JPH02170803A - Production of polyolefin - Google Patents
Production of polyolefinInfo
- Publication number
- JPH02170803A JPH02170803A JP32362288A JP32362288A JPH02170803A JP H02170803 A JPH02170803 A JP H02170803A JP 32362288 A JP32362288 A JP 32362288A JP 32362288 A JP32362288 A JP 32362288A JP H02170803 A JPH02170803 A JP H02170803A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- compound
- polymerization
- polyolefin
- prepolymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 32
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- -1 ethylene, propylene Chemical group 0.000 abstract description 11
- 150000003609 titanium compounds Chemical class 0.000 abstract description 11
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 18
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101150030514 GPC1 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、オレフィンを重合してポリオレフィンを製造
する方法に関し、更に詳しくは、高い立体規制性を有し
、かつ広い分子量分布を有する成形性の改良されたポリ
オレフィンを提供するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a polyolefin by polymerizing olefins, and more specifically to a method for producing polyolefins that have high stereoregulatory properties and a wide molecular weight distribution. The present invention provides an improved polyolefin.
（従来技術及び発明が解決しようとする課題）オレフィ
ンの重合触媒としてチーグラー型触媒は周知のものであ
り、その活性及び立体規則性を改善する方法が提案され
ている。中でも活性についての改善はチタン成分として
チタン、マグネシウム、及びハロゲンを必須成分とする
ことにより大幅な改善がなされている。しかし、この触
媒を用いてプロピレンなどの重合を行う場合、活性は非
常に高いものの得られる重合体の立体規則性がきわめて
低いことから、実用的価値が失われることも知られてい
る。一般に成形品の剛性、強度は重合体の結晶化度に強
く依存し、同時に固体結晶化度は重合体の立体規則性に
より決定される。従って、より高い剛性、強度の成形品
を得るために、より高結晶性のポリプロピレンが望まれ
ていた。(Prior Art and Problems to be Solved by the Invention) Ziegler type catalysts are well known as olefin polymerization catalysts, and methods for improving their activity and stereoregularity have been proposed. Among these, significant improvement in activity has been achieved by using titanium, magnesium, and halogen as essential titanium components. However, when polymerizing propylene or the like using this catalyst, it is known that although the activity is very high, the stereoregularity of the resulting polymer is extremely low, so that it loses its practical value. Generally, the rigidity and strength of a molded article strongly depend on the crystallinity of the polymer, and at the same time, the solid crystallinity is determined by the stereoregularity of the polymer. Therefore, in order to obtain molded products with higher rigidity and strength, polypropylene with higher crystallinity has been desired.
そこでチタン、マグネシウム、及びハロゲン含有のチタ
ン成分に種々のエステル、エーテル、アミンなどの電子
供与体を含有させることにより立体規則性を向上さセる
方法が提案されている。一方でこのようなチタン成分と
有機アルミニウムとによる重合においてエステル、エー
テル、アミン、有機ケイ素化合物などを添加する方法も
提案されている。このような方法により重合体の立体規
則性はかなり改善されてきた。しかしながら、これらの
触媒系を用いてオレフィンを重合して得られるポリオレ
フィンは、一般に分子量分布が狭く溶融時の流動性に劣
り、流動配向性が失われることから成形品の配向強度が
著しく低下する。その結果、射出成形品では、一般に剛
性の低下や又フィルムに於いては腰が弱い等の難点があ
った。Therefore, a method has been proposed in which the stereoregularity is improved by incorporating various electron donors such as esters, ethers, and amines into titanium, magnesium, and halogen-containing titanium components. On the other hand, methods have also been proposed in which esters, ethers, amines, organosilicon compounds, etc. are added to the polymerization of titanium components and organic aluminum. Such methods have significantly improved the stereoregularity of polymers. However, the polyolefins obtained by polymerizing olefins using these catalyst systems generally have a narrow molecular weight distribution and poor fluidity during melting, and because the flow orientation is lost, the orientation strength of molded articles is significantly reduced. As a result, injection molded products generally have drawbacks such as a decrease in rigidity, and films have weak stiffness.
