvent is added to the reaction product [A] in advance and diluted.
反応生成物〔Ｂ〕を得るために用いられる、親核的試薬
の使用量は反応生成物〔Ａ〕中のSi−Ｈ基1mol当り1.0m
ol以下であり、かつ、反応生成物〔Ａ〕中のマグネシウ
ム1mol当り0.5mol以上が好ましい。親核的試薬の使用量
が反応生成物〔Ａ〕中のマグネシウム1molに対して0.5m
ol以下では、グリニヤール試薬の溶媒であるエーテル化
合物の除去が不十分となり反応生成物が粘着性を帯び
る。The amount of the nucleophilic reagent used to obtain the reaction product [B] is 1.0 m per 1 mol of Si-H group in the reaction product [A].
It is preferably ol or less and 0.5 mol or more per 1 mol of magnesium in the reaction product [A]. The amount of the nucleophilic reagent used is 0.5 m with respect to 1 mol of magnesium in the reaction product [A].
If it is ol or less, the ether compound, which is the solvent of the Grignard reagent, is not sufficiently removed, and the reaction product becomes sticky.
また、使用量を反応生成物〔Ａ〕中のSi−Ｈ基1mol当り
1.0mol以上にしても触媒活性の低下や、反応生成物
〔Ｂ〕の炭化水素基への溶解度の低下を招く場合があっ
て好ましくない。Also, the amount used is based on 1 mol of Si-H groups in the reaction product [A].
Even if it is 1.0 mol or more, the catalytic activity may be lowered and the solubility of the reaction product [B] in the hydrocarbon group may be lowered, which is not preferable.
反応生成物〔Ａ〕と親核的試薬の反応混合物からグリニ
ヤール試薬の溶媒であるエーテル化合物を除去し、不活
性炭化水素に可溶または懸濁状の反応生成物〔Ｂ〕を得
る方法としては、反応混合物にエーテル化合物より高沸
点の不活性炭化水素を添加し、常圧下または減圧下で蒸
留し、エーテル化合物を留去する方法が好ましい。As a method for removing the ether compound which is the solvent of the Grignard reagent from the reaction mixture of the reaction product [A] and the nucleophilic reagent to obtain a reaction product [B] soluble or suspended in an inert hydrocarbon, It is preferable to add an inert hydrocarbon having a boiling point higher than that of the ether compound to the reaction mixture, distill under normal pressure or under reduced pressure, and distill off the ether compound.
反応生成物〔Ｂ〕が不活性炭化水素に可溶の場合は反応
混合物から直接エーテル化合物を蒸発除去した後、不活
性炭化水素に溶解させる事も可能である。When the reaction product [B] is soluble in an inert hydrocarbon, it is also possible to directly remove the ether compound from the reaction mixture by evaporation and then dissolve it in the inert hydrocarbon.
エーテル化合物留去時の釜温は150℃以下、特に100℃以
下が好ましい。釜温が150℃以上に上昇すると可溶性の
反応生成物〔Ｂ〕より不溶性物質が生成する場合がある
ので好ましくない。The kettle temperature at the time of distilling off the ether compound is preferably 150 ° C. or lower, particularly preferably 100 ° C. or lower. When the kettle temperature rises to 150 ° C. or higher, an insoluble substance may be produced from the soluble reaction product [B], which is not preferable.
反応生成物〔Ｂ〕中のエーテル化合物の残量は触媒活性
と密接な関係があり、少ない程良い。通常反応生成物
〔Ｂ〕中のマグネシウム１グラム原子当り0.4mol以下、
特に0.2mol以下が好ましい。The residual amount of the ether compound in the reaction product [B] is closely related to the catalytic activity, and the smaller the residual amount, the better. Usually 0.4 mol or less per gram atom of magnesium in the reaction product [B],
Particularly, 0.2 mol or less is preferable.
本発明に使用される遷移金属化合物は一般式Ti（OR7）l
X4-l（R7はC1〜C12の炭化水素基、Ｘはハロゲン原子、
かつ０≦ｌ≦４）で表わされるチタン化合物と一般式VO
（OR8）mX3-m（R8はC1〜C12の炭化水素基、Ｘはハロゲ
ン原子、かつ０≦ｍ≦３）、またはVX4（Ｘはハロゲン
原子）で表わされるバナジウム化合物と一般式Zr（O
R9）nX4-n（R9はC1〜C12の炭化水素基、Ｘはハロゲン原
子、かつ０≦ｎ≦４）で表わされるジルコニウム化合物
の混合物あるいはこれらの反応生成物である。これらの
具体例としては、チタン化合物としてTiCl4,TiBr4,Ti
（On−C4H9）3Cl,Ti（On−C4H9）2Cl2,Ti（On−C4H9）C
l3,Ti（Oi−C3H7）3Cl,Ti（On−C4H9）4,Ti（Oi−C
3H7）4,Ti（OC2H5）４等を、バナジウム化合物としてVO
Cl3,VO（OC2H5）Cl2,VO（OC2H5）2Cl,VO（Oi−C3H7）Cl
2,VO（On−C4H9）Cl2,VO（OC2H5）3,VO（On−C4H9）3,V
Cl4等を、ジルコニウム化合物としてZrCl4,Zr（On−C4H
9）4,Zr（OCH3）4,Zr（OC2H5）4,Zr（Oi−C3H7）4,Zr
（On−C3H7）４等を挙げることが出来る。チタン化合物
とバナジウム化合物とジルコニウム化合物は炭化水素溶
媒中、室温で混合するだけでも本発明の目的を達成する
ことは可能であるが、より好ましくは炭化水素溶媒の存
在下に十分反応させた後に使用する方がより安定して触
媒成分〔Ｃ〕を得ることが出来る。The transition metal compound used in the present invention has the general formula Ti (OR 7 ) l
X 4-l (R 7 is a C 1 -C 12 hydrocarbon group, X is a halogen atom,
And a titanium compound represented by 0 ≦ l ≦ 4) and the general formula VO
(OR 8 ) m X 3-m (R 8 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ m ≦ 3), or a vanadium compound represented by VX 4 (X is a halogen atom) And the general formula Zr (O
R 9 ) n X 4-n (R 9 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and a mixture of zirconium compounds represented by 0 ≦ n ≦ 4) or a reaction product thereof. Specific examples of these include titanium compounds such as TiCl 4 , TiBr 4 , and Ti.
(On-C 4 H 9) 3 Cl, Ti (On-C 4 H 9) 2 Cl 2, Ti (On-C 4 H 9) C
l 3, Ti (Oi-C 3 H 7) 3 Cl, Ti (On-C 4 H 9) 4, Ti (Oi-C
3 H 7 ) 4 , Ti (OC 2 H 5 ) 4, etc. as VO as a vanadium compound
Cl 3, VO (OC 2 H 5) Cl 2, VO (OC 2 H 5) 2 Cl, VO (Oi-C 3 H 7) Cl
2, VO (On-C 4 H 9) Cl 2, VO (OC 2 H 5) 3, VO (On-C 4 H 9) 3, V
Cl 4, etc. as ZrCl 4 , Zr (On-C 4 H
9 ) 4 , Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (Oi-C 3 H 7 ) 4 , Zr
(On-C 3 H 7) 4 and the like. The titanium compound, the vanadium compound, and the zirconium compound can achieve the object of the present invention only by mixing them in a hydrocarbon solvent at room temperature, but more preferably they are used after sufficiently reacting in the presence of a hydrocarbon solvent. It is possible to more stably obtain the catalyst component [C].
それぞれの反応成分の反応割合は、チタン化合物１モル
に対し、通常、バナジウム化合物は、0.1〜10モル、ジ
ルコニウム化合物は、0.1〜10モルであり、バナジウム
化合物が0.5〜5.0モルおよびジルコニウム化合物が0.5
〜5.0モルが好適範囲である。反応温度は一般に200℃以
下であり、20〜150℃が好ましい。この反応は不活性溶
媒の不存在下で実施することもできるが、反応を均一に
行なわしめるために、通常、ｎ−ヘキサン、ｎ−ヘプタ
ン、デカリン、ベンゼンおよびトルエンのごとき不活性
溶媒中で行なうことが望ましい。反応時間は、反応温
度、各成分の種類および反応割合ならびに不活性溶媒を
使用した場合、溶媒に対する各反応成分の濃度により異
なるが、一般には、15分〜５時間で充分である。The reaction ratio of each reaction component is usually 0.1 to 10 mol for the vanadium compound, 0.1 to 10 mol for the zirconium compound, 0.5 to 5.0 mol for the vanadium compound and 0.5 for the zirconium compound, relative to 1 mol of the titanium compound.
