JP2714992B2 - Method for producing polyolefin - Google Patents
Method for producing polyolefinInfo
- Publication number
- JP2714992B2 JP2714992B2 JP32386789A JP32386789A JP2714992B2 JP 2714992 B2 JP2714992 B2 JP 2714992B2 JP 32386789 A JP32386789 A JP 32386789A JP 32386789 A JP32386789 A JP 32386789A JP 2714992 B2 JP2714992 B2 JP 2714992B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- solid catalyst
- catalyst component
- polymerization
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229920000098 polyolefin Polymers 0.000 title claims description 11
- 239000011949 solid catalyst Substances 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 88
- 238000006116 polymerization reaction Methods 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000002245 particle Substances 0.000 description 29
- 238000009826 distribution Methods 0.000 description 21
- -1 magnesium halide Chemical class 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 230000005484 gravity Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 11
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000012685 gas phase polymerization Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 235000010724 Wisteria floribunda Nutrition 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229940075894 denatured ethanol Drugs 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CWPPDTVYIJETDF-UHFFFAOYSA-N 2,2,4-trimethylpentan-1-ol Chemical compound CC(C)CC(C)(C)CO CWPPDTVYIJETDF-UHFFFAOYSA-N 0.000 description 2
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-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
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 2
- ZKXITRNXHWEQJU-UHFFFAOYSA-N 3,5-dimethylheptan-4-ol Chemical compound CCC(C)C(O)C(C)CC ZKXITRNXHWEQJU-UHFFFAOYSA-N 0.000 description 2
- WETBJXIDTZXCBL-UHFFFAOYSA-N 3,5-dimethylhexan-1-ol Chemical compound CC(C)CC(C)CCO WETBJXIDTZXCBL-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-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
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-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
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BAJKSGJCPTWOMC-UHFFFAOYSA-L [F-].[F-].CCO[Ti++]OCC Chemical compound [F-].[F-].CCO[Ti++]OCC BAJKSGJCPTWOMC-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 2
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl 2-methoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 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
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N propyl benzoate Chemical compound CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- LLRZUDIHEZXFGV-UHFFFAOYSA-N (4-methylphenyl) benzoate Chemical compound C1=CC(C)=CC=C1OC(=O)C1=CC=CC=C1 LLRZUDIHEZXFGV-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
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- LFEHSRSSAGQWNI-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-ol Chemical compound CC(C)CC(C)CC(O)CC(C)C LFEHSRSSAGQWNI-UHFFFAOYSA-N 0.000 description 1
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- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- ZBVJIDOPGZCDDL-UHFFFAOYSA-N 4-methylpentan-2-ol pentan-1-ol Chemical compound CCCCCO.CC(C)CC(C)O ZBVJIDOPGZCDDL-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- PNCWZZXMSRPMDP-UHFFFAOYSA-M C1(C(C=CC=C1)C)(C)O[Ti]Cl Chemical compound C1(C(C=CC=C1)C)(C)O[Ti]Cl PNCWZZXMSRPMDP-UHFFFAOYSA-M 0.000 description 1
- NNXAUVIOTLCRFJ-UHFFFAOYSA-K CC(C)CO[Ti](Cl)(Cl)Cl Chemical compound CC(C)CO[Ti](Cl)(Cl)Cl NNXAUVIOTLCRFJ-UHFFFAOYSA-K 0.000 description 1
- KIDUHMAKCROADV-UHFFFAOYSA-L CC(C)O[Ti](Br)(Br)OC(C)C Chemical compound CC(C)O[Ti](Br)(Br)OC(C)C KIDUHMAKCROADV-UHFFFAOYSA-L 0.000 description 1
- BDBNCVOMHKVOST-UHFFFAOYSA-K CCCCCO[Ti](Cl)(Cl)Cl Chemical compound CCCCCO[Ti](Cl)(Cl)Cl BDBNCVOMHKVOST-UHFFFAOYSA-K 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- ZSBZSDFDORZFIG-UHFFFAOYSA-K CCO[Ti](F)(F)F Chemical compound CCO[Ti](F)(F)F ZSBZSDFDORZFIG-UHFFFAOYSA-K 0.000 description 1
- DPZIQFHCPYAEHV-UHFFFAOYSA-M CCO[Ti](F)(OCC)OCC Chemical compound CCO[Ti](F)(OCC)OCC DPZIQFHCPYAEHV-UHFFFAOYSA-M 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- 101100532679 Caenorhabditis elegans scc-1 gene Proteins 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- CJWANOYUFBSCHS-UHFFFAOYSA-L [Br-].[Br-].CCO[Ti+2]OCC Chemical compound [Br-].[Br-].CCO[Ti+2]OCC CJWANOYUFBSCHS-UHFFFAOYSA-L 0.000 description 1
- DJOXOOIJKINTOT-UHFFFAOYSA-K [Br-].[Br-].[Br-].CCO[Ti+3] Chemical compound [Br-].[Br-].[Br-].CCO[Ti+3] DJOXOOIJKINTOT-UHFFFAOYSA-K 0.000 description 1
- QSMLJCIHMPUAQG-UHFFFAOYSA-L [Cl-].[Cl-].CCCO[Ti+2]OCCC Chemical compound [Cl-].[Cl-].CCCO[Ti+2]OCCC QSMLJCIHMPUAQG-UHFFFAOYSA-L 0.000 description 1
- RTEOZDTUOYNHHJ-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CCCCC(CC)CO[Ti+3] Chemical compound [Cl-].[Cl-].[Cl-].CCCCC(CC)CO[Ti+3] RTEOZDTUOYNHHJ-UHFFFAOYSA-K 0.000 description 1
- OYMGHHRYTTWANU-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CCCCCCCCO[Ti+3] Chemical compound [Cl-].[Cl-].[Cl-].CCCCCCCCO[Ti+3] OYMGHHRYTTWANU-UHFFFAOYSA-K 0.000 description 1
- GKQZBJMXIUKBGB-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CCCO[Ti+3] Chemical compound [Cl-].[Cl-].[Cl-].CCCO[Ti+3] GKQZBJMXIUKBGB-UHFFFAOYSA-K 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 229940071248 anisate Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SWWYHGZVYNAAHI-UHFFFAOYSA-N benzyl 4-methoxybenzoate Chemical compound C1=CC(OC)=CC=C1C(=O)OCC1=CC=CC=C1 SWWYHGZVYNAAHI-UHFFFAOYSA-N 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- YBZROOQFBDFSHW-UHFFFAOYSA-L benzyl(dichloro)alumane Chemical compound [Cl-].[Cl-].[Al+2]CC1=CC=CC=C1 YBZROOQFBDFSHW-UHFFFAOYSA-L 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical group CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- ISFMCQATCMRFPY-UHFFFAOYSA-M chloro(diphenyl)alumane Chemical compound [Cl-].C=1C=CC=CC=1[Al+]C1=CC=CC=C1 ISFMCQATCMRFPY-UHFFFAOYSA-M 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 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
- MLOUXCNEZWLVJE-UHFFFAOYSA-N cyclopentyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCC1 MLOUXCNEZWLVJE-UHFFFAOYSA-N 0.000 description 1
- RQXXJDTUITUSMU-UHFFFAOYSA-M dibenzyl(chloro)alumane Chemical compound [Cl-].C=1C=CC=CC=1C[Al+]CC1=CC=CC=C1 RQXXJDTUITUSMU-UHFFFAOYSA-M 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- HRXSKIOIHQEGAI-UHFFFAOYSA-M diethylalumanylium;fluoride Chemical compound CC[Al](F)CC HRXSKIOIHQEGAI-UHFFFAOYSA-M 0.000 description 1
- PPQUYYAZSOKTQD-UHFFFAOYSA-M diethylalumanylium;iodide Chemical compound CC[Al](I)CC PPQUYYAZSOKTQD-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SOUAXOGPALPTTC-UHFFFAOYSA-N ethyl 2-methylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C SOUAXOGPALPTTC-UHFFFAOYSA-N 0.000 description 1
- WSJNYOVBJSOQST-UHFFFAOYSA-N ethyl 3-methylbenzoate Chemical compound CCOC(=O)C1=CC=CC(C)=C1 WSJNYOVBJSOQST-UHFFFAOYSA-N 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- 229940005667 ethyl salicylate Drugs 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-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
- 239000000155 melt Substances 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- RNHXTCZZACTEMK-UHFFFAOYSA-N methyl 4-ethoxybenzoate Chemical compound CCOC1=CC=C(C(=O)OC)C=C1 RNHXTCZZACTEMK-UHFFFAOYSA-N 0.000 description 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- HMRROBKAACRWBP-UHFFFAOYSA-N methyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1 HMRROBKAACRWBP-UHFFFAOYSA-N 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
- 229960001047 methyl salicylate Drugs 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- FCBBRODPXVPZAH-UHFFFAOYSA-N nonan-5-ol Chemical compound CCCCC(O)CCCC FCBBRODPXVPZAH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WOHDXQQIBRMRFA-UHFFFAOYSA-N phenyl 4-methylbenzoate Chemical compound C1=CC(C)=CC=C1C(=O)OC1=CC=CC=C1 WOHDXQQIBRMRFA-UHFFFAOYSA-N 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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- BPQPJXCUBLCZIB-UHFFFAOYSA-L phenylaluminum(2+);dichloride Chemical compound [Cl-].[Cl-].[Al+2]C1=CC=CC=C1 BPQPJXCUBLCZIB-UHFFFAOYSA-L 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 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
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本願発明は新規なポリオレフィンの製造方法に関す
る。さらに詳細には、本願発明は固体当たりの重合体収
量および遷移金属当たりの重合体収量を著しく増加さ
せ、その結果重合体中の触媒残渣を除去する工程を不要
ならしめ、また同時に生成重合体のかさ密度を高め、か
つ生成ポリマーの微粉状部分を減少させることができる
ばかりか、平均粒径が大きい良好な粒子性状を有するポ
リオレフィンを製造する方法に関する。The present invention relates to a novel method for producing a polyolefin. More specifically, the present invention significantly increases the polymer yield per solid and the polymer yield per transition metal, thereby eliminating the need for the step of removing catalyst residues in the polymer and, at the same time, reducing the amount of polymer formed. The present invention relates to a method for producing a polyolefin having a high average particle size and good particle properties, as well as capable of increasing the bulk density and reducing the finely powdered portion of the produced polymer.
（従来技術および発明が解決しようとする課題） 従来この種の技術分野においては、ハロゲン化マグネ
シウム、酸化マグネシウム、水酸化マグネシウムなどの
無機マグネシウム固体を担体としてこれにチタンまたは
バナジウムなどの遷移金属の化合物を担持させた触媒が
数多く知られている。しかしながら、これらの公知技術
においては、得られるポリオレフィンのかさ比重は一般
に小さく、また平均粒径も比較的小さく、粒径分布も概
して広いため微粒子状粉末部分が多く、生産性およびポ
リマーハンドリングの面から改良が強く望まれていた。
さらに、これらのポリマーを成形加工するさいにも粉塵
の発生、成形時の能率の低下等の問題を生ずるため、前
述したかさ密度の増大、微粒子状粉末部分の減少が強く
望まれていた。さらに、近年要求の高まっているペレッ
ト化工程を省略し、粉体ポリマーをそのまま加工機にか
けるためにはまだまだ改良が必要とされている。(Prior Art and Problems to be Solved by the Invention) Conventionally, in this kind of technical field, a compound of a transition metal such as titanium or vanadium is supported on an inorganic magnesium solid such as magnesium halide, magnesium oxide or magnesium hydroxide as a carrier. There are many known catalysts that support the compound. However, in these known techniques, the bulk specific gravity of the obtained polyolefin is generally small, the average particle size is relatively small, and the particle size distribution is generally wide, so that there are many fine powder portions, and from the viewpoint of productivity and polymer handling. Improvement was strongly desired.
Further, when forming these polymers, problems such as generation of dust and reduction in efficiency at the time of molding are caused. Therefore, it is strongly desired to increase the bulk density and to reduce the fine powder portion as described above. Further, in order to omit the pelletizing step, which has been increasing in recent years, and to apply the powder polymer to a processing machine as it is, improvement is still required.