（課題を解決するための手段）
本発明者らは、上記の課題についてポリオレフィンに高
い立体規則性と広い分子量分布を付与することによつい
て鋭意検討を行った結果、オレフィンの予備重合により
得られたチタン含有ポリオレフィンを用いて本重合する
際に、特定の有機ゲイ素化合物とケイ酸エチルを同時に
用いることにより、所期の目的が達成されることを見い
だし本発明を完成した。(Means for Solving the Problems) The present inventors have conducted intensive studies to solve the above problems by imparting high stereoregularity and wide molecular weight distribution to polyolefins. The present invention was completed based on the discovery that the desired object could be achieved by simultaneously using a specific organic gay compound and ethyl silicate during main polymerization using a titanium-containing polyolefin.
即ち、本発明は、
八 予備重合で得られたチタン含有ポリオレフィン
Ｂ 有機アルミニウム化合物
Ｃ−＠ 式 〔夏〕
Ｒ，１Ｓｉ（ＯＲ’）４−ａ （１）で
示される有機ケイ素化合物
Ｄ ケイ酸エチル
の存在下にオレフィンを重合することを特徴とするポリ
オレフィンの製造方法である。That is, the present invention provides: 8. Titanium-containing polyolefin B obtained by prepolymerization Organoaluminum compound C-@Organosilicon compound D represented by the formula [Summer] R,1Si(OR')4-a (1) Ethyl silicate This is a method for producing a polyolefin, which is characterized by polymerizing an olefin in the presence of.
本発明では、オレフィンの本重合に先だって予備重合を
行なうことが、広い分子量分布と高い立体規則性を有す
るポリオレフィンを得るために重要である。予備重合は
、公知の方法が何ら制限なく採用し得る、例えば、チタ
ン化合物と有機アルミニウム化合物の存在下にオレフィ
ンを予備重合する方法が一般的である。In the present invention, it is important to perform prepolymerization prior to the main polymerization of the olefin in order to obtain a polyolefin having a wide molecular weight distribution and high stereoregularity. For the prepolymerization, any known method may be employed without any restriction, for example, a method in which an olefin is prepolymerized in the presence of a titanium compound and an organoaluminum compound is generally used.
予備重合で用いられるチタン化合物は、プロピレンの重
合に使用されることが公知の化合物が何ら制限なく採用
される。特に、チタン、マグネシウム及びハロゲンを成
分とする触媒活性の高いチタン化合物が好適である。こ
のような触媒活性の高いチタン化合物は、ハロゲン化チ
タン、特に四塩化チタンを種々のマグネシウム化合物に
担持させたものとなっている。As the titanium compound used in the prepolymerization, any compound known to be used in propylene polymerization can be used without any restriction. In particular, titanium compounds with high catalytic activity containing titanium, magnesium, and halogen are suitable. Such titanium compounds with high catalytic activity are those in which titanium halide, particularly titanium tetrachloride, is supported on various magnesium compounds.
この触媒の製法は、公知の方法が何ら制限なく採用され
る。例えば、四塩化チタンを塩化マグネシウムのような
マグネシウム化合物と共粉砕する方法、アルコール、エ
ーテル、エステル、ケトン又はアルデヒド等の電子供与
体の存在下にハロゲン化チタンとマグネシウム化合物と
を共粉砕する方法、又は、溶媒中でハロ・ゲン化チタン
、マグネシウム化合物及び電子供与体を接触させる方法
等が挙げられる。For the production of this catalyst, any known method may be employed without any restriction. For example, a method of co-milling titanium tetrachloride with a magnesium compound such as magnesium chloride, a method of co-milling a titanium halide and a magnesium compound in the presence of an electron donor such as an alcohol, ether, ester, ketone or aldehyde, Alternatively, a method may be mentioned in which a titanium halide, a magnesium compound, and an electron donor are brought into contact with each other in a solvent.