The preferred range is ˜5.0 mol. The reaction temperature is generally 200 ° C or lower, preferably 20 to 150 ° C. This reaction can be carried out in the absence of an inert solvent, but in order to carry out the reaction uniformly, it is usually carried out in an inert solvent such as n-hexane, n-heptane, decalin, benzene and toluene. Is desirable. The reaction time varies depending on the reaction temperature, the type and reaction ratio of each component, and the concentration of each reaction component with respect to the solvent when an inert solvent is used, but 15 minutes to 5 hours is generally sufficient.
又、反応生成物〔Ａ〕または反応生成物〔Ｂ〕と遷移金
属化合物の配合割合について述べると、反応生成物
〔Ａ〕または反応生成物〔Ｂ〕中のMg1モルに対し、遷
移金属化合物の総和が、0.01〜１モルであり、0.05〜0.
5モルが好適範囲である。Further, the mixing ratio of the reaction product [A] or the reaction product [B] and the transition metal compound will be described. To 1 mol of Mg in the reaction product [A] or the reaction product [B], the transition metal compound The total sum is 0.01 to 1 mol and 0.05 to 0.
5 mol is the preferred range.
本発明の触媒成分〔Ｃ〕の調製に使用されるハロゲン化
ケイ素化合物は一般式R10 rSiX4-r（R10は水素原子また
はC1〜C8の炭化水素基、Ｘはハロゲン原子、かつ０≦ｒ
≦３）で表わされる化合物である。その具体例として
は、SiCl4,SiBr4,HSiCl3,CH3SiCl3,C2H5SiCl3,n−C3H7S
iCl3,C6H5SiCl3,（CH3）2SiCl2,（C2H5）2SiCl2および
（CH3）3SiCl等を挙げる事が出来る。The silicon halide compound used in the preparation of the catalyst component [C] of the present invention has the general formula R 10 r SiX 4-r (R 10 is a hydrogen atom or a C 1 to C 8 hydrocarbon group, X is a halogen atom, And 0 ≦ r
It is a compound represented by ≦ 3). Specific examples thereof include SiCl 4 , SiBr 4 , HSiCl 3 , CH 3 SiCl 3 , C 2 H 5 SiCl 3 , n-C 3 H 7 S.
Examples thereof include iCl 3 , C 6 H 5 SiCl 3 , (CH 3 ) 2 SiCl 2 , (C 2 H 5 ) 2 SiCl 2 and (CH 3 ) 3 SiCl.
又、本発明の触媒成分〔Ｃ〕の調製に使用されるハロゲ
ン化有機アルミニウム化合物は一般式R11 sAlX3-s（R11
はC1〜C12の炭化水素基、Ｘはハロゲン原子、かつ１≦
ｓ≦２）で表わされる化合物である。その具体例として
は、 （CH3）2AlCl,CH3AlCl2,（C2H5）2AlClC2H5AlCl,（C
2H5）1.5AlCl1.5，（ｉ−C4H9）2AlCl,i−C4H9AlCl2,
（ｎ−C8H17）2AlCl等を挙げることが出来る。The halogenated organoaluminum compound used in the preparation of the catalyst component [C] of the present invention has the general formula R 11 s AlX 3-s (R 11
Is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 1 ≦
It is a compound represented by s ≦ 2). Specific examples thereof include (CH 3 ) 2 AlCl, CH 3 AlCl 2 , and (C 2 H 5 ) 2 AlClC 2 H 5 AlCl, (C
2 H 5 ) 1.5 AlCl 1.5 , (i-C 4 H 9 ) 2 AlCl, i-C 4 H 9 AlCl 2 ,
(N-C 8 H 17) 2 AlCl and the like.
反応生成物〔Ａ〕または反応生成物〔Ｂ〕とハロゲン化
ケイ素化合物およびハロゲン化有機アルミニウム化合物
の配合割合について述べると、反応生成物〔Ａ〕または
反応生成物〔Ｂ〕中のMg1モルに対し、通常、ハロゲン
化ケイ素化合物は、0.1〜5.0モル、ハロゲン化有機アル
ミニウム化合物は、0.1〜50モルであり、ハロゲン化ケ
イ素化合物が0.5〜2.0モルおよびハロゲン化有機アルミ
ニウム化合物が0.5〜10モルが好適範囲である。The compounding ratio of the reaction product [A] or the reaction product [B] with the silicon halide compound and the organoaluminum halide compound will be described with respect to 1 mol of Mg in the reaction product [A] or the reaction product [B]. Usually, the silicon halide compound is 0.1 to 5.0 mol, the halogenated organoaluminum compound is 0.1 to 50 mol, the silicon halide compound is 0.5 to 2.0 mol, and the halogenated organoaluminum compound is preferably 0.5 to 10 mol. It is a range.
本発明の重合において使用される触媒成分〔Ｃ〕の調製
方法は、 成分〔Ｉ〕：反応生成物〔Ａ〕または反応生成物〔Ｂ〕 成分〔II〕：遷移金属化合物 成分〔III〕：ハロゲン化ケイ素化合物および／または
ハロゲン化有機アルミニウム化合物 の各成分を接触、反応させて得られるが、本願の目的を
十分達成するためには、次の反応手順をとることが必要
である。すなわち、まず成分〔Ｉ〕と成分〔II〕を反応
させ、しかる後に〔III〕を反応させる必要があり、ま
た成分〔III〕でハロゲン化ケイ素化合物とハロゲン化
有機アルミニウム化合物を併用する場合は、成分〔Ｉ〕
と成分〔II〕の反応生成物にハロゲン化ケイ素化合物を
反応させた後に、ハロゲン化有機アルミニウム化合物を
反応させる必要がある。それ以外の手順では活性の低下
や粉体特性の悪化等を招き好ましくない。The method for preparing the catalyst component [C] used in the polymerization of the present invention is as follows: component [I]: reaction product [A] or reaction product [B] component [II]: transition metal compound component [III]: halogen It can be obtained by contacting and reacting each component of a silicon oxide compound and / or an organoaluminum halide compound. However, in order to sufficiently achieve the object of the present application, the following reaction procedure is required. That is, it is necessary to first react the component [I] and the component [II], and then to react the [III], and when the silicon halide compound and the halogenated organoaluminum compound are used together in the component [III], Ingredient [I]
It is necessary to react the reaction product of the component [II] with the silicon halide compound, and then to react the halogenated organoaluminum compound. Any other procedure is not preferable because it causes a decrease in activity and deterioration of powder characteristics.
上記反応は、通常不活性炭化水素溶媒中で行われるが、
特にｎ−ヘキサン、ｎ−ヘプタン、デカリン、ベンゼ
ン、トルエン及びキシレン等の脂肪族または芳香族炭化
水素溶媒中で行う事が望ましい。The above reaction is usually carried out in an inert hydrocarbon solvent,
It is particularly desirable to carry out in an aliphatic or aromatic hydrocarbon solvent such as n-hexane, n-heptane, decalin, benzene, toluene and xylene.
又、何れの反応においても、その反応温度は10〜100
℃、反応時間は10分〜５時間で充分である。In any reaction, the reaction temperature is 10 to 100.
A reaction time of 10 minutes to 5 hours is sufficient at the temperature of ℃.
反応終了後、反応生成物はそのまま触媒成分〔Ｃ〕とし
て使用される。After completion of the reaction, the reaction product is used as it is as the catalyst component [C].
又、反応終了後、反応生成物を濾過し、可溶性成分をｎ
−ヘキサン、ｎ−ヘプタン及び灯油等の不活性炭化水素
溶媒で洗浄除去することにより固体成分として使用して
も本発明の目的を充分達成することが出来る。After completion of the reaction, the reaction product is filtered to remove the soluble component.
The object of the present invention can be sufficiently achieved even if it is used as a solid component by washing and removing with an inert hydrocarbon solvent such as -hexane, n-heptane and kerosene.
触媒成分〔Ｃ〕は、共触媒である有機アルミニウム化合
物〔Ｄ〕と共にエチレンの重合および共重合に使用され
る。The catalyst component [C] is used for the polymerization and copolymerization of ethylene with the organoaluminum compound [D] which is a cocatalyst.
本発明に使用される有機アルミニウム化合物〔Ｄ〕は一
般式Rc 12AlY3-c（R12はC1〜C12炭化水素基、Ｙは水素原
子、ハロゲン原子またはアルコキシド基、かつ１≦ｃ≦
３）で表わされる化合物である。その具体例としては、
Al（CH3）3,Al（C2H5）3,Al（ｉ−C4H9）3,（C2H5）2Al
Cl,（ｉ−C4H9）2AlCl,（C2H5）1.5AlCl1.5，（C2H5）2
AlH,（ｉ−C4H9）2AlH及び（C2H5）2Al（OC2H5）等を挙
げることが出来る。The organoaluminum compound [D] used in the present invention has the general formula R c 12 AlY 3-c (R 12 is a C 1 to C 12 hydrocarbon group, Y is a hydrogen atom, a halogen atom or an alkoxide group, and 1 ≦ c ≤
It is a compound represented by 3). As a concrete example,
Al (CH 3) 3, Al (C 2 H 5) 3, Al (i-C 4 H 9) 3, (C 2 H 5) 2 Al
Cl, (i-C 4 H 9) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H 5) 2
AlH, (i-C 4 H 9) 2 AlH , and (C 2 H 5) 2 Al (OC 2 H 5) or the like can be mentioned.