本発明者らは先に上記の欠点を改良した新規触媒成分
を見出し、既に種々の特許出願を行った（特公平１−11
651、特公平１−12289、特開昭60−149605、特開昭62−
32105、特開昭62−207306等）。この触媒成分を用いた
場合かさ密度が高く、平均粒径の大きいポリマーを得る
ことができるが、ペレット化工程を省略し、粉体ポリマ
ーをそのまま加工機にかけるためにはさらに改良が必要
とされた。The present inventors have previously found a novel catalyst component in which the above-mentioned drawbacks have been improved, and have already filed various patent applications (Japanese Patent Publication No. 1-11).
651, Japanese Patent Publication No. 1-12289, JP-A-60-149605, JP-A-62
32105, JP-A-62-207306). When this catalyst component is used, a polymer having a high bulk density and a large average particle size can be obtained, but further improvement is required in order to omit the pelletizing step and to apply the powder polymer to a processing machine as it is. Was.
本発明はこれらの欠点を改良し、さらにかさ密度が高
く、かつ粒径分布が狭く、ポリマーの微粒子状部分が著
しく少なく、流動性の良好な重合体を極めて高活性に得
ることを目的として鋭意研究の結果、本発明に到達した
ものである。The present invention solves these drawbacks, and further aims at obtaining a highly flowable polymer having a high bulk density, a narrow particle size distribution, a remarkably small amount of polymer fine particles, and a high fluidity. As a result of research, the present invention has been achieved.
すなわち、本発明は、固体触媒成分と有機金属化合物
を触媒としてオレフィンを重合または共重合する方法に
おいて、該固体触媒成分が ［Ｉ］（１） ケイ素酸化物および／またはアルミニウ
ム酸化物、 （２） ハロゲン化マグネシウムおよび一般式Me
（OR）nXz-n（ここでMeはNa、Mg、Ca、Zn、Cd、Ｂ、A
l、SiおよびSnからなる群から選ばれる元素、ｚは元素M
eの原子価、ｎは０＜ｎ≦ｚ、Ｘはハロゲン原子、Ｒは
炭素数１〜20の炭化水素基を示す）で表される化合物 を反応させて得られる反応生成物および （３） 一般式Ti（OR′）nX4-n（ここでＲ′
は、炭素数１〜20の炭化水素基、Ｘはハロゲン原子を表
わし、ｎは０≦ｎ＜４である）で表されるチタン化合物
を、 （４） 一般式ROH（ここでＲは炭素数６〜20の
炭化水素基、または、酸素、窒素、イオウ、塩素等の元
素を含む有機残基を示す）で表される化合物の存在下、 相互に反応させて得られる反応生成物に、 ［II］ 一般式AlRnX3-n（ここでＲは炭素数１〜24の炭
化水素基、Ｘはハロゲン原子を表わし、ｎは０＜ｎ≦３
である）で表わされる有機アルミニウム化合物を反応さ
せて得られる物質からなることを特徴とするポリオレフ
ィンの製造方法。That is, the present invention provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component comprises: [I] (1) a silicon oxide and / or an aluminum oxide; Magnesium halide and general formula Me
(OR) n X zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from the group consisting of l, Si and Sn, and z is an element M
e), n is 0 <n ≦ z, X is a halogen atom, and R is a hydrocarbon group having 1 to 20 carbon atoms). General formula Ti (OR ') n X 4-n (where R'
Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number of 0 ≦ n <4). (4) A general formula ROH (where R represents a number of carbon atoms) 6-20, or an organic residue containing an element such as oxygen, nitrogen, sulfur, chlorine, etc.) in the presence of a compound represented by the following formula: II] General formula AlR n X 3-n (where R represents a hydrocarbon group having 1 to 24 carbon atoms, X represents a halogen atom, and n represents 0 <n ≦ 3)
Which comprises reacting the organoaluminum compound represented by the formula (1).
本発明の方法を用いることにより、平均粒径が比較的
大きく、粒度分布が狭く、微粒子状部分が少ないポリオ
レフィンが極めて高活性に得られ、また生成ポリオレフ
ィンのかさ比重は高く、自由流動性も良好等、重合操作
上非常に有利となり、さらにペレットとして用いる場合
はもちろんのこと粉体状のままでも成形加工に供するこ
とができ、成形加工時のトラブルも少なく、きわめて有
利にポリオレフィンを製造することができる。By using the method of the present invention, a polyolefin having a relatively large average particle size, a narrow particle size distribution, and a small number of fine particles can be obtained with extremely high activity, and the produced polyolefin has a high bulk specific gravity and a good free-flowing property. It is very advantageous in polymerization operation, etc., and can be used for molding even if it is in powder form as well as when used as pellets, there are few troubles during molding, and it is extremely advantageous to produce polyolefin. it can.
本発明の触媒を用いて得られるポリマーは分子量分布
がきわめて狭く、また、ヘキサン抽出量が少なく、低重
合物の副生が非常に少ないことも特徴である。したがっ
て本発明の方法で得られた分子量分布の狭いポリオレフ
ィンをフィルム用に供した場合には、強度が高く、透明
性にすぐれ、かつ抗ブロッキング性およびヒートシール
性がすぐれているなど多くの長所を有する。The polymer obtained by using the catalyst of the present invention is characterized in that the molecular weight distribution is extremely narrow, the amount of hexane extracted is small, and the by-product of low polymer is very small. Therefore, when a polyolefin having a narrow molecular weight distribution obtained by the method of the present invention is used for a film, it has many advantages such as high strength, excellent transparency, and excellent antiblocking and heat sealing properties. Have.
以下、本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically.
本発明のポリオレフィンの製造方法において用いる触
媒は、 ［Ｉ］（１）ケイ素酸化物および／またはアルミニウム
酸化物、 （２）ハロゲン化マグネシウムと一般式Me（OR）
nXz-nで表わされる化合物を反応させて得られる反応生
成物および（３）一般式Ti（OR′）nX4-nで表されるチ
タン化合物を、（４）一般式ROHで表される化合物の存
在下、相互に反応させて得られる物質（第［Ｉ］成
分）、および ［II］ 一般式AlRnX3-nで表される有機アルミニウム化
合物（第［II］成分）を反応させて得られる物質からな
る固体触媒成分と有機金属化合物よりなる。The catalyst used in the method for producing a polyolefin of the present invention includes: [I] (1) a silicon oxide and / or an aluminum oxide, (2) a magnesium halide and a general formula Me (OR)
A reaction product obtained by reacting a compound represented by n X zn and (3) a titanium compound represented by the general formula Ti (OR ′) n X 4-n are converted into (4) a ROH represented by the general formula ROH In the presence of the compound, a substance (component [I]) obtained by reacting with each other and [II] an organoaluminum compound (component [II]) represented by the general formula AlR n X 3-n are reacted. And an organometallic compound.
＜１＞ 固体触媒成分 1. 第［Ｉ］成分 （１） 本発明において用いるケイ素酸化物とはシリカ
もしくは、ケイ素と周期律表Ｉ〜VIII族の少なくとも一
種の他の金属との複酸化物である。<1> Solid catalyst component 1. Component [I] (1) The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one other metal of Groups I to VIII of the periodic table. is there.
本発明において用いるアルミニウム酸化物とはアルミ
ナもしくはアルミニウムと周期律表Ｉ〜VIII族の少なく
とも一種の他の金属との複酸化物である。The aluminum oxide used in the present invention is a double oxide of alumina or aluminum and at least one other metal of Groups I to VIII of the periodic table.
ケイ素またはアルミニウムと周期律表Ｉ〜VIII族の少
なくとも一種の他の金属との複酸化物の代表的なものと
してはAl2O3・MgO,Al2O3・CaO,Al2O3・SiO2,Al2O3・MgO
・CaO,Al2O3・MgO・SiO2,Al2O3・CuO,Al2O3・Fe2O3,Al2
O3・NiO,SiO2・MgOなどの天然または合成の各種複酸化
物を例示することができる。ここで上記の式は分子式で
はなく、組成のみを表わすものであって、本発明におい
て用いられる複酸化物の構造および成分比率は特に限定
されるものではない。なお、当然のことながら、本発明
において用いるケイ素酸化物および／またはアルミニウ
ム酸化物は少量の水分を吸着していても差し支えなく、
また少量の不純物を含有していても支障なく使用でき
る。Representative examples of the complex oxide of silicon or aluminum and at least one other metal of Group I to VIII of the periodic table include Al 2 O 3 .MgO, Al 2 O 3 .CaO, Al 2 O 3 .SiO 2 , Al 2 O 3・ MgO
・ CaO, Al 2 O 3・ MgO ・ SiO 2 , Al 2 O 3・ CuO, Al 2 O 3・ Fe 2 O 3 , Al 2
Various natural or synthetic double oxides such as O 3 .NiO and SiO 2 .MgO can be exemplified. Here, the above formula is not a molecular formula, but only a composition, and the structure and component ratio of the double oxide used in the present invention are not particularly limited. It should be noted that the silicon oxide and / or aluminum oxide used in the present invention may adsorb a small amount of water,
Even if it contains a small amount of impurities, it can be used without any problem.
また、これらのケイ素酸化物および／またはアルミニ
ウム酸化物の性状は、本発明の目的を損なわない限り等
に限定されないが、好ましくは粒径が１〜200μｍ、細
孔容積が0.3ml/g以上、表面積が50m2/g以上のシリカが
望ましい。また使用するにあたって予め200〜800℃で常
法により焼成処理を施すことが望ましい。Further, the properties of these silicon oxides and / or aluminum oxides are not limited as long as the object of the present invention is not impaired, but preferably the particle size is 1 to 200 μm, the pore volume is 0.3 ml / g or more, Silica having a surface area of 50 m 2 / g or more is desirable. In use, it is desirable to previously perform a baking treatment at 200 to 800 ° C. by a conventional method.
（２） 本発明に使用されるハロゲン化マグネシウムと
しては実質的に無水のものが用いられ、フッ化マグネシ
ウム、塩化マグネシウム、臭化マグネシウム、およびヨ
ウ化マグネシウムがあげられ、とくに塩化マグネシウム
が好ましい。(2) As the magnesium halide used in the present invention, a substantially anhydrous magnesium halide is used, and examples thereof include magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, and magnesium chloride is particularly preferred.
また本発明において、これらのハロゲン化マグネシウ
ムはアルコール、エステル、ケトン、カルボン酸、エー
テル、アミン、ホスフィンなどの電子供与体で処理した
ものであってもよい。In the present invention, these magnesium halides may be those treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether, amine and phosphine.