次に有機アルミニウム化合物も、プロピレンの重合に使
用されることが公知の化合物が何ら制限なく採用される
。例えば、トリメチルアルミニウム、トリエチルアルミ
ニウム、トリーｎブチルアルミニウム、トリーｎブチル
アルミニウム、トリーｎブチルアルミニウム、トリーｎ
ブチルアルミニウム、トリーｎオクチルアルミニウム、
トリーｎデシルアルミニウム等のトリアルキルアルミニ
ウム類；ジエチルアルミニウムモノクロライド等のジエ
チルアルミニウムモノハライド類；メチルアルミニウム
セスキクロライド、エチルアルミニウムセスキクロライ
ド、エチルアルミニウムジクロライド等のアルキルアル
ミニウムハライド類などがあげられる。他にモノエトキ
シジエチルアルミニウム、ジェトキシモノエチルアルミ
ニウム等のアルコキシアルミニウム類を用いることがで
きる。中でもトリエチルアルミニウムが最も好ましい。Next, as the organoaluminum compound, any compound known to be used in the polymerization of propylene can be employed without any restriction. For example, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum
Butyl aluminum, tri-octyl aluminum,
Examples include trialkylaluminums such as tri-n-decylaluminum; diethylaluminum monohalides such as diethylaluminum monochloride; and alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, and ethylaluminum dichloride. In addition, alkoxyaluminums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can be used. Among them, triethylaluminum is most preferred.
有機アルミニウム化合物の使用量はチタン化合物中のＴ
ｔ原子に対しＮ、／Ｔｉ（モル比）で１〜１００好まし
くは２〜２０であることが好適である。The amount of organic aluminum compound used is T in the titanium compound.
It is suitable that N/Ti (mole ratio) is 1 to 100, preferably 2 to 20, with respect to t atoms.
本発明の予備重合においては、上記したチタン化合物、
有機アルミニウム化合物に加えて、下記−儀式（ｎ）
Ｒ“−１（ＩＩ）
〔但し、Ｒ′はヨウ素原子又は炭化水素基である。In the prepolymerization of the present invention, the above titanium compound,
In addition to the organoaluminum compound, the following formula (n) R''-1 (II) [wherein R' is an iodine atom or a hydrocarbon group] can be used.
で示されるヨウ素化合物を用いることが、得られるポリ
オレフィンの結晶性がさらに高くなるために好ましい。It is preferable to use an iodine compound represented by the following formula because the crystallinity of the obtained polyolefin is further increased.
前記−儀式（ＩＩ）中、Ｒ“は、アルキル基、アルケニ
ル基、アルキニル基又はアリール基等の炭化水素基であ
る。本発明で好適に使用し得るヨウ素化合物を具体的に
示すと次のとおりである。例えばヨウ素、ヨウ化メチル
、ヨウ化エチル、ヨウ化プロピル、ヨウ化ブチル、ヨー
ドベンゼン、ｐヨウ化トルエン等である。中でもヨウ化
メチル、ヨウ化エチルが好ましい。ヨウ素化合物の使用
量はチタン化合物中のチタン原子に対し、Ｉ／、Ｔｉ（
モル比）で、０．１〜１００、好ましくは０．５〜５０
である。In the above-mentioned formula (II), R" is a hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Specific examples of iodine compounds that can be suitably used in the present invention are as follows. For example, iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, iodobenzene, p-iodized toluene, etc. Among them, methyl iodide and ethyl iodide are preferable.The amount of the iodine compound to be used is For the titanium atom in the titanium compound, I/, Ti(
molar ratio) from 0.1 to 100, preferably from 0.5 to 50
It is.