本発明のエチレンの重合または共重合に使用される触媒
は触媒成分〔Ｃ〕と有機アルミニウム化合物〔Ｄ〕とを
接触させる事により容易に調製できる。The catalyst used for the polymerization or copolymerization of ethylene of the present invention can be easily prepared by bringing the catalyst component [C] and the organoaluminum compound [D] into contact with each other.
エチレンの重合及び共重合触媒として好ましい両者の割
合は、触媒成分〔Ｃ〕中のTi、ＶおよびZrの総和１モル
当たり有機アルミニウム化合物〔Ｄ〕中のAlが１〜1000
モル、好ましくは10〜200モルである。The preferable ratio of both as a polymerization and copolymerization catalyst of ethylene is 1 to 1000 of Al in the organoaluminum compound [D] per 1 mol of the total of Ti, V and Zr in the catalyst component [C].
The molar amount is preferably 10 to 200 mol.
本発明のエチレンの重合および共重合方法は、一般のチ
ーグラー型触媒を使用する場合と同様であり、スラリー
重合法、気相重合法等の方法がとれる。また、重合反応
を反応条件が異なる２段階以上に分けて実施することも
出来る。The method for polymerizing and copolymerizing ethylene of the present invention is the same as when using a general Ziegler type catalyst, and a method such as a slurry polymerization method or a gas phase polymerization method can be adopted. Also, the polymerization reaction can be carried out in two or more stages under different reaction conditions.
スラリー重合法により重合を行う場合には、本発明の触
媒をヘキサン、ヘプタン及び灯油等の適当な不活性炭化
水素溶媒に分散し、これにエチレンまたはエチレンとα
−オレフィンを送入する事により容易に行われる。重合
温度は30〜100℃、好ましくは60〜90℃である。When the polymerization is carried out by the slurry polymerization method, the catalyst of the present invention is dispersed in a suitable inert hydrocarbon solvent such as hexane, heptane and kerosene, and ethylene or ethylene and α
-Easily done by feeding in olefins. The polymerization temperature is 30 to 100 ° C, preferably 60 to 90 ° C.
又、重合圧力は常圧〜50kg/cm2が好ましい。この場合、
溶媒１当たり有機アルミニウム化合物〔Ｄ〕が0.05〜
10mmol、好ましくは0.1〜5mmolで使用される。The polymerization pressure is preferably atmospheric pressure to 50 kg / cm 2 . in this case,
The amount of the organoaluminum compound [D] is 0.05 to 1 per solvent.
It is used at 10 mmol, preferably 0.1-5 mmol.
本発明の方法で生成する重合体の分子量は、重合温度、
触媒の使用量及び重合系への水素の添加により調節する
事ができるが、水素の添加が最も効果的な調節方法であ
る。The molecular weight of the polymer produced by the method of the present invention, the polymerization temperature,
It can be adjusted by the amount of the catalyst used and the addition of hydrogen to the polymerization system, but the addition of hydrogen is the most effective adjustment method.
本発明の方法は、エチレンの重合、およびエチレンとエ
チレンに対し約20重量％以下のプロピレン、ブテン−
１、ヘキセン−１およびオクテン−１等のα−オレフィ
ンとの共重合によるエチレン系共重合体の製造に有用で
ある。The process of the present invention comprises the polymerization of ethylene and ethylene and up to about 20% by weight of ethylene of propylene, butene-
It is useful for producing an ethylene-based copolymer by copolymerization with α-olefins such as 1, 1, hexene-1 and octene-1.
（ホ） 実施例 次に、本発明について実施例を挙げて詳細に説明する
が、本発明はこれらに限定されるものではない。(E) Examples Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
以下、実験の結果は第１表に実施例１〜６、および比較
例１〜５をまとめて示す。Hereinafter, the results of the experiment are shown in Table 1 together with Examples 1 to 6 and Comparative Examples 1 to 5.
また、第２表に実施例７〜11、および比較例６〜７をま
とめてある。Further, Table 2 summarizes Examples 7 to 11 and Comparative Examples 6 to 7.
なお、実施例１〜６、実施例７〜11の触媒の調製は本願
に基づく方法に準拠したものである。他方、比較例１〜
４は、特願昭62−146065号に準拠し、比較例６〜７は特
願昭60−77963号に準拠したものである。The catalysts of Examples 1 to 6 and Examples 7 to 11 were prepared according to the method of the present invention. On the other hand, Comparative Examples 1 to
4 is based on Japanese Patent Application No. 62-146065, and Comparative Examples 6 to 7 are based on Japanese Patent Application No. 60-77963.
以下の実施例および比較例における共通の測定方法は次
の通りである。The common measuring method in the following examples and comparative examples is as follows.
MFR:ASTM−Ｄ−1238−65T 温度190℃、荷重2.16kgの時のメルトインデックス 溶融張力（メルトテンション）：東洋精機製作所製メル
トテンションテスターを用い、樹脂温度190℃、押出速
度10mm/min、巻取り速度6.28m/min、ノズル径1.0mmφ、
ノズル長さ5.0mmの条件で測定した。MFR: ASTM-D-1238-65T Melt index at a temperature of 190 ° C and a load of 2.16 kg Melt tension: Using a melt tension tester manufactured by Toyo Seiki Seisakusho, resin temperature 190 ° C, extrusion speed 10 mm / min, winding Taking speed 6.28m / min, nozzle diameter 1.0mmφ,
The measurement was performed under the condition that the nozzle length was 5.0 mm.
溶融弾性（ダイスウェル比）：メルトインデックス測定
装置を用い樹脂温度190℃、剪断速度300sec-1で押し出
したパリソンの冷却後の径のオリフィス径に対する半径
方向の膨張度（％）で以下の式により算出した。Melt elasticity (die swell ratio): The expansion coefficient (%) of the diameter of the parison extruded at a resin temperature of 190 ° C and a shear rate of 300 sec -1 after cooling with a melt index measuring device in the radial direction (%) according to the following formula It was calculated.
（D0:オリフィス径、D:ストランド径） 実施例１ （１） 反応生成物〔Ｂ〕の製造 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にｎ−ブチルマグネシウムクロライドのジ−イソプロ
ピルエーテル溶液800ml（市販品:n−ブチルマグネシウ
ムクロライドとして1.34mol）を採取し、攪拌しながら
末端をトリメチルシリル基で封鎖したメチルヒドロポリ
シロキサン（25℃での粘度が約30センチストークス）8
0.5ml（Siとして1.34mol）を、室温を保ちながら、１時
間で滴下した。滴下後、１時間攪拌を続け褪色透明な反
応生成物〔Ａ〕を得た。 (D 0 : Orifice diameter, D: Strand diameter) Example 1 (1) Production of reaction product [B] Di-isopropyl ether of n-butylmagnesium chloride was added to a glass reactor whose interior was well dried and purged with nitrogen. 800 ml of solution (commercial product: 1.34 mol as n-butylmagnesium chloride) was sampled, and the end was blocked with methylhydropolysiloxane with a trimethylsilyl group (viscosity at 25 ° C is about 30 centistokes) 8
0.5 ml (1.34 mol as Si) was added dropwise over 1 hour while maintaining room temperature. After the dropping, stirring was continued for 1 hour to obtain a fading and transparent reaction product [A].
反応生成物〔Ａ〕の赤外線吸収スペクトルを測定したと
ころ、Si−Ｈ結合（2100cm-1）とSi−CH3結合（1250cm
-1）の吸収強度比（Si−Ｈ結合/Si−CH3結合）は1.10で
あった。When the infrared absorption spectrum of the reaction product [A] was measured, it was found that the Si-H bond (2100 cm -1 ) and the Si-CH 3 bond (1250 cm
−1 ) absorption intensity ratio (Si—H bond / Si—CH 3 bond) was 1.10.
こうして得られた反応生成物〔Ａ〕の溶液に、ｎ−ヘプ
タン500mlを添加、希釈した後、室温で２−エチルヘキ
サノール1.34molを１時間かけて滴下した。To the solution of the reaction product [A] thus obtained, 500 ml of n-heptane was added and diluted, and then 1.34 mol of 2-ethylhexanol was added dropwise at room temperature over 1 hour.