本発明に使用される一般式Me（OR）nXz-n（ここでMe
はMa、Mg、Ca、Zn、Cd、Ｂ、Al、SiおよびSnからなる群
から選なれる元素、ｚは元素Meの原子価、ｎは０＜ｎ≦
ｚ、Ｘはハロゲン原子を示す。またＲは炭素数１〜20、
好ましくは１〜８のアルキル基、アリール基、アラルキ
ル基等の炭化水素基を示し、それぞれ同一でもまた異な
っていてもより）で表わされる化合物としては、たとえ
ばNaOR,Mg（OR）2,Mg（OR）X,Ca（OR）2,Zn（OR）2,Cd
（OR）2,B（OR）2,Al（OR）3,Al（OR）2X,Al（OR）X2,S
i（OR）4,Si（OR）3X,Si（OR）2X2,Si（OR）X3,Sn（O
R）４などで示される各種の化合物をあげることができ
る。これらの好ましい具体例としては、Mg（OC2H5）2,M
g（OC2H5）Cl,Al（OCH3）3,Al（OC2H5）3,Al（On−C
3H7）3,Al（Oi−C3H7）3,Al（On−C4H9）3,Al（Osec−C
4H9）3,Al（Ot−C4H9）2,Al（OCH3）2Cl,Al（OC2H5）2C
l,Al（OC2H5）Cl2,Al（Oi−C3H7）2Cl,Al（Oi−C3H7）C
l2,Al（OC6H5）3,Al（OC6H5）2Cl,Al（OC6H5）Cl2,Al
（OC6H4CH3）3,Al（OC6H4CH3）2Cl,Al（OC6H4CH3）Cl2,
Al（COH2C6H5）3,Si（OC2H5）4,Si（OC2H5）3Cl,Si（OC
2H5）2Cl2,Si（OC2H5）Cl3,Si（OC6H5）4,Si（OC6H5）3
Cl,Si（OC6H5）2Cl2,Si（OC2H5）Cl3,Si（COH2C6H5）４
などの化合物をあげることができる。The general formula Me (OR) n X zn (where Me
Is an element selected from the group consisting of Ma, Mg, Ca, Zn, Cd, B, Al, Si and Sn, z is the valence of the element Me, and n is 0 <n ≦
z and X represent a halogen atom. R has 1 to 20 carbon atoms;
Preferred examples of the compound represented by 1 to 8 hydrocarbon groups such as an alkyl group, an aryl group, and an aralkyl group, which may be the same or different) include, for example, NaOR, Mg (OR) 2 , Mg ( OR) X, Ca (OR) 2 , Zn (OR) 2 , Cd
(OR) 2 , B (OR) 2 , Al (OR) 3 , Al (OR) 2 X, Al (OR) X 2 , S
i (OR) 4 , Si (OR) 3 X, Si (OR) 2 X 2 , Si (OR) X 3 , Sn (O
R) Various compounds represented by 4, etc. can be mentioned. Preferred examples of these include Mg (OC 2 H 5 ) 2 , M
g (OC 2 H 5 ) Cl, Al (OCH 3 ) 3 , Al (OC 2 H 5 ) 3 , Al (On-C
3 H 7) 3, Al ( Oi-C 3 H 7) 3, Al (On-C 4 H 9) 3, Al (Osec-C
4 H 9) 3, Al ( Ot-C 4 H 9) 2, Al (OCH 3) 2 Cl, Al (OC 2 H 5) 2 C
l, Al (OC 2 H 5 ) Cl 2, Al (Oi-C 3 H 7) 2 Cl, Al (Oi-C 3 H 7) C
l 2 , Al (OC 6 H 5 ) 3 , Al (OC 6 H 5 ) 2 Cl, Al (OC 6 H 5 ) Cl 2 , Al
(OC 6 H 4 CH 3 ) 3 , Al (OC 6 H 4 CH 3 ) 2 Cl, Al (OC 6 H 4 CH 3 ) Cl 2 ,
Al (COH 2 C 6 H 5 ) 3, Si (OC 2 H 5) 4, Si (OC 2 H 5) 3 Cl, Si (OC
2 H 5) 2 Cl 2, Si (OC 2 H 5) Cl 3, Si (OC 6 H 5) 4, Si (OC 6 H 5) 3
Cl, Si (OC 6 H 5 ) 2 Cl 2 , Si (OC 2 H 5 ) Cl 3 , Si (COH 2 C 6 H 5 ) 4
And the like.
ハロゲン化マグネシウムと一般式Me（OR）nXz-nで表
わされる化合物との反応割合は、Me/Mg（モル比）が0.0
1〜10、好ましくは0.1〜５の範囲が望ましい。The reaction ratio between the magnesium halide and the compound represented by the general formula Me (OR) n X zn is such that Me / Mg (molar ratio) is 0.0
A range of 1 to 10, preferably 0.1 to 5 is desirable.
ハロゲン化マグネシウムと一般式Me（OR）nXz-nで表
わされる化合物との反応方法は特に限定されるものでは
なく、不活性の炭化水素溶媒の存在下または不存在下、
両者を温度０〜200℃にて30分〜50時間、ボールミル、
振動ミル、ロッドミル、衝撃ミルなどを用いて共粉砕す
る方法を用いてもよく、また、不活性炭化水素、アルコ
ール類、フェノール類、エーテル類、ケトン類、エステ
ル類、アミン類、ニトリル類等あるいはそれらの混合物
からなる有機溶媒中で両者を20〜400℃、好ましくは50
〜300℃の温度で５分〜10時間混合加熱反応させ、しか
る後溶媒を蒸発除去する方法を用いてもよい。The method of reacting the magnesium halide with the compound represented by the general formula Me (OR) n X zn is not particularly limited, and in the presence or absence of an inert hydrocarbon solvent,
Both at a temperature of 0 to 200 ° C for 30 minutes to 50 hours, ball mill,
A method of co-milling using a vibration mill, a rod mill, an impact mill, or the like may be used, and an inert hydrocarbon, alcohols, phenols, ethers, ketones, esters, amines, nitriles, or the like, or Both in an organic solvent consisting of a mixture thereof at 20 to 400 ° C., preferably 50
A method of mixing and reacting at a temperature of 300300 ° C. for 5 minutes to 10 hours and then removing the solvent by evaporation may be used.
本発明においては両者を共粉砕する方法が好ましく用
いられる。In the present invention, a method in which both are pulverized is preferably used.
（３） 本発明において用いる一般式Ti（OR′）nX4-n
（ここでＲ′は、炭素数１〜20、好ましくは１〜12のア
ルキル基、アリール基、アラルキル基等の炭化水素基、
Ｘはハロゲン原子を示し、ｎは０≦ｎ＜４である）で表
わされるチタン化合物としては、具体的には、四塩化チ
タン、四臭化チタン、四ヨウ化チタン等のテトラハロゲ
ン化チタン、モノメトキシトリクロロチタン、ジメトキ
シジクロロチタン、トリメトキシモノクロロチタン、モ
ノエトキシトリクロロチタン、モノエトキシトリフルオ
ロチタン、モノエトキシトリブロモチタン、ジエトキシ
ジフルオロチタン、ジエトキシジクロロチタン、ジエト
キシジブロモチタン、ジエトキシジフルオロチタン、ト
リエトキシフルオロチタン、トリエトキシクロロチタ
ン、モノプロポキシトリクロロチタン、モノイソプロポ
キシトリクロロチタン、ジプロポキシジクロロチタン、
ジイソプロポキシジクロロチタン、ジイソプロポキシジ
ブロモチタン、トリイソプロポキシフルオロチタン、ト
リプロポキシクロロチタン、モノブトキシトリクロロチ
タン、モノイソブトキシトリクロロチタン、ジブトキシ
ジクロロチタン、ジイソプロポキシジクロロチタン、ト
リブトキシブルオロチタン、トリブトキシクロロチタ
ン、トリイソブトキシトリクロロチタン、モノペントキ
シトリクロロチタン、ジペントキシジクロロチタン、ト
リペントキシモノクロロチタン、モノオクチルオキシト
リクロロチタン、ジオクチルオクチルジクロロチタン、
トリオクチルオキシモノクロロチタン、モノ−２−エチ
ルヘキシルオキシトリクロロチタン、ジ−２−エチルヘ
キシルオキシジクロロチタン、トリ−２−エチルヘキシ
ルオキシモノクロロチタン、モノフェノキシトリクロロ
チタン、ジフェノキシジクロロチタン、トリフェノキシ
クロロチタン、トリ−ｏ−キシレンオキシクロロチタン
または、これらの任意混合物などが例示され、好ましく
は、四塩化チタン、モノエトキシトリクロロチタン、ジ
エトキシジクロロチタン、モノブトキシトリクロロチタ
ン、ジブトキシジクロロチタンが望ましい。(3) General formula Ti (OR ') nX4 -n used in the present invention
(Where R ′ is a hydrocarbon group such as an alkyl group having 1 to 20, preferably 1 to 12 carbon atoms, an aryl group, an aralkyl group,
X represents a halogen atom, and n represents 0 ≦ n <4). Specific examples of the titanium compound include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like; Monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, monoethoxytrichlorotitanium, monoethoxytrifluorotitanium, monoethoxytribromotitanium, diethoxydifluorotitanium, diethoxydichlorotitanium, diethoxydibromotitanium, diethoxydifluorotitanium , Triethoxyfluorotitanium, triethoxychlorotitanium, monopropoxytrichlorotitanium, monoisopropoxytrichlorotitanium, dipropoxydichlorotitanium,
Diisopropoxydichlorotitanium, diisopropoxydibromotitanium, triisopropoxyfluorotitanium, tripropoxychlorotitanium, monobutoxytrichlorotitanium, monoisobutoxytrichlorotitanium, dibutoxydichlorotitanium, diisopropoxydichlorotitanium, tribubutoxy blue titanium , Tributoxychlorotitanium, triisobutoxytrichlorotitanium, monopentoxytrichlorotitanium, dipentoxydichlorotitanium, tripentoxymonochlorotitanium, monooctyloxytrichlorotitanium, dioctyloctyldichlorotitanium,
Trioctyloxymonochlorotitanium, mono-2-ethylhexyloxytrichlorotitanium, di-2-ethylhexyloxydichlorotitanium, tri-2-ethylhexyloxymonochlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxychlorotitanium, tri- Examples thereof include o-xyleneoxychlorotitanium or an arbitrary mixture thereof. Preferably, titanium tetrachloride, monoethoxytrichlorotitanium, diethoxydichlorotitanium, monobutoxytrichlorotitanium, and dibutoxydichlorotitanium are desirable.
（４） 本発明の第［Ｉ］成分は、前記（１）ケイ素酸
化物および／またはアルミニウム酸化物（成分［Ｉ］−
（１））、（２）ハロゲン化マグネシウムと一般式Me
（OR）nXz-nで表わされる化合物を反応させて得られる
反応生成物（成分［Ｉ］−（２））および（３）一般式
Ti（OR′）nX4-nで表わされるチタン化合物（成分
［Ｉ］−（３））を、一般式ROHで表わされる化合物の
存在下、相互に反応させることにより得る。(4) The component [I] of the present invention comprises the aforementioned (1) silicon oxide and / or aluminum oxide (component [I]-
(1)), (2) Magnesium halide and general formula Me
A reaction product (component [I]-(2)) obtained by reacting a compound represented by (OR) n X zn and (3) a general formula
Ti (OR ') a titanium compound represented by n X 4-n (component [I] - (3)) to give the presence of a compound represented by the general formula ROH, by reacting with one another.
一般式ROHで表わされる化合物としては、式中のＲが
炭素数６〜20、好ましくは６〜12の有機残基であり、炭
化水素基または酸素、窒素、イオウ、塩素等の元素を含
む有機残基がある。該炭化水素基としてはアルキル基、
アルケニル基、アリール基、アラルキル基等が望まし
く、特に分枝構造を有する炭化水素基であることが好ま
しい。上記一般式で表わされる化合物としては、具体的
には、１−ヘキサノール、２−メチル−１−ペンタノー
ル、４−メチル−１−ペンタノール、４−メチル−２−
ペンタノール、２−エチル−１−ブタノール、１−ヘプ
タノール、２−ヘプタノール、３−ヘプタノール、４−
ヘプタノール、2,4−ジメチル−３−ペンタノール、１
−オクタノール、２−オクタノール、２−エチル−１−
ヘキサノール、3,5−ジメチル−１−ヘキサノール、2,
2,4−トリメチル−１−ペンタノール、１−ノナノー
ル、５−ノナノール、3,5−ジメチル−４−ヘプタノー
ル、2,6−ジメチル−４−ヘプタノール、3,5,5−トリメ
チル−１−ヘキサノール、１−デカノール、１−ウンデ
カノール、１−ドデカノール、2,6,8−トリメチル−４
−ノナノール、１−トリデカノール、１−ペンタデカノ
ール、１−ヘキサデカノール、１−ヘプタデカノール、
１−オクタデカノール、１−ノナデカノール、１−エイ
コサノール、フェノール、クロロフェノール、ベンジル
アルコール、メチルセロソルブまたはこれらの任意混合
物などが挙げられ、好ましくは、２−メチル−１−ペン
タノール、４−メチル−１−ペンタノール、４−メチル
−２−ペンタノール、２−エチル−１−ブタノール、2,
4−ジメチル−３−ペンタノール、２−エチル−１−ヘ
キサノール、3,5−ジメチル−１−ヘキサノール、2,2,4
−トリメチル−１−ペンタノール、3,5−ジメチル−４
−ヘプタノール、2,6−ジメチル−４−ヘプタノール、
3,5,5−トリメチル−１−ヘキサノーウなどが望まし
い。As the compound represented by the general formula ROH, R in the formula is an organic residue having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and an organic group containing a hydrocarbon group or an element such as oxygen, nitrogen, sulfur, or chlorine. There are residues. As the hydrocarbon group, an alkyl group,
An alkenyl group, an aryl group, an aralkyl group and the like are desirable, and a hydrocarbon group having a branched structure is particularly preferred. As the compound represented by the above general formula, specifically, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol
Pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-
Heptanol, 2,4-dimethyl-3-pentanol, 1
-Octanol, 2-octanol, 2-ethyl-1-
Hexanol, 3,5-dimethyl-1-hexanol, 2,
2,4-trimethyl-1-pentanol, 1-nonanol, 5-nonanol, 3,5-dimethyl-4-heptanol, 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol , 1-decanol, 1-undecanol, 1-dodecanol, 2,6,8-trimethyl-4
-Nonanol, 1-tridecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol,
1-octadecanol, 1-nonadecanol, 1-eicosanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve or an arbitrary mixture thereof, and the like, preferably 2-methyl-1-pentanol, 4-methyl- 1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 2,
4-dimethyl-3-pentanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2,2,4
-Trimethyl-1-pentanol, 3,5-dimethyl-4
-Heptanol, 2,6-dimethyl-4-heptanol,
3,5,5-Trimethyl-1-hexanol is desirable.