滴下終了後、圧力120−240mmHgで減圧蒸留を行い、１
を留出させた。ｎ−ヘプタンで希釈し、無色透明の反応
生成物〔Ｂ〕のｎ−ヘプタン溶液を得た。マグネシウム
の濃度は0.782mol/であり、ガスクロマトグラフィー
による分析の結果、ジイソプロピルエーテルは存在しな
かった。また反応生成物〔Ｂ〕の赤外線吸収スペクトル
を測定したところ、Si−Ｈ結合/Si−CH3結合の吸収強度
比は0.10であり、大部分のSi−Ｈ結合が２−エチルヘキ
サノールと反応していた。After completion of dropping, perform vacuum distillation at a pressure of 120-240 mmHg and
Was distilled. The reaction mixture was diluted with n-heptane to obtain a colorless transparent reaction product [B] in an n-heptane. The concentration of magnesium was 0.782 mol /, and as a result of analysis by gas chromatography, diisopropyl ether was not present. In addition, the infrared absorption spectrum of the reaction product [B] was measured. As a result, the absorption intensity ratio of Si—H bond / Si—CH 3 bond was 0.10, and most of the Si—H bond reacted with 2-ethylhexanol. Was there.
（２） 遷移金属化合物の調製 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にｎ−ヘプタン200mlを採取し、攪拌しながらTiCl411
ml（100mmol）、Zr（On−C4H9）436.5ml（100mmol）お
よびVOCl39.5ml（100mmol）を順次加え、80℃で１時間
攪拌しながら、反応を行なった。反応終了後、反応系を
室温に冷却し、黒褐色の溶液を得た。(2) Preparation of transition metal compound 200 ml of n-heptane was sampled in a glass reactor whose inside was thoroughly dried and purged with nitrogen, and TiCl 4 11 was added while stirring.
ml (100mmol), Zr (On -C 4 H 9) were added sequentially 4 36.5 ml (100 mmol) and VOCl 3 9.5ml (100mmol), while stirring for 1 hour at 80 ° C., the reaction was conducted. After completion of the reaction, the reaction system was cooled to room temperature to obtain a blackish brown solution.
（３） 触媒成分〔Ｃ〕の調製 あらかじめ、内部を乾燥、窒素置換したガラス反応器に
ｎ−ヘプタン30ml、および（１）で得られた反応生成物
〔Ｂ〕をマグネシウム基準で10mmol採取した。攪拌しな
がら（２）で得られた遷移金属化合物のｎ−ヘプタン溶
液2.6mlを室温で添加し、そのまま30分攪拌を続け、反
応を行なった。続いて温度を25℃に保持し、ｎ−ヘプタ
ンで希釈した（C2H5）1.5AlCl1.5溶液（Al換算で濃度が
1mol/）を20ml添加した。さらに１時間反応を行な
い、触媒成分〔Ｃ〕を得た。(3) Preparation of catalyst component [C] 30 mmol of n-heptane and 10 mmol of the reaction product [B] obtained in (1) were sampled in a glass reactor whose inside was dried and purged with nitrogen. 2.6 ml of an n-heptane solution of the transition metal compound obtained in (2) was added with stirring at room temperature, and stirring was continued for 30 minutes to carry out the reaction. Subsequently, the temperature was kept at 25 ° C, and (C 2 H 5 ) 1.5 AlCl 1.5 solution diluted with n-heptane (concentration in terms of Al
20 ml of 1 mol /) was added. The reaction was further continued for 1 hour to obtain a catalyst component [C].
（４） エチレンの重合 内部を乾燥し、エチレン置換した１のステンレス製オ
ートクレーブにｎ−ヘキサン600mlを仕込み、60℃に昇
温後、Al（ｉ−C4H9）30.7mmolと（３）で得られた触媒
成分〔Ｃ〕0.2ml、（Ti＋Ｖ＋Zr換算で0.00316mmol）を
順次添加した。続いて水素を0.7kg/cm2導入し、75℃に
昇温後、エチレンを連続的に導入しながら、4kg/cm
2（ゲージ圧）で１時間、重合を行なった。(4) Polymerization of Ethylene 600 ml of n-hexane was charged into a stainless steel autoclave of 1 in which ethylene was replaced with ethylene, the temperature was raised to 60 ° C., and then 0.7 mmol of Al (i—C 4 H 9 ) 3 was added (3). 0.2 ml of the catalyst component [C] obtained in (1) and (0.00316 mmol in terms of Ti + V + Zr) were sequentially added. Then, introduce hydrogen at 0.7 kg / cm 2 , raise the temperature to 75 ° C, and continuously introduce ethylene at 4 kg / cm 2.
Polymerization was carried out at 2 (gauge pressure) for 1 hour.
生成物を溶媒より分離後乾燥し、白色粉末状ポリエチレ
ン128gを得た。このポリエチレンのMFRは0.22g/10分、
メルトテンションは4.9g、ダイスウェル比は90％であっ
た。The product was separated from the solvent and dried to obtain 128 g of white powdery polyethylene. The MFR of this polyethylene is 0.22g / 10 minutes,
The melt tension was 4.9 g and the die swell ratio was 90%.
又、触媒の重合活性は213kgPE/g−遷移金属・hrであっ
た。The polymerization activity of the catalyst was 213 kg PE / g-transition metal · hr.
実施例２および３ 触媒成分〔Ｃ〕の調製、およびエチレンの重合実施例１
−（２）でTiCl4添加量をそれぞれ7.7ml（70mmol）、お
よび5.5ml（50mmol）に変更した以外は実施例１と同一
条件で触媒成分〔Ｃ〕の調製を行なった。実施例１−
（４）で導入した水素圧をそれぞれ0.8kg/cm2、および
0.9kg/cm2とした以外は実施例１と同一条件でエチレン
の重合を行なった。Examples 2 and 3 Preparation of catalyst component [C] and polymerization of ethylene Example 1
The catalyst component [C] was prepared under the same conditions as in Example 1 except that the amounts of TiCl 4 added were changed to 7.7 ml (70 mmol) and 5.5 ml (50 mmol) in (2). Example 1-
The hydrogen pressure introduced in (4) was 0.8 kg / cm 2 , and
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the amount was 0.9 kg / cm 2 .
実施例４ 触媒成分〔Ｃ〕の調製、およびエチレンの重合 実施例−１（２）でTiCl4の代りにTi（Oi−C3H7）419.9
g（70mmol）を用い、Zr（On−C4H9）４の代りにZr（On
−C4H9）2Cl230.8g（100mmol）を用い、（C2H5）1.5AlC
l1.5溶液の添加量を50mlとした以外は実施例１と同一条
件で触媒成分〔Ｃ〕の調製を行なった。実施例１−
（４）で導入した水素圧を0.7kg/cm2とした以外は実施
例１と同一条件でエチレンの重合を行なった。Example 4 Preparation of Catalyst Component [C] and Polymerization of Ethylene Instead of TiCl 4 in Example-1 (2), Ti (Oi-C 3 H 7 ) 4 19.9
g (70 mmol), Zr (On-C 4 H 9 ) 4 instead of Zr (On
-C 4 H 9 ) 2 Cl 2 30.8 g (100 mmol) was used, and (C 2 H 5 ) 1.5 AlC
The catalyst component [C] was prepared under the same conditions as in Example 1 except that the amount of the 1.5 solution added was 50 ml. Example 1-
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the hydrogen pressure introduced in (4) was 0.7 kg / cm 2 .
実施例５ 触媒成分〔Ｃ〕の調製、およびエチレンの重合 実施例１−（２）でVOCl3の代りにVO（Oi−C3H7）324.4
g（100mmol）を用い、Zr（On−C4H9）４の代りにZr（On
−C4H9）2Cl230.8g（100mmol）を用い、（C2H5）1.5AlC
l1.5溶液の添加量を50mlとした以外は実施例１と同一条
件で触媒成分〔Ｃ〕の調製を行なった。実施例１−
（４）で導入した水素圧を0.8kg/cm2とした以外は実施
例１と同一条件でエチレンの重合を行なった。Example 5 Preparation of catalyst component [C] and polymerization of ethylene VO (Oi—C 3 H 7 ) 3 24.4 instead of VOCl 3 in Example 1- (2)
g (100 mmol), Zr (On-C 4 H 9 ) 4 instead of Zr (On
-C 4 H 9 ) 2 Cl 2 30.8 g (100 mmol) was used, and (C 2 H 5 ) 1.5 AlC
The catalyst component [C] was prepared under the same conditions as in Example 1 except that the amount of the 1.5 solution added was 50 ml. Example 1-
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the hydrogen pressure introduced in (4) was 0.8 kg / cm 2 .
実施例６ （１） 反応生成物〔Ａ〕の製造 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にｎ−ヘプタン35mlとｎ−ブチルエチルマグネシウム
のｎ−ヘプタン溶液36ml（市販品:n−ブチルエチルマグ
ネシウムとして50mmol）を採取し、攪拌しながらトリエ
チルアルミニウムのｎ−ヘプタン溶液5ml（トリエチル
アルミニウムとして5mmol）を添加した。ついで温度を3
0℃に保ちながら、末端をトリメチルシリル基で封鎖し
たメチルヒドロポリシロキサン（25℃での粘度が約30セ
ンチストークス）のヘプタン溶液21ml（Siとして110mmo
l）を15分かけて滴下した。全量滴下後、70℃で１時間
攪拌を続け、年稠な溶液を得た。得られた溶液をｎ−ヘ
プタンで希釈し、反応生成物〔Ａ〕のｎ−ヘプタン溶液
100ml（Mgとして0.5mol/）を得た。Example 6 (1) Production of reaction product [A] 36 ml of n-heptane solution of 35 ml of n-heptane and n-butylethylmagnesium (commercially available product: n- 50 mmol of butylethylmagnesium) was collected, and 5 ml of a solution of triethylaluminum in n-heptane (5 mmol of triethylaluminum) was added with stirring. Then set the temperature to 3
21 ml of a heptane solution of methylhydropolysiloxane (with a viscosity at 25 ° C of about 30 centistokes) capped with trimethylsilyl groups at the temperature of 0 ° C (110 mmo as Si)
l) was added dropwise over 15 minutes. After dropping the whole amount, stirring was continued at 70 ° C. for 1 hour to obtain a viscous solution. The obtained solution was diluted with n-heptane, and the reaction product [A] was dissolved in n-heptane.
100 ml (0.5 mol / Mg) was obtained.
（２） 遷移金属化合物の調製 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にｎ−ヘプタン200mlを採取し、攪拌しながらTi（Oi
−C3H7）429.9ml（100mmol）、Zr（On−C4H9）436.5ml
（100mmol）、およびVOCl39.5ml（100mmol）を順次加
え、80℃で１時間攪拌しながら、反応を行なった。反応
終了後、反応系を室温に冷却し、均一溶液を得た。(2) Preparation of transition metal compound 200 ml of n-heptane was sampled in a glass reactor whose inside was thoroughly dried and purged with nitrogen, and Ti (Oi)
-C 3 H 7 ) 4 29.9 ml (100 mmol), Zr (On-C 4 H 9 ) 4 36.5 ml
(100 mmol) and 9.5 ml (100 mmol) of VOCl 3 were sequentially added, and the reaction was carried out while stirring at 80 ° C. for 1 hour. After completion of the reaction, the reaction system was cooled to room temperature to obtain a uniform solution.
（３） 触媒成分〔Ｃ〕の調製 あらかじめ、内部を乾燥、窒素置換したガラス反応器に
ｎ−ヘプタン10ml、および上記反応生成物〔Ａ〕のｎ−
ヘプタン溶液20mlを採取した。攪拌しながら実施例１−
（２）で得た遷移金属化合物のｎ−ヘプタン溶液2.8ml
を室温で添加し、そのまま30分攪拌を続け、反応を行な
った。続いて温度を25℃に保持し、ｎ−ヘプタンで希釈
したエチルアルミニウムジクロリド溶液（Al換算で濃度
が1mol/）を40ml添加した。さらに１時間反応を行な
い、触媒成分〔Ｃ〕を得た。(3) Preparation of catalyst component [C] 10 ml of n-heptane and n-heptane of the above reaction product [A] were placed in a glass reactor whose interior was previously dried and purged with nitrogen.
20 ml of heptane solution was collected. Example 1 with stirring
2.8 ml of n-heptane solution of the transition metal compound obtained in (2)
Was added at room temperature, and stirring was continued for 30 minutes to carry out the reaction. Then, the temperature was maintained at 25 ° C., and 40 ml of an ethylaluminum dichloride solution diluted with n-heptane (concentration: 1 mol / in terms of Al) was added. The reaction was further continued for 1 hour to obtain a catalyst component [C].
（４） エチレンの重合 上記の触媒成分〔Ｃ〕を使用し、導入した水素圧を1.9k
g/cm2とした以外は実施例１と同一条件でエチレンの重
合を行なった。(4) Polymerization of ethylene Using the above catalyst component [C], the introduced hydrogen pressure is 1.9 k
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that g / cm 2 was used.
比較例１ 触媒成分の調製、およびエチレンの重合 遷移金属化合物としてTiCl4単独とした以外は実施例１
と同様に触媒成分の調製を行なった。得られたポリエチ
レンのメルトテンションおよびダイスウェル比の値は実
施例１〜５に比べ著しく小さいものであった。Comparative Example 1 Preparation of catalyst component and polymerization of ethylene Example 1 except using TiCl 4 alone as the transition metal compound
The catalyst component was prepared in the same manner as in. The values of melt tension and die swell ratio of the obtained polyethylene were significantly smaller than those of Examples 1-5.
比較例２〜４ 実施例１において遷移金属化合物を各二成分の組合せと
した以外は実施例１と同様に触媒成分の調製を行った。
かくして得られた触媒を用い、第１表に示す触媒添加量
及び水素圧とした以外は実施例１と同一条件でエチレン
の重合を行なった。チタン化合物とバナジウム化合物の
二成分系およびチタン化合物とジルコニウム化合物の二
成分系では、得られたポリエチレンのメルトテンション
およびダイスウェル比の値は実施例１〜５に比べ、明ら
かに小さいものであった。また、バナジウム化合物とジ
ルコニウム化合物の二成分系では実質的な活性を示さ
ず、メルトテンションおよびダイスウェル比の測定がで
きなかった。Comparative Examples 2 to 4 Catalyst components were prepared in the same manner as in Example 1 except that the transition metal compound in Example 1 was a combination of two components.
Using the catalyst thus obtained, ethylene was polymerized under the same conditions as in Example 1 except that the catalyst addition amount and hydrogen pressure shown in Table 1 were used. In the binary system of titanium compound and vanadium compound and the binary system of titanium compound and zirconium compound, the values of melt tension and die swell ratio of the obtained polyethylene were obviously smaller than those of Examples 1-5. . Further, the binary system of the vanadium compound and the zirconium compound did not show substantial activity, and the melt tension and the die swell ratio could not be measured.
比較例５ 触媒成分の調製、およびエチレンの重合 実施例６−（１）で得た反応生成物〔Ａ〕を使用し、遷
移金属化合物としてTi（Oi−C3H7）４のみを使用した以
外は実施例６と同様に触媒成分の調製を行なった。この
触媒成分を用い、導入した水素圧を1.5kg/cm2とした以
外は実施例１と同一条件でエチレンの重合を行なった。
実施例６に比べ得られたポリエチレンのメルトテンショ
ンおよびダイスウェル比の値は小さいものであった。Comparative Example 5 Preparation of Catalyst Component and Polymerization of Ethylene The reaction product [A] obtained in Example 6- (1) was used, and only Ti (Oi-C 3 H 7 ) 4 was used as the transition metal compound. The catalyst components were prepared in the same manner as in Example 6 except for the above. Using this catalyst component, ethylene was polymerized under the same conditions as in Example 1 except that the introduced hydrogen pressure was 1.5 kg / cm 2 .
The values of melt tension and die swell ratio of the obtained polyethylene were smaller than those of Example 6.
実施例７ （１） 反応生成物〔Ａ〕の製造 予め内部を良く乾燥、窒素置換したガラス反応器にｎ−
ブチルマグネシウムクロライド（0.670mol）のテトラヒ
ドロフラン溶液300mlを仕込み、末端をトリメチルシリ
ル基で置換したメチルヒドロポリシロキサン〔SiO.7g原
子、粘度約30センチストークス（25℃）〕42.0mlを攪拌
下冷却しながら徐々に滴下した。全量添加後、70℃で１
時間攪拌し、室温まで冷却して暗褐色透明溶液を得た。
この溶液にトルエン400mlを添加後、160〜170mmHgの減
圧下でテトラヒドロフランとトルエンの混合溶液480ml
を蒸留除去した。さらに、トルエン480mlを添加後、同
様にしてテトラヒドロフランとトルエンの混合溶液480m
lを蒸溜除去した。得られた溶液をトルエンで希釈し、
反応生成物〔Ａ〕のトルエン溶液495ml（Mg1.35mol/
）を得た。Example 7 (1) Production of reaction product [A] n- was added to a glass reactor whose interior had been thoroughly dried and whose atmosphere had been replaced with nitrogen.
300 ml of a tetrahydrofuran solution of butylmagnesium chloride (0.670 mol) was charged, and 42.0 ml of methylhydropolysiloxane [SiO.7g atom, viscosity of about 30 centistokes (25 ° C)] whose terminal was substituted with a trimethylsilyl group was gradually cooled with stirring. Was added dropwise. After adding the whole amount, 1 at 70 ℃
Stir for hours and cool to room temperature to give a dark brown transparent solution.