第［Ｉ］成分を得る際の成分［Ｉ］−（１）〜［Ｉ］
−（３）の反応方法は、一般式ROHで表わされる化合物
の存在下において行う限り等に制限されるものではな
く、反応順序としては、 （Ａ） 成分［Ｉ］−（１）〜成分［Ｉ］−（３）を同
時に接触させる方法、 （Ｂ） 成分［Ｉ］−（１）と成分［Ｉ］−（２）を接
触したのち、成分［Ｉ］−（３）をさらに接触させる方
法、 （Ｃ） 成分［Ｉ］−（１）と成分［Ｉ］−（３）を接
触したのち、成分［Ｉ］−（２）をさらに接触させる方
法、 （Ｄ） 成分［Ｉ］−（２）と成分［Ｉ］−（３）を接
触したのち、成分［Ｉ］−（１）をさらに接触させる方
法 のいずれでもよいが、好ましくは、上記のうち（Ｄ）の
方法が望ましく、さらに好ましくは一般式ROHで表わさ
れる化合物を溶媒として用い、成分［Ｉ］−（２）およ
び成分［Ｉ］−（３）を予め溶解接触させたのち成分
［Ｉ］−（１）を接触させる方法が望ましく、また、こ
のときの一般式ROHで表わされる化合物への［Ｉ］−
（２）および成分［Ｉ］−（３）の溶解順序は、特に制
限されるものではなく、両者を同時に溶解してもよく、
いずれか一方を先に溶解させてもよい。また、成分
［Ｉ］−（２）および／または成分［Ｉ］−（３）を予
め前記一般式ROHで表わされる化合物よりも炭素数の少
ない（すなわち、炭素数が１〜５の）炭素水素基を有す
る該化合物、いわゆる低級アルコールに溶解させたの
ち、一般式ROHで表わされる化合物の存在下、成分
［Ｉ］−（２）および／または成分［Ｉ］−（３）を含
む低級アルコール溶液を他の成分と相互に接触させる方
法も好適に用いられる。なお、この際用いる低級アルコ
ールとしては、炭素数が１〜５のアルキル基を有するア
ルコールが好ましく、メタノール、エタノール、１−プ
ロパノール、２−プロパノール、１−ブタノール、２−
ブタノール、２−メチル−１−プロパノール、２−メチ
ル−２−プロパノール、１−ペンタノール、２−ペンタ
ノール、３−ペンタノール、２−メチル−１−ブタノー
ル、３−メチル−１−ブタノール、２−メチル−２−ブ
タノール、３−メチル−２−ブタノール、2,2−ジメチ
ル−１−プロパノールなどが挙げられ、もちろん、工業
用アルコールとして市販されているメタノール変性エタ
ノール、ヘキサン変性エタノール等各種変性アルコール
も何ら支障なく用いることができる。Components [I]-(1) to [I] for obtaining the component [I]
The reaction method of-(3) is not limited as long as it is carried out in the presence of the compound represented by the general formula ROH, and the reaction order is as follows: (A) Component [I]-(1) to Component [ (B) a method of contacting the component [I]-(1) with the component [I]-(2), and further contacting the component [I]-(3). (C) a method of contacting the component [I]-(3) with the component [I]-(3) and then further contacting the component [I]-(2), (D) the component [I]-(2) ) And the component [I]-(3), and then the component [I]-(1) is further contacted, but the method (D) is preferable, and the method is more preferable. Uses a compound represented by the general formula ROH as a solvent, and converts component [I]-(2) and component [I]-(3) Component mixture was allowed to fit dissolved contact [I] - (1) a method of contacting is desirable, also, [I] to the compound represented by the general formula ROH in this case -
The order of dissolution of (2) and component [I]-(3) is not particularly limited, and both may be dissolved simultaneously.
Either one may be dissolved first. Further, the component [I]-(2) and / or the component [I]-(3) are previously converted to a hydrocarbon having a smaller number of carbon atoms (that is, 1 to 5 carbon atoms) than the compound represented by the general formula ROH. A lower alcohol solution containing a component [I]-(2) and / or a component [I]-(3) in the presence of a compound represented by the general formula ROH after being dissolved in the compound having a group, so-called lower alcohol. Is preferably used also in a method in which is brought into contact with other components. The lower alcohol used at this time is preferably an alcohol having an alkyl group having 1 to 5 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2 -Methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol and the like, and of course, various denatured alcohols such as methanol-denatured ethanol and hexane-denatured ethanol which are commercially available as industrial alcohols Can be used without any problem.
これら成分［Ｉ］−（１）〜［Ｉ］−（３）の接触方
法としては、一般式ROHで表わされる化合物の存在下、
成分［Ｉ］−（１）、成分［Ｉ］−（２）および成分
［Ｉ］−（３）を前記接触順序に従い、20〜300℃、好
ましくは50〜150℃の温度で１分〜48時間、好ましくは
１〜５時間混合反応し、しかるのち、一般式ROHで表わ
される化合物を減圧および／または加熱等の手法により
除去すべく操作を行うことが望ましい。As a method for contacting these components [I]-(1) to [I]-(3), in the presence of a compound represented by the general formula ROH,
Component [I]-(1), component [I]-(2) and component [I]-(3) are subjected to the above-mentioned contact sequence at a temperature of 20 to 300 ° C., preferably 50 to 150 ° C. for 1 minute to 48 hours. It is desirable to carry out the mixing reaction for a period of time, preferably 1 to 5 hours, and then to carry out an operation to remove the compound represented by the general formula ROH by a technique such as reduced pressure and / or heating.
また、各成分の反応割合については、まず、成分
［Ｉ］−（１）と成分［Ｉ］−（２）とは、分［Ｉ］−
（１）1gあたり、成分［Ｉ］−（２）中のMgのモル数が
0.01〜20mmol、好ましくは0.1〜10mmolさらに好ましく
は0.2〜4.0mmolとなるように反応させることが望まし
い。In addition, regarding the reaction ratio of each component, first, the component [I]-(1) and the component [I]-(2) are separated by the component [I]-
(1) The mol number of Mg in the component [I]-(2) per 1 g
The reaction is desirably performed so as to be 0.01 to 20 mmol, preferably 0.1 to 10 mmol, and more preferably 0.2 to 4.0 mmol.
また、成分［Ｉ］−（１）と成分［Ｉ］−（３）と
は、成分［Ｉ］−（１）の焼成処理の有無またはその焼
成処理条件により異なるが、成分［Ｉ］−（１）1gあた
り、成分［Ｉ］−（３）を0.01〜10.0mmol、好ましくは
0.1〜5.0mmol、さらに好ましくは0.2〜2.0mmol用い、反
応させることが望ましい。The component [I]-(1) and the component [I]-(3) differ depending on whether or not the component [I]-(1) has been subjected to the calcination treatment or the calcination conditions thereof. 1) Component [I]-(3) is contained in an amount of 0.01 to 10.0 mmol, preferably 1 g, per 1 g.
It is desirable to use 0.1 to 5.0 mmol, more preferably 0.2 to 2.0 mmol, for the reaction.
また、一般式ROHで表わされる化合物の使用量は、通
常成分［Ｉ］−（２）1gに対し、一般式ROHで表わされ
る化合物を５〜50g、好ましくは10〜30g用いることが望
ましい。The amount of the compound represented by the general formula ROH is preferably 5 to 50 g, and more preferably 10 to 30 g, of the compound represented by the general formula ROH per 1 g of the component [I]-(2).
2. 第［II］成分 本発明において使用される一般式AlRnX3-nで表わされ
る有機アルミニウム化合物としては、Ｒが炭素数１〜2
4、好ましくは１〜12のアルキル基、アリール基、アラ
ルキル基等の炭化水素基、Ｘが水素原子またはハロゲン
原子を示すものであり、かつｎが０＜ｎ≦３を示すもの
である。2. As the organoaluminum compound represented by the [II] Formula used in component present invention AlR n X 3-n, R is carbon atoms 1-2
4, preferably 1 to 12 hydrocarbon groups such as alkyl, aryl and aralkyl groups, X represents a hydrogen atom or a halogen atom, and n represents 0 <n ≦ 3.
これらの有機アルミニウム化合物としては、トリメチ
ルアルミニウム、トリエチルアルミニウム、トリ−ｎ−
プロピルアルミニウム、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、トリ−ｎ−ヘキシル
アルミニウム、トリ−ｎ−オクチルアムミニウム、ジエ
チルアルミニウムハイドライド、ジイソブチルアルミニ
ウムハイドライド、ジメチルアルミニウムクロライド、
ジエチルアルミニウムフルロライド、ジエチルアルミニ
ウムクロリド、ジエチルアルミニウムブロミド、ジエチ
ルアルミニウムアイオダイド、ジイソブチルアルミニウ
ムクロリド、メチルアルミニウムセスキクロリド、エチ
ルアルミニウムセスキブロミド、メチルアルミニウムジ
クロリド、エチルアルミニウムジクロリド、イソブチル
アルミニウムジクロリド、フエニルアルミニウムジクロ
リド、ジフエニルアルミニウムクロリド、ベンジルアル
ミニウムジクロリド、ジベンジルアルミニウムクロリド
またはこれらの任意混合物などを挙げることが出来、特
に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、エチルアルミニウムジクロリドが好ま
しい。As these organic aluminum compounds, trimethylaluminum, triethylaluminum, tri-n-
Propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylammonium, diethylaluminum hydride, diisobutylaluminum hydride, dimethylaluminum chloride,
Diethylaluminum fluoride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquibromide, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, phenylaluminum dichloride, Examples thereof include diphenylaluminum chloride, benzylaluminum dichloride, dibenzylaluminum chloride and an arbitrary mixture thereof, and particularly preferred are ethylaluminum sesquichloride, diethylaluminum chloride, and ethylaluminum dichloride.
3. 固体触媒成分の製造 本発明において用いる固体触媒成分は、前記第［Ｉ］
成分および第［II］成分を反応させることにより得られ
る。この場合の接触方法としては特に限定されるもので
はないが、例えばペンタン、ヘキサン、シクロヘキサ
ン、ヘプタン、オクタン、ノナン、デカン、ベンゼン、
トルエン、キシレン等、またはこれらの混合物等の一般
のZiegler触媒に不活性ないわゆる不活性炭化水素溶媒
の存在下または不存在下、温度０〜300℃、好ましくは2
0〜150℃にて５分〜10時間混合加熱反応させ、しかる
後、溶媒を蒸発除去する方法が好ましく用いられる。3. Production of Solid Catalyst Component The solid catalyst component used in the present invention is the above-mentioned [I]
It is obtained by reacting the component and the component [II]. Although the contact method in this case is not particularly limited, for example, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene,
In the presence or absence of a so-called inert hydrocarbon solvent inert to common Ziegler catalysts such as toluene, xylene or the like, or a mixture thereof, at a temperature of 0 to 300 ° C., preferably 2 ° C.