After adding 400 ml of toluene to this solution, 480 ml of a mixed solution of tetrahydrofuran and toluene under reduced pressure of 160 to 170 mmHg.
Was distilled off. Furthermore, after adding 480 ml of toluene, a mixed solution of tetrahydrofuran and toluene of 480 m
l was distilled off. The resulting solution is diluted with toluene,
Toluene solution of reaction product [A] 495 ml (Mg 1.35 mol /
) Got.
（２） 遷移金属化合物の調製 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にトルエン200mlを採取し、攪拌しながらTi（Oi−C3H
7）429.9ml（100mmol）、VOCl39.5ml（100mmol）、およ
びZr（On−C4H9）436.5ml（100mmol）を順次加え、80℃
で１時間反応を行なった。反応系を室温に冷却し、均一
溶液を得た。(2) Preparation advance of the transition metal compound, well-dried interior, 200ml of toluene were taken in a glass reactor was purged with nitrogen, with stirring Ti (Oi-C 3 H
7 ) 4 29.9 ml (100 mmol), VOCl 3 9.5 ml (100 mmol), and Zr (On-C 4 H 9 ) 4 36.5 ml (100 mmol) are added sequentially, and the temperature is 80 ° C.
The reaction was carried out for 1 hour. The reaction system was cooled to room temperature to obtain a uniform solution.
（３） 触媒成分〔Ｃ〕の調製 あらかじめ、内部を乾燥し、窒素置換したガラス反応器
にトルエン40ml、および上記（１）で得た反応生成物
〔Ａ〕をマグネシウム基準で67.6mmol採取した。攪拌し
ながら上記（２）で得た遷移金属化合物のトルエン溶液
18.6mlを仕込み、50℃で１時間反応させた。ついで、Si
Cl467.6mmolを含むトルエン溶液17.7mlを30分間で滴下
し、50℃で１時間攪拌し、反応を行なった。続いてC2H5
AlCl2270.4mmolを含むトルエン溶液78.6mlを30分で滴下
し、滴下終了後、70℃に昇温し、１時間攪拌した。(3) Preparation of catalyst component [C] 40 ml of toluene and 67.6 mmol of the reaction product [A] obtained in (1) above were sampled in a glass reactor whose inside was dried and whose atmosphere was replaced with nitrogen. A toluene solution of the transition metal compound obtained in (2) above with stirring
18.6 ml was charged and reacted at 50 ° C for 1 hour. Then Si
17.7 ml of a toluene solution containing 67.6 mmol of Cl 4 was added dropwise over 30 minutes, and the mixture was stirred at 50 ° C. for 1 hour to carry out a reaction. Then C 2 H 5
78.6 ml of a toluene solution containing 270.4 mmol of AlCl 2 was added dropwise over 30 minutes, and after the addition was completed, the temperature was raised to 70 ° C. and the mixture was stirred for 1 hour.
得られたスラリーにｎ−ヘキサンを加え、可溶性成分を
傾斜濾別した。この操作を６回繰返して固体の触媒成分
〔Ｃ〕を得た。N-Hexane was added to the obtained slurry, and soluble components were filtered off by decantation. This operation was repeated 6 times to obtain a solid catalyst component [C].
（４） エチレンの重合 上記固体の触媒成分〔Ｃ〕を6mg使用し、水素の仕込量
を3.3kg/cm2、全圧を8kg/cm2（ゲージ圧）、重合温度を
85℃とした以外は実施例１と同一の条件でエチレンの重
合を行ない、白色粉末状ポリエチレン103gを得た。この
ポリエチレンのMFRは0.24g/10分、メルトテンションは
5.2g、ダイスウェル比は96％であった。又、触媒の重合
活性は17.2kgPE/g−固体触媒・hrであった。(4) Polymerization of ethylene Using 6 mg of the above solid catalyst component [C], the hydrogen charging amount is 3.3 kg / cm 2 , the total pressure is 8 kg / cm 2 (gauge pressure), and the polymerization temperature is
Ethylene was polymerized under the same conditions as in Example 1 except that the temperature was 85 ° C. to obtain 103 g of white powdery polyethylene. This polyethylene has an MFR of 0.24g / 10 minutes and a melt tension of
The weight was 5.2 g and the die swell ratio was 96%. The polymerization activity of the catalyst was 17.2 kgPE / g-solid catalyst · hr.
実施例8,9 触媒成分〔Ｃ〕の調製、およびエチレンの重合 実施例７−（２）でTi（Oi−C3H7）４の添加量をそれぞ
れ20.9ml（70mmol）および14.9ml（50mmol）に変更した
以外は実施例７と同一条件で固体の触媒成分〔Ｃ〕の調
製を行なった。実施例７−（４）で水素圧をそれぞれ3.
5kg/cm2、および3.7kg/cm2とした以外は実施例７と同一
条件でエチレンの重合を行なった。Examples 8 and 9 Preparation of Catalyst Component [C] and Polymerization of Ethylene In Example 7- (2), the addition amounts of Ti (Oi—C 3 H 7 ) 4 were 20.9 ml (70 mmol) and 14.9 ml (50 mmol, respectively). The solid catalyst component [C] was prepared under the same conditions as in Example 7, except that the above procedure was changed to (4). In Example 7- (4), the hydrogen pressure was adjusted to 3.
Polymerization of ethylene was carried out under the same conditions as in Example 7, except that 5 kg / cm 2 and 3.7 kg / cm 2 were used.
実施例10 （１） 遷移金属化合物の調製 実施例７−（２）でTi（Oi−C3H7）４の代りにTiCl411m
l（100mmol）を使用した以外は実施例７と同一条件で遷
移金属化合物の調製を行なった。Example 10 (1) Preparation Example of the transition metal compound 7- (2) Ti (Oi- C 3 H 7) 4 in place of TiCl 4 11m
A transition metal compound was prepared under the same conditions as in Example 7 except that 1 (100 mmol) was used.
（２） 触媒成分〔Ｃ〕の調製 あらかじめ、内部をよく乾燥、窒素置換したガラス反応
器にトルエン40ml、および実施例７−（１）で得た反応
生成物〔Ａ〕をマグネシウム基準で67.6mmol採取した。
攪拌しながら上記（１）で得た遷移金属化合物のトルエ
ン溶液17.3mlを仕込み、50℃で１時間反応させた。つい
で、（C2H5）1.5AlCl1.5135.2mmolを含むトルエン溶液5
0mlを30分で滴下し、滴下終了後、70℃に昇温し、１時
間攪拌した。(2) Preparation of catalyst component [C] 40 ml of toluene in a glass reactor whose inside was thoroughly dried and nitrogen-substituted in advance, and the reaction product [A] obtained in Example 7- (1) was 67.6 mmol based on magnesium. It was collected.
With stirring, 17.3 ml of a toluene solution of the transition metal compound obtained in (1) above was charged and reacted at 50 ° C. for 1 hour. Then, a toluene solution containing (C 2 H 5 ) 1.5 AlCl 1.5 135.2 mmol 5
0 ml was added dropwise over 30 minutes, and after the addition was completed, the temperature was raised to 70 ° C. and the mixture was stirred for 1 hour.
得られたスラリーにｎ−ヘキサンを加え、可溶性成分を
傾斜濾別した。この操作を６回繰返して固体の触媒成分
〔Ｃ〕を得た。N-Hexane was added to the obtained slurry, and soluble components were filtered off by decantation. This operation was repeated 6 times to obtain a solid catalyst component [C].
（３） エチレンの重合 水素の仕込量を3.0kg/cm2とした以外は実施例７と同一
の条件でエチレンの重合を行ない、白色粉末状ポリエチ
レン109gを得た。このポリエチレンのMFRは0.31g/10
分、メルトテンションは4.5g、ダイスウェル比は91％で
あった。又、触媒の重合活性は18.2kgPE/g−固体触媒・
hrであった。(3) Polymerization of ethylene Ethylene was polymerized under the same conditions as in Example 7 except that the charged amount of hydrogen was 3.0 kg / cm 2 , to obtain 109 g of white powdery polyethylene. The MFR of this polyethylene is 0.31g / 10
Min, melt tension was 4.5 g, and die swell ratio was 91%. Also, the polymerization activity of the catalyst is 18.2 kg PE / g-solid catalyst.
It was hr.
実施例11 触媒成分の調製、およびエチレンの重合 触媒成分〔Ｃ〕の調製およびエチレンの重合 実施例10−（１）でTiCl4の添加量を5.5ml（50mmol）に
変更した以外は実施例10と同一条件で固体の触媒成分
〔Ｃ〕の調製を行なった。水素の仕込量を3.2kg/cm2と
した以外は実施例７と同一条件でエチレンの重合を行な
った。Example 11 Preparation of catalyst component and polymerization of ethylene Preparation of catalyst component [C] and polymerization of ethylene Example 10- (1) except that the addition amount of TiCl 4 was changed to 5.5 ml (50 mmol). Solid catalyst component [C] was prepared under the same conditions as described above. Polymerization of ethylene was carried out under the same conditions as in Example 7 except that the charged amount of hydrogen was 3.2 kg / cm 2 .
比較例６ 触媒成分の調製、およびエチレンの重合 遷移金属化合物としてTi（Oi−C3H7）４単独とした以外
は実施例７と同様に固体の触媒成分の調製を行なった。Preparation of Comparative Example 6 Catalyst components, and except that the Ti (Oi-C 3 H 7 ) 4 alone as the polymerization the transition metal compound of ethylene was carried out the preparation of catalyst component as well solid as in Example 7.
この固体の触媒成分を使用し、導入した水素圧を2.3kg/
cm2とした以外は実施例７と同一条件でエチレンの重合
を行なった。Using this solid catalyst component, the introduced hydrogen pressure is 2.3 kg /
Polymerization of ethylene was carried out under the same conditions as in Example 7 except that cm 2 was used.
得られたポエチレンのメルトテンションおよびダイスウ
ェル比の値は実施例７に比べ小さいものであった。The values of melt tension and die swell ratio of the obtained polyethylene were smaller than those in Example 7.
比較例７ 触媒成分の調製、およびエチレンの重合 遷移金属化合物としてTiCl4単独とした以外は実施例10
と同様に固体の触媒成分の調製を行なった。この固体の
触媒成分を使用し、水素の仕込量を2.5kg/cm2とした以
外は実施例７と同一条件でエチレンの重合を行なった。
ポリエチレンのメルトテンションおよびダイスウェル比
の値は実施例10に比べ小さいものであった。Comparative Example 7 Preparation of catalyst component and polymerization of ethylene Example 10 except that TiCl 4 alone was used as the transition metal compound
A solid catalyst component was prepared in the same manner as in. Using this solid catalyst component, ethylene was polymerized under the same conditions as in Example 7 except that the amount of hydrogen charged was 2.5 kg / cm 2 .
The values of melt tension and die swell ratio of polyethylene were smaller than those of Example 10.
（ヘ） 発明の効果 先行技術である特願昭62−146065号に準じた方法の結果
（第１表）と特願昭60−77963号に準じた方法の結果
（第２表）のどちらにおいても以下の効果は明白であ
る。 (F) Effects of the Invention In either the result of the method according to the prior art Japanese Patent Application No. 62-146065 (Table 1) or the result of the method according to Japanese Patent Application No. 60-77963 (Table 2). Also, the following effects are clear.
A.触媒活性 触媒活性はｇ−遷移金属・hr当りの重合体収量が100kg
以上、もしくはｇ−固体触媒・hr当りの重合体収量が10
kg以上であり、高活性触媒として遜色のないものであ
る。A. Catalytic activity As for catalytic activity, the polymer yield per g-transition metal / hr is 100 kg.
Or more, or the polymer yield per g-solid catalyst / hr is 10
It weighs more than kg and is comparable to a highly active catalyst.
B.メルトテンションおよびダイスウェル比 本発明の方法では、MFRが0.22〜0.31g/10分でメルトテ
ンションの値が4.5g以上およびダイスウェル比が90％以
上であり、メルトテンションとダイスウェル比の両方の
値が同時に高いポリエチレンが得られる。B. Melt tension and die swell ratio In the method of the present invention, the MFR is 0.22 to 0.31 g / 10 minutes, the value of melt tension is 4.5 g or more and the die swell ratio is 90% or more. Polyethylene with both high values is obtained at the same time.
特願昭62−146065号に準じて行った実施例１〜６と比較
例１および５を比較すると、実施例１〜６では活性、メ
ルトテンションおよびダイスウエル比の値がいずれも高
いが比較例１および５では活性が比較的高いものの、メ
ルトテンションおよびダイスウエル比の値が極めて小さ
い。Comparing Examples 1 to 6 and Comparative Examples 1 and 5 conducted according to Japanese Patent Application No. 62-146065, Examples 1 to 6 have high activity, melt tension and die swell ratio, but Comparative Example 1 In and 5, the activity was relatively high, but the values of melt tension and die swell ratio were extremely small.
比較例２〜４は遷移金属化合物として二成分の組合せを
変えて、その効果を調べたものである。チタン化合物並
びにバナジウム化合物、またはジルコニウム化合物から
選ばれた二成分系（比較例２及び３）では活性は比較的
高いものの、メルトテンションおよびダイスウエル比の
値は実施例１〜５に比べ明らかに劣っている。また、バ
ナジウム化合物とジルコニウム化合物の二成分系（比較
例４）では、実質的な活性が得られず実用上興味のない
ものである。このように遷移金属化合物としてチタン化
合物、バナジウム化合物およびジルコニウム化合物の三
成分を併用する本発明の方法によってはじめてこれらの
効果が発揮されるものである。また、特願昭60−77963
号に準じて行った実施例７〜９と比較例６、実施例10〜
11と比較例７を比較すると、活性・メルトテンションお
よびダイスウエル比の値がいずれにおいても実施例の値
が比較例の値よりも高く、本発明の効果は顕著である。
かくして、触媒活性が高く、メルトテンションおよびダ
イスウエル比の値を同時に高くすることを目的とした本
発明の効果は十分に達成された。In Comparative Examples 2 to 4, the effect was investigated by changing the combination of two components as the transition metal compound. Although the binary compounds (comparative examples 2 and 3) selected from titanium compounds and vanadium compounds or zirconium compounds have relatively high activity, the values of melt tension and die swell ratio are clearly inferior to those of Examples 1-5. There is. Further, the binary system of the vanadium compound and the zirconium compound (Comparative Example 4) is not of practical interest because no substantial activity is obtained. Thus, these effects are exhibited only by the method of the present invention in which the three components of the titanium compound, the vanadium compound and the zirconium compound are used in combination as the transition metal compound. In addition, Japanese Patent Application Sho 60-77963
Nos. 7-9, Comparative Example 6, and Example 10-
Comparing No. 11 with Comparative Example 7, the values of Example are higher than those of Comparative Example in any of the values of activity / melt tension and die swell ratio, and the effect of the present invention is remarkable.
Thus, the effect of the present invention, which has a high catalytic activity and simultaneously increases the values of the melt tension and the die swell ratio, was sufficiently achieved.
第１図は本発明のフローチャートを示す。 第２図は本発明の先行技術である特願昭60−77963号お
よび特願昭62−146065号をまとめたフローチャートを示
したものである。FIG. 1 shows a flow chart of the present invention. FIG. 2 is a flow chart summarizing Japanese Patent Application Nos. 60-77963 and 62-146065, which are prior arts of the present invention.
Claims (12)
応で得られる反応生成物〔Ａ〕、または反応生成物
〔Ａ〕にさらにアルコール、アルデヒドおよびケトンよ
り選ばれる少くとも一種類以上の親核的試薬を反応させ
て得られる反応生成物〔Ｂ〕 〔II〕遷移金属化合物 〔III〕ハロゲン化ケイ素化合物、および／またはハロ
ゲン化有機アルミニウム化合物 を接触させて得られる触媒成分〔Ｃ〕と有機アルミニウ
ム化合物〔Ｄ〕を用いて、エチレンまたはエチレンと他
のα−オレフィンを重合、もしくは共重合する方法にお
いて、成分〔II〕として、（１）一般式Ti（OR7）lX4-l
（R7はC1〜C12の炭化水素基、Ｘはハロゲン原子、かつ
０≦ｌ≦４）で表わされるチタン化合物、（２）一般式
VO（OR8）mX3-m（R8はC1〜C12の炭化水素基、Ｘはハロ
ゲン原子、かつ０≦ｍ≦３）またはVX4（Ｘはハロゲン
原子）で表わされるバナジウム化合物、および（３）一
般式Zr（OR9）nX4-n（R9はC1〜C12の炭化水素基、Ｘは
ハロゲン原子、かつ０≦ｎ≦４）で表わされるジルコニ
ウム化合物の混合物あるいはこれらの反応生成物を用
い、まず成分〔Ｉ〕と成分〔II〕を反応させ、しかる後
に〔III〕を反応させ、さらに成分〔III〕でハロゲン化
ケイ素化合物とハロゲン化有機アルミニウム化合物を併
用する場合は、成分〔Ｉ〕と成分〔II〕の反応生成物に
ハロゲン化ケイ素化合物を反応させた後に、ハロゲン化
有機アルミニウム化合物を反応させることを特徴とす
る、エチレン系重合体の製造方法。1. A reaction product [A] obtained by the reaction of the following components [I] to [III] [I] hydropolysiloxane with a Grignard reagent, or an alcohol, an aldehyde and Reaction product obtained by reacting at least one kind of nucleophilic reagent selected from ketone [B] [II] Transition metal compound [III] Silicon halide compound, and / or halogenated organoaluminum compound In the method of polymerizing or copolymerizing ethylene or ethylene and another α-olefin by using the catalyst component [C] and the organoaluminum compound [D] thus obtained, the component [II] is represented by the general formula (1): Ti (OR 7 ) l X 4-l
(R 7 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ l ≦ 4), a titanium compound represented by the formula (2).