A method of mixing and reacting at 0 to 150 ° C. for 5 minutes to 10 hours and then removing the solvent by evaporation is preferably used.
なお、第［Ｉ］成分と第［II］成分の反応割合は、第
［II］成分／第［Ｉ］成分中の成分［Ｉ］−（３）｝
（モル比）が0.01〜100、好ましくは0.2〜10、さらに好
ましくは0.5〜５となるようにすることが望ましい。The reaction ratio between the component [I] and the component [II] is determined by the ratio of the component [I]-(3) in the component [II] / the component [I].
(Molar ratio) is desirably 0.01 to 100, preferably 0.2 to 10, and more preferably 0.5 to 5.
もちろん、第［Ｉ］成分および固体触媒成分の調製に
関する各反応操作は、不活性ガス雰囲気中で行うべきで
あり、また湿気はできるだけ避けるべきである。Of course, each reaction operation for preparing the component [I] and the solid catalyst component should be performed in an inert gas atmosphere, and moisture should be avoided as much as possible.
＜２＞ 有機金属化合物 本発明に用いる触媒は前記固体触媒成分と、有機金属
化合物からなり、有機金属化合物としてはチグラー触媒
の一成分として知られている周期律表第Ｉ〜IV族の有機
金属化合物を使用できるがとくに有機アルミニウム化合
物および有機亜鉛化合物が好ましい。具体的な例として
は一般式R3Al,R2AlX,RAlX2,R2AlOR,RAl（OR）ＸおよびR
3Al2X3の有機アルミニウム化合物（ただしＲは炭素数１
〜20のアルキル基またはアリール基、Ｘはハロゲン原子
を示し、Ｒは同一でもまた異なってもよい）または一般
式R2Zn（ただしＲは炭素数１〜20のアルキル基であり二
者同一でもまた異なっていてもよい）の有機亜鉛化合物
で示されるもので、トリメチルアルミニウム、トリエチ
ルアルミニウム、トリイソプロピルアルミニウム、トリ
イソブチルアルミニウム、トリsec−ブチルアルミニウ
ム、トリtert−ブチルアルミニウム、トリヘキシルアル
ミニウム、トリオクチルアルミニウム、ジエチルアルミ
ニウムクロリド、ジイソプロピ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、ジエチル亜鉛
およびこれらの混合物等があげられる。有機金属化合物
の使用量はとくに制限はないが通常チタン化合物に対し
て0.1〜1000mol倍使用することができる。<2> Organometallic Compound The catalyst used in the present invention comprises the solid catalyst component and an organometallic compound, and the organometallic compound is an organic metal belonging to Groups I to IV of the periodic table, which is known as one component of a Ziegler catalyst. Although compounds can be used, organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formulas R 3 Al, R 2 AlX, RAlX 2 , R 2 AlOR, RAl (OR) X and R
3 Al 2 X 3 organoaluminum compound (where R is 1 carbon atom)
20 alkyl group or aryl group, X represents a halogen atom, R represents or different may be) or the general formula R 2 Z n (provided that R be the same is an alkyl group having 1 to 20 carbon atoms two parties same And may also be different), such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctyl Examples include aluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc and a mixture thereof. The amount of the organometallic compound to be used is not particularly limited, but it can be generally used in an amount of 0.1 to 1000 mol times the titanium compound.
本発明においては、有機金属化合物成分は、前記有機
金属化合物と有機酸エステルとの混合物もしくは付加化
合物として用いることも好ましく採用することができ
る。In the present invention, the organometallic compound component can also be preferably used as a mixture or an additional compound of the organometallic compound and an organic acid ester.
この時有機金属化合物と有機酸エステルを混合物とし
て用いる場合には、有機金属化合物１モルに対して、有
機酸エステルを通常0.1〜１モル、好ましくは0.2〜0.5
モル使用する。また、有機金属化合物と有機酸エステル
との付加化合物として用いる場合は、有機金属化合物：
有機酸エステルのモル比が2:1〜1:2のものが好ましい。When the organic metal compound and the organic acid ester are used as a mixture at this time, the organic acid ester is usually used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5, per mol of the organic metal compound.
Use moles. When used as an addition compound of an organometallic compound and an organic acid ester, the organometallic compound:
Those having a molar ratio of the organic acid ester of 2: 1 to 1: 2 are preferred.
この時に用いられる有機酸エステルとは、炭素数が１
〜24の飽和もしくは不飽和の一塩基性ないし二塩基性の
有機カルボン酸素と炭素数１〜30のアルコールとのエス
テルである。具体的には、ギ酸メチル、酢酸エチル、酢
酸アミル、酢酸フェニル、酢酸オクチル、メタクリル酸
メチル、ステアリン酸エチル、安息香酸メチル、安息香
酸エチル、安息香酸ｎ−プロピル、安息香酸ジ−プロピ
ル、安息香酸ブチル、安息香酸ヘキシル、安息香酸シク
ロペンチル、安息香酸シクロヘキシル、安息香酸フェニ
ル、安息香酸４−トリル、サリチル酸メチル、サリチル
酸エチル、ｐ−オキシ安息香酸メチル、ｐ−オキシ安息
香酸エチル、サリチル酸ベンジル、α−レゾルシン酸エ
チル、アニス酸メチル、アニス酸エチル、アニス酸フェ
ニル、アニス酸ベンジル、ｏ−メトキシ安息香酸エチ
ル、ｐ−エトキシ安息香酸メチル、ｐ−トルイル酸メチ
ル、ｐ−トルイル酸エチル、ｐ−トルイル酸フェニル、
ｏ−トルイル酸エチル、ｍ−トルイル酸エチル、ｐ−ア
ミノ安息香酸メチル、ｐ−アミノ安息香酸エチル、安息
香酸ビニル、安息香酸アリル、安息香酸ベンジル、ナン
フトエ酸メチル、ナフトエ酸エチルなどを上げることが
できる。これらの中でも特に好ましいのは安息香酸、ｏ
−またはｐ−トルイル酸またはｐ−アニス酸のアルキル
エステルであり、とくにこれらのメチルエステル、エチ
ルエステルが好ましい。The organic acid ester used at this time has 1 carbon atom.
Esters of a saturated or unsaturated monobasic or dibasic organic carboxylic oxygen having 1 to 24 carbon atoms and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, di-propyl benzoate, benzoic acid Butyl, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, benzyl salicylate, α-resorcinol Ethyl acrylate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate ,
Ethyl o-toluate, ethyl m-toluate, methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, ethyl naphthoate, etc. it can. Of these, benzoic acid and o are particularly preferred.
-Or an alkyl ester of p-toluic acid or p-anisic acid, of which methyl ester and ethyl ester are particularly preferred.
＜３＞ オレフィンの重合 本発明の触媒を使用してのオレフィンの重合はスラリ
ー重合、溶液重合または気相重合にて行うことができ
る。特に本発明の触媒は気相重合に好適に用いることが
でき、重合反応は通常のチグラー型触媒によるオレフィ
ン重合反応と同様にして行われる。すなわち反応はすべ
て実質的に酸素、水などを絶った状態で不活性炭化水素
の存在化、あるいは不存在下で行われる。オレフィン重
合条件は温度は20ないし120℃、好ましくは50ないし100
℃であり、圧力は常圧ないし70kg/cm2、好ましくは２な
いし60kg/cm2である。分子量の調節は重合温度、触媒の
モル比などの重合条件を変えることによってある程度調
節できるが重合系中に水素を添加することにより効果的
に行われる。もちろん、本発明の触媒を用いて、水素濃
度、重合温度など重合条件の異なった２段階ないしそれ
以上の他段階の重合反応も何ら支障なく実施できる。<3> Polymerization of olefin The polymerization of olefin using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization. In particular, the catalyst of the present invention can be suitably used for gas phase polymerization, and the polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a Ziegler catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons with substantially no oxygen, water or the like. As for the olefin polymerization conditions, the temperature is 20 to 120 ° C, preferably 50 to 100 ° C.
° C, and the pressure is from normal pressure to 70 kg / cm 2 , preferably 2 to 60 kg / cm 2 . The molecular weight can be controlled to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but can be effectively controlled by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, the polymerization reaction in two or more stages with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.
本発明の方法はチグラー触媒で重合できるすべてのオ
レフィンの重合に適用可能であり、特に炭素数２〜12の
α−オレフィンが好ましく、たとえばエチレン、プロピ
レン、１−ブテン、ヘキセン−１、４−メチルペンテン
−１などのα−オレフィン類の単独重合およびエチレン
とプロピレン、エチレンと１−ブテン、エチレンとヘキ
セン−１、エチレンと４−メチルペンテン−１等のエチ
レンと炭素数３〜12のα−オレフィンの共重合、プロピ
レンと１−ブテンの共重合およびエチレンと他の２種類
以上のα−オレフィンとの共重合などに好適に使用され
る。The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with a Ziegler catalyst, and particularly preferred are α-olefins having 2 to 12 carbon atoms, for example, ethylene, propylene, 1-butene, hexene-1,4-methyl. Homopolymerization of α-olefins such as pentene-1, ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1 and other ethylene and α-olefins having 3 to 12 carbon atoms And copolymerization of propylene with 1-butene and ethylene with two or more other α-olefins.
また、ポリオレフィンの改質を目的とする場合のジエ
ンとの共重合も好ましく行われる。この時使用されるジ
エン化合物の例としてはブタジエン、1,4−ヘキサジエ
ン、エチリデンノルボルネン、ジシクロペンタジエン等
を挙げることができる。Copolymerization with a diene for the purpose of modifying polyolefin is also preferably performed. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene and the like.
なお、共重合の際のコモノマー含有率は任意に選択で
きうるものであるが、例えば、エチレンと炭素数３〜12
のα−オレフィンとの共重合の場合、エチレン・α−オ
レフィン共重合体中のα−オレフィン含有量は０〜40モ
ル％、好ましくは０〜30モル％とするのが望ましい。The comonomer content at the time of copolymerization can be arbitrarily selected. For example, ethylene and C 3-12
In the case of the copolymerization with an α-olefin, the content of the α-olefin in the ethylene / α-olefin copolymer is preferably 0 to 40 mol%, more preferably 0 to 30 mol%.
＜実施例＞ 以下に実施例をのべるが、これらは本発明を実施する
ための説明用のものであって本発明はこれらに制限され
るものではない。<Examples> Examples will be described below, but these are for the purpose of describing the present invention, and the present invention is not limited thereto.
実施例 １ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、アルミニウムト
リエトキシド4.2gを入れ窒素雰囲気下、室温で16時間ボ
ールミリングを行い反応生成物を得た。攪はん機および
還流冷却器をつけた三ツ口フラスコを窒素置換し、この
中に脱水した２−メチル−１−ペンタノール100g、ジエ
トキシジクロロチタン10.0gをいれ室温で１時間攪はん
後、上記の無水塩化マグネシウムとアルミニウムトリエ
トキシドの反応物5.0gを入れ、80℃、１時間反応させ
た。室温に冷却後、400℃で３時間焼成したシリカ（富
士デビソン、＃955）46gを入れ、再び80℃で２時間反応
させた後、120℃で２時間減圧乾燥を行い固体粉末を得
た。次に脱水したヘキサン100ccおよびジエチルアルミ
ニウムクロリド10.6gを加えて室温で１時間反応させ、
その後60℃で３時間窒素ブローを行い、ヘキサンを除去
して固体触媒成分を得た。Example 1 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. Ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 100 g of dehydrated 2-methyl-1-pentanol and 10.0 g of diethoxydichlorotitanium were added thereto and stirred at room temperature for 1 hour. 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and aluminum triethoxide was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted at 80 ° C. for 2 hours again, and dried at 120 ° C. for 2 hours under reduced pressure to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.6 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour.
Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 気相重合装置としては攪はん機付きステンレススチー
製オートクレーブを用い、ブロワー、流量調節器および
乾式サイクロンでループをつくり、オートクレーブはジ
ャケットに温水を流すことによって温度を調節した。80
℃に調節したオートクレーブに上記固体触媒成分を250m
g/hr、およびトリエチルアルミニウム50mmol/hrの速度
で供給し、またオートクレーブ気相中のブテン−1/エチ
レンモル比を0.25に、さらに水素を全圧の15％となるよ
うに調整しながら各々のガスを供給し、全圧を8kg/cm2G
に保ちながらプロワーにより系内のガスを循環させ、生
成ポリマーを間欠的に抜き出しながら10時間の連続重合
を行った。(B) Gas phase polymerization A stainless steel autoclave with a stirrer was used as a gas phase polymerization apparatus, and a loop was formed with a blower, a flow controller and a dry cyclone. The temperature of the autoclave was adjusted by flowing hot water through a jacket. . 80
250 m of the above solid catalyst component in an autoclave adjusted to
g / hr, and 50 mmol / hr of triethylaluminum, and while adjusting the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.25, and further adjusting the hydrogen to 15% of the total pressure, each gas was And the total pressure is 8kg / cm 2 G
The gas in the system was circulated by a prower while maintaining the temperature, and continuous polymerization was performed for 10 hours while intermittently extracting the produced polymer.
生成したエチレン共重合体は、メルトフローレイト
（MFR）1.04g/10min、密度0.9206g/cm3であり、かさ密
度0.44g/cm3、平均粒径860μｍの形状の丸い粒状物であ
った。触媒効率は230,000g共重合体/gTiと、きわめて高
活性であった。また、10時間の連続重合後、オートクレ
ーブ内部の点検を行ったところ、内壁および攪はん機に
は全くポリマーは付着していなかった。The resulting ethylene copolymer has a melt flow rate (MFR) 1.04g / 10min, a density of 0.9206g / cm 3, a bulk density of 0.44 g / cm 3, was a round particulate matter having the shape of an average particle diameter of 860μm. The catalytic efficiency was very high, 230,000g copolymer / gTi. After 10 hours of continuous polymerization, the inside of the autoclave was inspected. As a result, no polymer was adhered to the inner wall and the agitator.
この共重合体をASTM−D1238−65Tの方法により、190
℃、荷重2.16kgで測定したメルトフローレイト（MFR
2.16）と荷重10kgで測定したメルトフローレイト（MFR
10）との比で表わされるFR値（FR＝MFR10/MFR2.16）は
7.4であり、分子量分布はきわめて狭いものであった。
また、この共重合体の融点は121.7℃ヘキサン抽出量は
2.7wt％であった。According to the method of ASTM-D1238-65T, this copolymer was 190
Melt flow rate (MFR) measured at a load of 2.16 kg
2.16 ) and melt flow rate (MFR) measured at a load of 10 kg
10 ) and the FR value (FR = MFR 10 / MFR 2.16 )
It was 7.4 and the molecular weight distribution was extremely narrow.
The melting point of this copolymer is 121.7 ° C.
2.7 wt%.
実施例 ２ 実施例１においてジエトキシジクロロチタンの代わり
にジブトキシジクロロチタン15.0gを用いることを除い
ては、実施例１と同様な方法で固体触媒成分を調製し
た。上記固体触媒成分を用いて実施例１と同様な方法で
重合を行ったところ、触媒効率は210,000g共重合体/gTi
と高活性で、MFR0.97g/10min、密度0.9215g/cm3で、か
さ比重0.43g/cm3、平均粒径880μｍの形状の丸い粒状物
が得られた。また、FRは7.5と分子量分布が狭く、融点
は121.9℃、ヘキサン抽出量は2.8wt％であった。Example 2 A solid catalyst component was prepared in the same manner as in Example 1 except that 15.0 g of dibutoxydichlorotitanium was used instead of diethoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 210,000 g copolymer / gTi
Thus, a round granular material having a high activity, an MFR of 0.97 g / 10 min, a density of 0.9215 g / cm 3 , a bulk specific gravity of 0.43 g / cm 3 , and an average particle size of 880 μm was obtained. FR had a narrow molecular weight distribution of 7.5, a melting point of 121.9 ° C., and a hexane extraction of 2.8 wt%.
実施例 ３ 実施例１においてジエトキシジクロロチタンの代わり
に四塩化チタン10.0gを用いることを除いては、実施例
１と同様な方法で固体触媒成分を調製した。上記固体触
媒成分を用いて実施例１と同様な方法で重合を行ったと
ころ、触媒効率は270,000g共重合体/gTiと高活性で、MF
R0.88g/10min、密度0.9209g/cm3で、かさ比重0.42g/c
m3、平均粒径930μｍの形状の丸い粒状物が得られた。
また、FRは7.6と分子量分布が狭く、融点は122.2℃、ヘ
キサン抽出量は3.1wt％であった。Example 3 A solid catalyst component was prepared in the same manner as in Example 1 except that 10.0 g of titanium tetrachloride was used instead of diethoxydichlorotitanium. When the polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was 270,000 g copolymer / gTi, which was high activity.
R0.88g / 10min, a density 0.9209g / cm 3, a bulk specific gravity of 0.42 g / c
Round granules having a shape of m 3 and an average particle size of 930 μm were obtained.
Further, FR had a narrow molecular weight distribution of 7.6, the melting point was 122.2 ° C., and the hexane extraction amount was 3.1% by weight.
実施例 ４ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、アルミニウムト
リエトキシド4.2を入れ窒素雰囲気下、室温で16時間ボ
ールミリングを行い反応生成物を得た。攪はん機および
還流冷却器をつけた三ツ口フラスコを窒素置換し、この
中にメタノールを5wt％含む変性エタノール140ml、２−
メチル−１−ペンタノール20.0g、ジエトキシジクロロ
チタン8.0gをいれ室温で１時間攪はん後、上記の無水塩
化マグネシウムとアルミニウムトリエトキシドの反応物
5.0gを入れ、80℃、１時間反応させた。室温に冷却後、
400℃で３時間焼成したシリカ（富士デビソン、＃955）
46gを入れ、再び80℃で２時間反応させた後、120℃で２
時間減圧乾燥を行い固体粉末を得た。次に脱水したヘキ
サン100ccおよびジエチルアルミニウムクロリド10.0gを
加えて室温で１時間反応させ、その後60℃で３時間窒素
ブローを行い、ヘキサンを除去して固体触媒成分を得
た。Example 4 (a) Production of solid catalyst component A commercially available stainless steel pot having a capacity of 25 ml containing 25 stainless steel balls having a diameter of 1/2 inch was charged with 10 g of commercially available anhydrous magnesium chloride and 4.2 aluminum triethoxide. Ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 ml of denatured ethanol containing 5 wt% of methanol, 2-
After adding 20.0 g of methyl-1-pentanol and 8.0 g of diethoxydichlorotitanium and stirring at room temperature for 1 hour, the reaction product of the above anhydrous magnesium chloride and aluminum triethoxide was added.
5.0 g was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature
Silica fired at 400 ° C for 3 hours (Fuji Devison, # 955)
Add 46 g and react again at 80 ° C for 2 hours.
Drying was performed under reduced pressure for a time to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added, and reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は220,000g共重合体/gTiと
高活性で、MFR0.94g/10min、密度0.9222g/cm3で、かさ
比重0.43g/cm3、平均粒径820μｍの形状の丸い粒状物が
得られた。また、FRは7.4と分子量分布が狭く、融点は1
21.5℃、ヘキサン抽出量は2.6wt％であった。(B) Gas-phase polymerization Polymerization was carried out in the same manner as in Example 1 using the solid catalyst component. The catalyst efficiency was as high as 220,000 g copolymer / gTi, MFR 0.94 g / 10 min, density 0.9222. in g / cm 3, bulk density 0.43 g / cm 3, a round particulate matter having the shape of an average particle diameter of 820μm was obtained. FR has a narrow molecular weight distribution of 7.4 and a melting point of 1
At 21.5 ° C, the amount of hexane extracted was 2.6 wt%.
実施例 ５ 実施例４において２−メチル−１−ペンタノールの代
わりに3,5−ジメチル−１−ヘキソノール20.0gを用いる
ことを除いては、実施例４と同様な方法で固体触媒成分
を調製した。上記固体触媒成分を用いて実施例１と同様
な方法で重合を行ったところ、触媒効率は230.000g共重
合体/gTiと高活性で、MFR1.07g/10min、密度0.9211g/cm
3で、かさ比重0.42g/cm3、平均粒径840μｍの形状の丸
い粒状物が得られた。また、FRは7.4と分子量分布が狭
く、融点は122.0℃、ヘキサン抽出量は3.0wt％であっ
た。Example 5 A solid catalyst component was prepared in the same manner as in Example 4, except that 20.0 g of 3,5-dimethyl-1-hexonol was used instead of 2-methyl-1-pentanol in Example 4. did. When the polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 230.000 g copolymer / gTi, MFR 1.07 g / 10 min, density 0.9211 g / cm
In step 3 , round granular materials having a bulk specific gravity of 0.42 g / cm 3 and an average particle size of 840 μm were obtained. In addition, FR had a narrow molecular weight distribution of 7.4, a melting point of 122.0 ° C, and a hexane extraction amount of 3.0 wt%.
実施例 ６ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、アルミニウムト
リエトキシド4.2gを入れ窒素雰囲気下、室温で16時間ボ
ールミリングを行い反応生成物を得た。攪はん機および
還流冷却器をつけた三ツ口フラスコを窒素置換し、この
中にエタノール140ml、２−メチル−１−ヘキサノール1
7.0g、ジエトキシジクロロチタン12.0gをいれ室温で１
時間攪はん後、上記の無水塩化マグネシウムとアルミニ
ウムトリエトキシドの反応物4.2gを入れ、80℃、１時間
反応させた。室温に冷却後、400℃で３時間焼成したシ
リカ（富士デビソン、＃955）46gを入れ、再び80℃で２
時間反応させた後、120℃で２時間減圧乾燥を行い固体
粉末を得た。次に脱水したヘキサン100ccおよびジエチ
ルアルミニウムクロリド10.0gを加えて室温で１時間反
応させ、その後60℃で３時間窒素ブローを行い、ヘキサ
ンを除去して固体触媒成分を得た。Example 6 (a) Production of solid catalyst component 10 g of anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. Ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 140 ml of ethanol and 2-methyl-1-hexanol 1 were added.
Add 7.0 g, 12.0 g of diethoxydichlorotitanium and add 1 at room temperature.
After stirring for a period of time, 4.2 g of the above-mentioned reaction product of anhydrous magnesium chloride and aluminum triethoxide was added, and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, and the mixture was heated again at 80 ° C.
After reacting for an hour, it was dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added, and reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は270,000g共重合体/gTiと
高活性で、MFR0.89g/10min、密度0.9211g/cm3で、かさ
比重0.44g/cm3、平均粒径910μｍの形状の丸い粒状物が
得られた。またFRは7.4と分子量分布が狭く、融点は12
1.8℃、ヘキサン抽出量は2.9wt％であった。(B) Gas phase polymerization Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component. The catalyst efficiency was 270,000 g copolymer / gTi, high activity, MFR 0.89 g / 10 min, density 0.9211. in g / cm 3, bulk density 0.44 g / cm 3, a round particulate matter having the shape of an average particle diameter of 910μm was obtained. FR has a narrow molecular weight distribution of 7.4 and a melting point of 12
At 1.8 ° C, the hexane extraction amount was 2.9 wt%.