Vanadium compound represented by VO (OR 8 ) m X 3-m (R 8 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ m ≦ 3) or VX 4 (X is a halogen atom) And (3) a mixture of zirconium compounds represented by the general formula Zr (OR 9 ) n X 4-n (R 9 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 0 ≦ n ≦ 4) Alternatively, using these reaction products, first, the component [I] and the component [II] are reacted, and then the [III] is reacted, and the silicon halide compound and the organoaluminum halide compound are used in combination in the component [III]. In this case, the method for producing an ethylene polymer is characterized in that the reaction product of the component [I] and the component [II] is reacted with a silicon halide compound and then with a halogenated organoaluminum compound.
はフェノキシ基、ａは０、１、または２、ｂは１、２ま
たは３で、かつａ＋ｂ≦３）で表わされる構造単位をも
つ鎖状または環状の化合物であることを特徴とする、請
求項１記載のエチレン系重合体の製造方法。2. Hydropolysiloxane has the general formula (R 1 is a C 1 to C 12 hydrocarbon group or an alkoxy group, or a phenoxy group, a is 0, 1, or 2, b is 1, 2 or 3, and a + b ≦ 3) The method for producing an ethylene-based polymer according to claim 1, wherein the ethylene-based polymer is a chain or cyclic compound.
（MgR2X）ｑ（R2はC1〜C12の炭化水素基、Ｘはハロゲン
原子、またｐおよびｑはそれぞれ、０〜１の数でｐ＋ｑ
＝１）で示される有機マグネシウム化合物であることを
特徴とする、請求項１記載のエチレン系重合体の製造方
法。3. The Grignard reagent has the general formula (MgR 2 2 ) p.
(MgR 2 X) q (R 2 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and p and q are each a number of 0 to 1 and p + q.
It is an organomagnesium compound shown by = 1), The manufacturing method of the ethylene polymer of Claim 1 characterized by the above-mentioned.
ぞれ水素原子またはC1〜C17の炭化水素基を表わし相互
に同じでも異なっていてもよい）、および一般式 （R5はC3〜C17の２価の炭化水素基）で示されるアルデ
ヒド、またはケトン、あるいは一般式R6OH（R6はC1〜C
13の炭化水素基）で示されるアルコールであることを特
徴とする、請求項１記載のエチレン系重合体の製造方
法。4. The nucleophilic reagent has the general formula R 3 COR 4 (R 3 and R 4 each represent a hydrogen atom or a C 1 to C 17 hydrocarbon group and may be the same or different from each other), and General formula (R 5 is a C 3 to C 17 divalent hydrocarbon group), an aldehyde or a ketone, or a general formula R 6 OH (R 6 is C 1 to C
13. The method for producing an ethylene polymer according to claim 1, which is an alcohol represented by 13 hydrocarbon groups.
4-r（R10は水素原子またはC1〜C8の炭化水素基、Ｘはハ
ロゲン原子、かつ０≦ｒ≦３）であることを特徴とす
る、請求項１記載のエチレン系重合体の製造方法。5. A silicon halide compound is represented by the general formula R 10 r SiX.
4-r (R 10 is a hydrogen atom or a C 1 to C 8 hydrocarbon group, X is a halogen atom, and 0 ≦ r ≦ 3), wherein the ethylene-based polymer according to claim 1 Production method.
式R11 sAlX3-s（R11はC1〜C12の炭化水素基、Ｘはハロゲ
ン原子、かつ１≦ｓ≦２）であることを特徴とする、請
求項１記載のエチレン系重合体の製造方法。6. A halogenated organoaluminum compound has the general formula R 11 s AlX 3-s (R 11 is a C 1 to C 12 hydrocarbon group, X is a halogen atom, and 1 ≦ s ≦ 2). The method for producing an ethylene-based polymer according to claim 1, which is characterized in that:
12 cAlY3-c（R12はC1〜C12の炭化水素基、Ｙは水素原
子、ハロゲン原子またはアルコキシド基、かつ１≦ｃ≦
３）であることを特徴とする、請求項１記載のエチレン
系重合体の製造方法。7. An organoaluminum compound [D] is represented by the general formula R
12 c AlY 3-c (R 12 is a C 1 to C 12 hydrocarbon group, Y is a hydrogen atom, a halogen atom or an alkoxide group, and 1 ≦ c ≦
The method for producing an ethylene-based polymer according to claim 1, which is 3).
との反応において、両者の量論的比率が、MgR2:Siのmol
比として1:1〜20の範囲であることを特徴とする、請求
項１記載のエチレン系重合体の製造方法。8. In the reaction of hydropolysiloxane and Grignard reagent, the stoichiometric ratio of the two is MgR 2 : Si mol.
The method for producing an ethylene polymer according to claim 1, wherein the ratio is in the range of 1: 1 to 20.
生成物〔Ｂ〕を合成するに当り、親核的試薬の添加量が
反応生成物〔Ａ〕中のSi−Ｈ基1mol当り1.0mol以下であ
り、鏡筒、反応生成物〔Ａ〕中のMg1mol当り0.5mol以上
の範囲であることを特徴とする、請求項１記載のエチレ
ン系重合体の製造方法。9. When the reaction product [B] is synthesized from the reaction product [A] and the nucleophilic reagent, the amount of the nucleophilic reagent added is the Si—H group in the reaction product [A]. The method for producing an ethylene polymer according to claim 1, wherein the amount is 1.0 mol or less per 1 mol, and the range is 0.5 mol or more per 1 mol of Mg in the reaction product [A] in the lens barrel.
合が、Ti:V:Zrの原子比として1:0.1〜10:0.1〜10の範囲
であることを特徴とする、請求項１記載のエチレン系重
合体の製造方法。10. The ethylene according to claim 1, wherein the reaction ratio of each component of the transition metal compound is 1: 0.1 to 10: 0.1 to 10 as an atomic ratio of Ti: V: Zr. Of producing a base polymer.
せて触媒成分〔Ｃ〕を調製するに当り、〔Ｉ〕のマグネ
シウム1mol当り、〔II〕が0.01〜1molであり、かつ
〔Ｉ〕と〔III〕の比率がそれぞれSi/Mg molで0.1〜
５、Al/Mg mol比で0.1〜50を満足する範囲であることを
特徴とする、請求項１記載のエチレン系重合体の製造方
法。11. When the catalyst component [C] is prepared by bringing [I], [II] and [III] into contact with each other, the amount of [II] is 0.01 to 1 mol per 1 mol of magnesium of [I], and The ratio of [I] and [III] is 0.1 to 0.1 in Si / Mg mol, respectively.
5. The method for producing an ethylene polymer according to claim 1, characterized in that the Al / Mg mol ratio is in the range of 0.1 to 50.
ィンがプロピレン，ブテン−1,ヘキセン−1,4−メチル
ペンテン−1,オクテン−１およびデセン−１の群の中か
ら一種類または二種類以上選ばれたものであることを特
徴とする、請求項１記載のエチレン系重合体の製造方
法。12. The other α-olefin to be copolymerized with ethylene is one or two selected from the group consisting of propylene, butene-1, hexene-1,4-methylpentene-1, octene-1 and decene-1. The method for producing an ethylene-based polymer according to claim 1, wherein one or more kinds are selected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22741588A JPH0757772B2 (en) | 1988-09-13 | 1988-09-13 | Method for producing ethylene-based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22741588A JPH0757772B2 (en) | 1988-09-13 | 1988-09-13 | Method for producing ethylene-based polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0275606A JPH0275606A (en) | 1990-03-15 |
| JPH0757772B2 true JPH0757772B2 (en) | 1995-06-21 |
Family
ID=16860484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22741588A Expired - Fee Related JPH0757772B2 (en) | 1988-09-13 | 1988-09-13 | Method for producing ethylene-based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757772B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0253613A (en) * | 1988-08-11 | 1990-02-22 | Sumitomo Rubber Ind Ltd | tire |
| JP2716615B2 (en) * | 1991-10-25 | 1998-02-18 | 丸善ポリマー株式会社 | Method for producing ethylene polymer composition |
-
1988
- 1988-09-13 JP JP22741588A patent/JPH0757772B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH0275606A (en) | 1990-03-15 |
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