実施例 ７ 実施例６においてジエトキシジクロロチタンの代わり
にジブトキシジクロロチタン15.0gを用いることを除い
ては、実施例６と同様な方法で固体触媒成分を調製し
た。上記固体触媒成分を用いて実施例１と同様な方法で
重合を行ったところ、触媒効率は260.000g共重合体/gTi
と高活性で、MFR1.12g/10min、密度0.9211g/cm3で、か
さ比重0.40g/cm3、平均粒径880μｍの形状の丸い粒状物
が得られた。また、FRは7.5と分子量分布が狭く、融点
は122.1℃、ヘキサン抽出量は3.0wt％であった。Example 7 A solid catalyst component was prepared in the same manner as in Example 6, except that 15.0 g of dibutoxydichlorotitanium was used instead of diethoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 260.000 g copolymer / gTi
And highly active, MFR1.12g / 10min, a density 0.9211g / cm 3, bulk density 0.40 g / cm 3, a round particulate matter having the shape of an average particle diameter of 880μm was obtained. In addition, FR had a narrow molecular weight distribution of 7.5, a melting point of 122.1 ° C, and a hexane extraction amount of 3.0 wt%.
実施例 ８ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、アルミニウムト
リエトキシド4.2gを入れ窒素雰囲気下、室温で16時間ボ
ールミリングを行い反応生成物を得た。攪はん機および
還流冷却器をつけた三ツ口フラスコを窒素置換し、この
中にメタノールを5wt％含む変性エタノール140ml、２−
メチル−１−ヘキサノール17.0g、ジブトキシジクロロ
チタン15.0gをいれ室温で１時間攪はん後、上記の無水
塩化マグネシウムとアルミニウムトリエトキシドの反応
物5.0gを入れ、80℃、１時間反応させた。室温に冷却
後、400℃で３時間焼成したシリカ（富士デビソン、＃9
55）46gを入れ、再び80℃で２時間反応させた後、120℃
で２時間減圧乾燥を行い固体粉末を得た。次に脱水した
ヘキサン100ccおよびジエチルアルミニウムクロリド10.
0gを加えて室温で１時間反応させ、その後60℃で３時間
窒素ブローを行い、ヘキサンを除去して固体触媒成分を
得た。Example 8 (a) Production of solid catalyst component 10 g of anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. Ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 ml of denatured ethanol containing 5 wt% of methanol, 2-
After 17.0 g of methyl-1-hexanol and 15.0 g of dibutoxydichlorotitanium were added and stirred at room temperature for 1 hour, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and aluminum triethoxide was added, and the mixture was reacted at 80 ° C. for 1 hour. Was. Silica calcined at 400 ° C for 3 hours after cooling to room temperature (Fuji Devison, # 9
55) Add 46 g, react at 80 ° C again for 2 hours, then 120 ° C
And dried under reduced pressure for 2 hours to obtain a solid powder. Then 100 cc of dehydrated hexane and diethylaluminum chloride 10.
After adding 0 g, the mixture was reacted at room temperature for 1 hour, and then nitrogen was blown at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は240,000g共重合体/gTiと
高活性で、MFR1.14g/10min、密度0.9230g/cm3で、かさ
比重0.42g/cm3、平均粒径830μｍの形状の丸い粒状物が
得られた。また、FRは7.3と分子量分布が狭く、融点は1
21.6℃、ヘキサン抽出量は2.7wt％であった。(B) Gas phase polymerization The polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component. The catalyst efficiency was as high as 240,000 g copolymer / gTi, MFR 1.14 g / 10 min, density 0.9230. As a result, a round granular material having a g / cm 3 , a bulk specific gravity of 0.42 g / cm 3 and an average particle size of 830 μm was obtained. FR has a narrow molecular weight distribution of 7.3 and a melting point of 1
At 21.6 ° C, the amount of hexane extracted was 2.7 wt%.
実施例 ９ 実施例８においてジエトキシジクロロチタンの代わり
にジエトキシジクロロチタン10.0gを用いることを除い
ては、実施例８と同様な方法で固体触媒成分を調製し
た。上記固体触媒成分を用いて実施例１と同様な方法で
重合を行ったところ、触媒効率は250,000g共重合体/gTi
と高活性で、MFR0.97g/10min、密度0.9205g/cm3で、か
さ比重0.44g/cm3、平均粒径780μｍの形状の丸い粒状物
が得られた。また、FRは7.5と分子量分布が狭く、融点
は122.4℃、ヘキサン抽出量は3.1wt％であった。Example 9 A solid catalyst component was prepared in the same manner as in Example 8, except that 10.0 g of diethoxydichlorotitanium was used instead of diethoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 250,000 g copolymer / gTi
And highly active, MFR0.97g / 10min, a density 0.9205g / cm 3, bulk density 0.44 g / cm 3, a round particulate matter having the shape of an average particle diameter of 780μm was obtained. Further, FR had a narrow molecular weight distribution of 7.5, a melting point of 122.4 ° C., and a hexane extraction amount of 3.1 wt%.
実施例 10 実施例６においてジエトキシジクロロチタンの代わり
にジ−２−エチルヘキシルオキシジクロロチタン15.0g
を用いることを除いては、実施例６と同様な方法で固体
触媒成分を調製した。上記固体触媒成分を用いて実施例
１と同様な方法で重合を行ったところ、触媒効率は200,
000g共重合体/gTiと高活性で、MFR0.88g/10min、密度0.
9200g/cm3で、かさ比重0.43g/cm3、平均粒径800μｍの
形状の丸い粒状物が得られた。また、FRは7.6と分子量
分布が狭く、融点は122.1℃、ヘキサン抽出量は3.3wt％
であった。Example 10 In Example 6, 15.0 g of di-2-ethylhexyloxydichlorotitanium was used instead of diethoxydichlorotitanium.
A solid catalyst component was prepared in the same manner as in Example 6, except for using. When polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was 200,
High activity with 000g copolymer / gTi, MFR 0.88g / 10min, density 0.
A round granular material having a shape of 9200 g / cm 3 , a bulk specific gravity of 0.43 g / cm 3 and an average particle size of 800 μm was obtained. FR has a narrow molecular weight distribution of 7.6, melting point of 122.1 ° C, and hexane extraction of 3.3 wt%.
Met.
実施例 11 （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、トリエトキシボ
ロン5.0gを入れ窒素雰囲気下、室温で16時間ボールミリ
ングを行い反応生成物を得た。攪はん機および還流冷却
器をつけた三ツ口フラスコを窒素置換し、この中に脱水
した２−メチル−１−ペンタノール100g、ジエトキシジ
クロロチタン10.0gをいれ室温で１時間攪はん後、上記
の無水塩化マグネシウムとトリエトキシボロンの反応物
5.0gを入れ、80℃、１時間反応させた。室温に冷却後、
400℃で３時間焼成したシリカ（富士デビソン、＃955）
46gを入れ、再び80℃で２時間反応させた後、120℃で２
時間減圧乾燥を行い固体粉末を得た。次に脱水したヘキ
サン100ccおよびジエチルアルミニウムクロリド10.0gを
加えて室温で１時間反応させ、その後60℃で３時間窒素
ブローを行い、ヘキサンを除去して固体触媒成分を得
た。Example 11 (a) Production of solid catalyst component A commercially available stainless steel pot having an inner volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch was charged with 10 g of commercially available anhydrous magnesium chloride and 5.0 g of triethoxyboron. Ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 100 g of dehydrated 2-methyl-1-pentanol and 10.0 g of diethoxydichlorotitanium were added thereto and stirred at room temperature for 1 hour. Reaction product of the above anhydrous magnesium chloride and triethoxyboron
5.0 g was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature
Silica fired at 400 ° C for 3 hours (Fuji Devison, # 955)
Add 46 g and react again at 80 ° C for 2 hours.
Drying was performed under reduced pressure for a time to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added, and reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は210,000g共重合体/gTiと
高活性で、MFR0.97g/10min、密度0.9207g/cm3で、かさ
比重0.44g/cm3、平均粒径800μｍの形状の丸い粒状物が
得られた。また、FRは7.6と分子量分布が狭く、融点は1
22.0℃、ヘキサン抽出量は3.2wt％であった。(B) Gas phase polymerization The polymerization was carried out in the same manner as in Example 1 using the solid catalyst component. The catalyst efficiency was as high as 210,000 g copolymer / gTi, MFR 0.97 g / 10 min, density 0.9207. in g / cm 3, bulk density 0.44 g / cm 3, a round particulate matter having the shape of an average particle diameter of 800μm was obtained. FR has a narrow molecular weight distribution of 7.6 and a melting point of 1
At 22.0 ° C, the amount of hexane extracted was 3.2 wt%.
実施例 12 実施例11においてトリエトキシボロンの代わりにジエ
トキシマグネシウム7.5gを用いることを除いては、実施
例11と同様な方法で固体触媒成分を調製した。上記固体
触媒成分を用いて実施例１と同様な方法で重合を行った
ところ、触媒効率は220,000g共重合体/gTiと高活性で、
MFR1.08g/10min、密度0.9232g/cm3で、かさ比重0.42g/c
m3、平均粒径800μｍの形状の丸い粒状物が得られた。
また、FRは7.5と分子量分布が狭く、融点は122.2℃、ヘ
キサン抽出量は2.8wt％であった。Example 12 A solid catalyst component was prepared in the same manner as in Example 11, except that 7.5 g of diethoxymagnesium was used instead of triethoxyboron. When the polymerization was carried out in the same manner as in Example 1 using the solid catalyst component, the catalyst efficiency was 220,000 g copolymer / gTi, which was high activity.
MFR1.08g / 10min, a density 0.9232g / cm 3, a bulk specific gravity of 0.42 g / c
A round granular material having a shape of m 3 and an average particle size of 800 μm was obtained.
Further, FR had a narrow molecular weight distribution of 7.5, a melting point of 122.2 ° C., and a hexane extraction amount of 2.8 wt%.
実施例 13 実施例６においてシリカの代わりにシリカアルミナを
用いることを除いては、実施例６と同様な方法で固体触
媒成分を調製した。上記固体触媒成分を用いて実施例１
と同様な方法で重合を行ったところ、触媒効率は190,00
0g共重合体/gTiと高活性で、MFR0.77g/10min、密度0.92
35g/cm3で、かさ比重0.40g/cm3、平均粒径770μｍの形
状の丸い粒状物が得られた。また、FRは7.5と分子量分
布が狭く、融点は122.3℃、ヘキサン抽出量は2.9wt％で
あった。Example 13 A solid catalyst component was prepared in the same manner as in Example 6, except that silica alumina was used instead of silica. Example 1 using the above solid catalyst component
When the polymerization was carried out in the same manner as described above, the catalyst efficiency was 190,00
High activity with 0g copolymer / gTi, MFR 0.77g / 10min, density 0.92
A round granular material having a shape of 35 g / cm 3 , a specific gravity of 0.40 g / cm 3 and an average particle size of 770 μm was obtained. Further, FR had a narrow molecular weight distribution of 7.5, a melting point of 122.3 ° C., and a hexane extraction amount of 2.9 wt%.
実施例 14 実施例６においてシリカの代わりにアルミナを用いる
ことを除いては、実施例６と同様な方法で固体触媒成分
を調製した。上記固体触媒成分を用いて実施例１と同様
な方法で重合を行ったところ、触媒効率は200,000g共重
合体/gTiと高活性で、MFR0.86g/10min、密度0.9199g/cm
3で、かさ比重0.40g/cm3、平均粒径780μｍの形状の丸
い粒状物が得られた。また、FRは7.6と分子量分布が狭
く、融点は122.5℃、ヘキサン抽出量は3.2wt％であっ
た。Example 14 A solid catalyst component was prepared in the same manner as in Example 6, except that alumina was used instead of silica in Example 6. Polymerization was carried out in the same manner as in Example 1 using the solid catalyst component. The catalyst efficiency was as high as 200,000 g copolymer / gTi, MFR 0.86 g / 10 min, density 0.9199 g / cm
In Step 3 , round granular materials having a bulk specific gravity of 0.40 g / cm 3 and an average particle size of 780 μm were obtained. Further, FR had a narrow molecular weight distribution of 7.6, the melting point was 122.5 ° C., and the hexane extraction amount was 3.2 wt%.
実施例 15 実施例１においてジエチルアルミニウムクロリドの代
わりにエチルアルミニウムクロリド14.5gを用いること
を除いては、実施例１と同様な方法で固体触媒成分を調
製した。上記固体触媒成分を用いて実施例１と同様な方
法で重合を行ったところ、触媒効率は250,000g共重合体
/gTiと高活性で、MFR1.11g/10min、密度0.9201g/cm
3で、かさ比重0.42g/cm3、平均粒径890μｍの形状の丸
い粒状物が得られた。また、FRは7.4と分子量分布が狭
く、融点は122.1℃、ヘキサン抽出量は3.0wt％であっ
た。Example 15 A solid catalyst component was prepared in the same manner as in Example 1 except that 14.5 g of ethylaluminum chloride was used instead of diethylaluminum chloride. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 250,000 g copolymer.
/ gTi and high activity, MFR1.11g / 10min, density 0.9201g / cm
In step 3 , round granular materials having a bulk specific gravity of 0.42 g / cm 3 and an average particle size of 890 μm were obtained. Further, FR had a narrow molecular weight distribution of 7.4, a melting point of 122.1 ° C., and a hexane extraction amount of 3.0 wt%.
比較例 １ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、アルミニウムト
リエトキシド4.2gを入れ窒素雰囲気下、室温で16時間ボ
ールミリングを行い反応生成物を得た。攪拌機、および
還流冷却器をつけた三ツ口フラスコを窒素置換し、この
三ツ口フラスコに上記反応生成物5gおよび600℃で焼成
したSiO2（富士デビソン、＃952）5gを入れ、次いでテ
トラヒドロフラン100mlを加えて、60℃で２時間反応さ
せたのち、120℃で減圧乾燥を行い、テトラヒドロラン
を除去した。次に、ヘキサン50ccを加えて攪拌したのち
に四塩化チタンを1.1mlを加えてヘキサン還流下で２時
間反応させて、固体触媒成分を得た。得られた固体触媒
成分1g中のチタンの含有量は40mgであった。Comparative Example 1 (a) Production of solid catalyst component A commercially available stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch was charged with 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide. Ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen. 5 g of the above reaction product and 5 g of SiO 2 (Fuji Devison, # 952) calcined at 600 ° C. were added to the three-necked flask, and then 100 ml of tetrahydrofuran was added. After reacting at 60 ° C. for 2 hours, the mixture was dried at 120 ° C. under reduced pressure to remove tetrahydrolan. Next, after adding 50 ml of hexane and stirring, 1.1 ml of titanium tetrachloride was added and reacted under reflux of hexane for 2 hours to obtain a solid catalyst component. The content of titanium in 1 g of the obtained solid catalyst component was 40 mg.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は112,000g共重合体/gTiと
低活性で、MFR1.2g/10min、密度0.921g/cm3で、かさ密
度0.41g/cm3、平均粒径700μｍ、FR7.6の不定形な粒状
物が得られた。また融点は123.2℃で、ヘキサン抽出量
は4.2wt％であった。(B) Gas phase polymerization The polymerization was carried out using the above solid catalyst component in the same manner as in Example 1. The catalyst efficiency was as low as 112,000 g copolymer / gTi, MFR 1.2 g / 10 min, density 0.921. At g / cm 3 , amorphous particles having a bulk density of 0.41 g / cm 3 , an average particle size of 700 μm, and FR7.6 were obtained. The melting point was 123.2 ° C., and the amount of hexane extracted was 4.2 wt%.
比較例 ２ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10g、トリエトキシア
ルミニウム4.3gを入れ窒素雰囲気下、室温で16時間ボー
ルミリングを行い反応生成物を得た。攪拌機、および還
流冷却器をつけた三ツ口フラスコを窒素置換し、この中
に脱水したエタノール140cc、脱水した２−メチル−１
−ペンタノール100g、テトラｎ−エトキシチタン2.0g、
上記の無水塩化マグネシウムとトリエトキシアルミニウ
ムの反応物5.0gを入れ、80℃、１時間反応させた後、12
0℃で２時間減圧乾燥を行い固体粉末を得た。次に脱水
したヘキサン100ccおよびジエチルアルミニウムクロリ
ド2.0gを加えて室温で１時間反応させ、その後60℃で３
時間窒素ブローを行い、ヘキサンを除去して固体触媒成
分を得た。Comparative Example 2 (a) Production of solid catalyst component A commercially available stainless steel pot of 10 g and 4.3 g of triethoxyaluminum were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. Ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 cc of dehydrated ethanol and 2-methyl-1 dehydrated were placed therein.
-Pentanol 100 g, tetra-n-ethoxy titanium 2.0 g,
5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum was added, and reacted at 80 ° C. for 1 hour.
Drying under reduced pressure at 0 ° C. for 2 hours gave a solid powder. Next, 100 cc of dehydrated hexane and 2.0 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour.
Nitrogen was blown for an hour to remove hexane to obtain a solid catalyst component.
上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、重合開始後30分で攪拌機の回転が不
能となり、重合を停止せざるをえなかった。オートクレ
ーブ内部を点検したところ攪拌翼にメルトしたポリマー
が付着していた。When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, rotation of the stirrer became impossible 30 minutes after the start of polymerization, and the polymerization had to be stopped. Inspection of the inside of the autoclave revealed that the melted polymer had adhered to the stirring blade.
比較例 ３ （ａ） 固体触媒成分の製造 1/2インチ直径を有するステンレススチール製ボール
が25コ入った内容積400mlのステンレススチール製ポッ
トに市販の無水塩化マグネシウム10gを入れ窒素雰囲気
下、室温で16時間ボールミリングを行った。撹拌機、お
よび還流冷却器をつけた三ツ口フラスコを窒素置換し、
この中に脱水したエタノール140cc、脱水した２−エチ
ル−１−ヘキサノール17.0g、テトラエトキシチタン12.
0gを入れ室温で１時間攪拌後、上記の無水塩化マグネシ
ウム粉砕物7.5gを入れ、80℃、１時間反応させた。室温
に冷却後、400℃で３時間焼成したシリカ（富士デビソ
ン、＃955）46gを入れ、再び80℃で２時間反応させた
後、120℃で２時間減圧乾燥を行い固体粉末を得た。次
に脱水したヘキサン100ccおよびジエチルアルミニウム
クロリド10.0gを加えて室温で１時間反応させ、その後6
0℃で３時間窒素ブローを行い、ヘキサンを除去して固
体触媒成分を得た。Comparative Example 3 (a) Production of Solid Catalyst Component 10 g of commercially available anhydrous magnesium chloride was placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch and placed at room temperature under a nitrogen atmosphere. Ball milling was performed for 16 hours. A three-necked flask equipped with a stirrer and a reflux condenser is purged with nitrogen,
140 cc of dehydrated ethanol, 17.0 g of dehydrated 2-ethyl-1-hexanol and tetraethoxytitanium 12.
After adding 0 g and stirring at room temperature for 1 hour, 7.5 g of the above-mentioned anhydrous magnesium chloride pulverized product was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted at 80 ° C. for 2 hours again, and dried at 120 ° C. for 2 hours under reduced pressure to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour.
Nitrogen was blown at 0 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.
（ｂ） 気相重合 上記固体触媒成分を用いて実施例１と同様な方法で重
合を行ったところ、触媒効率は140,000g共重合体/gTi
で、MFR0.98g/10min、密度0.9220g/cm3で、かさ比重0.3
8g/cm3、平均粒径710μｍの不定形な粒状物が得られ
た。また、FRは8.2と分子量分布は比較的広く、融点は1
23.0℃で、ヘキサン抽出量は4.0wt％であった。(B) Gas phase polymerization Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, and the catalyst efficiency was 140,000 g copolymer / gTi.
In, MFR0.98g / 10min, a density 0.9220g / cm 3, a bulk specific gravity of 0.3
As a result, amorphous particles having an average particle size of 8 g / cm 3 and an average particle size of 710 μm were obtained. In addition, FR has a relatively wide molecular weight distribution of 8.2, and a melting point of 1
At 23.0 ° C., the hexane extraction was 4.0 wt%.
第１図は本発明の触媒の製造工程を示すフローチャート
である。FIG. 1 is a flowchart showing the production process of the catalyst of the present invention.
フロントページの続き (72)発明者 清水 浩之 東京都品川区南大井２―12―10―627 (72)発明者 松浦 一雄 東京都大田区東雪谷２―22―18Continued on the front page (72) Inventor Hiroyuki Shimizu 2-12-10-627 Minamioi, Shinagawa-ku, Tokyo (72) Inventor Kazuo Matsuura 2-22-18, Higashiyukiya, Ota-ku, Tokyo
Claims (1)
てオレフィンを重合または共重合する方法において、該
固体触媒成分が 〔Ｉ〕（１）ケイ素酸化物および／またはアルミニウム
酸化物、 （２）ハロゲン化マグネシウムおよび一般式Me（OR）nX
z-n （ここでMeはNa、Mg、Ca、Zn、Cd、Ｂ、Al、SiおよびSn
からなる群から選ばれる元素、ｚは元素Meの原子価、ｎ
は０＜ｎ≦ｚ、Ｘはハロゲン原子、Ｒは炭素数１〜20の
炭化水素基を示す）で表される化合物 を反応させて得られる反応生成物および （３）一般式Ti（OR′）nX4-n（ここでＲ′は、炭素数
１〜20の炭化水素基、Ｘはハロゲン原子を表し、ｎは０
≦ｎ＜４である）で表されるチタン化合物を、 （４）一般式ROH（ここでＲは炭素数６〜20の有機基を
示す）で表される化合物の存在下、 相互に反応させて得られる反応生成物に、 〔II〕一般式AlRnX3-n（ここでＲは炭素数１〜24の炭化
水素基、Ｘはハロゲン原子を表し、ｎは０＜ｎ≦３であ
る）で表される有機アルミニウム化合物を反応させて得
られる物質からなることを特徴とするポリオレフィンの
製造方法。1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as catalysts, wherein the solid catalyst component comprises (I) (1) a silicon oxide and / or an aluminum oxide, and (2) a halogen. Magnesium iodide and general formula Me (OR) n X
zn (where Me is Na, Mg, Ca, Zn, Cd, B, Al, Si and Sn
An element selected from the group consisting of: z is the valence of the element Me, n
Is a reaction product obtained by reacting a compound represented by the formula: (3) a compound represented by the general formula Ti (OR ′), wherein 0 <n ≦ z, X represents a halogen atom, and R represents a hydrocarbon group having 1 to 20 carbon atoms. ) N X 4-n (where R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents 0)
≦ n <4) are reacted with each other in the presence of a compound represented by the general formula ROH (where R represents an organic group having 6 to 20 carbon atoms): the reaction product obtained Te, [II] the general formula AlR n X 3-n (wherein R is a hydrocarbon group having 1 to 24 carbon atoms, X represents a halogen atom, n represents is 0 <n ≦ 3 A method for producing a polyolefin, comprising a substance obtained by reacting an organoaluminum compound represented by the formula (1).
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32386789A JP2714992B2 (en) | 1989-12-15 | 1989-12-15 | Method for producing polyolefin |
| CA002029639A CA2029639C (en) | 1989-11-13 | 1990-11-09 | Process for preparing polyolefins |
| KR1019900018345A KR100197641B1 (en) | 1989-11-13 | 1990-11-13 | Method for producing polyolefin |
| EP90312364A EP0428375B1 (en) | 1989-11-13 | 1990-11-13 | Process for preparing polyolefins |
| CN90109754A CN1040443C (en) | 1989-11-13 | 1990-11-13 | Process for preparing polyolefins |
| DE69018933T DE69018933T2 (en) | 1989-11-13 | 1990-11-13 | Process for the production of polyolefins. |
| US08/881,936 US5804679A (en) | 1989-11-13 | 1997-06-25 | Process for preparing polyolefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32386789A JP2714992B2 (en) | 1989-12-15 | 1989-12-15 | Method for producing polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03185004A JPH03185004A (en) | 1991-08-13 |
| JP2714992B2 true JP2714992B2 (en) | 1998-02-16 |
Family
ID=18159481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32386789A Expired - Fee Related JP2714992B2 (en) | 1989-11-13 | 1989-12-15 | Method for producing polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2714992B2 (en) |
-
1989
- 1989-12-15 JP JP32386789A patent/JP2714992B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03185004A (en) | 1991-08-13 |
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