予備重合で用いるオレフィン類としては、エチレン、プ
ロピレン、１−ブテン、ｌ−ペンテン、〕
ｌ−ヘキセン、４−メチルペンテン＝１などがあげられ
る。また、上記のオレフィンを２種類以上同時に使用す
ることも可能であるが、立体規則性゛の向上を勘案する
と１種のオレフィンを９０モル％以上用いることが好ま
しい。予備重合では水素を共存させることも可能である
。予備重合での重合量はチタン化合物１ｇ当り１〜１０
０ｇが好ましく、工業的には２〜５０ｇの範囲が好適で
ある。Examples of the olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 4-methylpentene=1. It is also possible to use two or more of the above-mentioned olefins at the same time, but in consideration of improvement in stereoregularity, it is preferable to use 90 mol % or more of one type of olefin. It is also possible to coexist hydrogen in the prepolymerization. The amount of polymerization in prepolymerization is 1 to 10 per gram of titanium compound.
0 g is preferable, and the range of 2 to 50 g is industrially suitable.
予備重合は通常スラリー重合を適用させるのが好ましく
、溶媒として、ヘキサン、ヘプタン、シクロヘキサン、
ベンゼン、トルエンなどの飽和脂肪族炭化水素若しくは
芳香族炭化水素を単独で、またはこれらの混合？容・媒
を用いることができる。Prepolymerization is usually preferably carried out by slurry polymerization, using hexane, heptane, cyclohexane,
Saturated aliphatic hydrocarbons or aromatic hydrocarbons such as benzene and toluene alone or in combination? A container/medium can be used.
予備重合温度は、−２０〜１００℃、特に０〜６０℃の
温度が好ましい。予備重合時間は、予備重合温度及び予
備重合での重合量に応じ適宜決定すれば良く、予備重合
における圧力は、限定されるものではないが、スラリー
の重合の場合は、般に大気圧〜５ ｋｇ ／ ｃｏ！程
度である。また予備重合時に、エーテル、アミン、アミ
ド、ニトリル、カルボン酸、含硫黄化合物、酸アミド、
酸エステル、酸無水物、有機ケイ素化合物などの電子供
与体を共存させてもよい。予備重合終了後には、ヘキサ
ン、ヘプタン、シクロヘキサン、ベンゼン、トルエン等
の飽和脂肪族炭化水素若しくは芳香族炭化水素を単独で
、またはこれらの混合溶媒で洗浄することが好ましく、
洗浄回数は通常の場合５〜６回が好ましい。Prepolymerization temperature is preferably -20 to 100°C, particularly 0 to 60°C. The prepolymerization time may be appropriately determined depending on the prepolymerization temperature and the polymerization amount in the prepolymerization, and the pressure in the prepolymerization is not limited, but in the case of slurry polymerization, it is generally atmospheric pressure to 5. kg/co! That's about it. Also, during prepolymerization, ether, amine, amide, nitrile, carboxylic acid, sulfur-containing compound, acid amide,
Electron donors such as acid esters, acid anhydrides, and organosilicon compounds may also be present. After completion of prepolymerization, it is preferable to wash with a saturated aliphatic hydrocarbon or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, toluene alone or with a mixed solvent thereof,
The number of washings is usually preferably 5 to 6 times.
上記予備重合の後に本重合が行なわれる。本重合は、上
記の予備重合により得られたチタン含有ポリオレフィン
、有機アルミニウム化合物、有機ケイ素化合物及びケイ
酸エチルの存在下に行なわれる。Main polymerization is performed after the above preliminary polymerization. The main polymerization is carried out in the presence of the titanium-containing polyolefin, organoaluminum compound, organosilicon compound, and ethyl silicate obtained by the above prepolymerization.
本重合で用いられる有機アルミニウム化合物は、前述の
予備重合に用いたものが使用でき、最も好ましくはトリ
エチルアルミニウムである。有機アルミニウム化合物の
使用量はチタン含有ポリオレフィン中のチタン原子に対
し、＃！／Ｔｉ（モル比）で、１０〜１０００、好まし
くは、５０〜５００である。As the organoaluminum compound used in the main polymerization, those used in the prepolymerization described above can be used, and triethylaluminum is most preferred. The amount of organoaluminum compound used is #! with respect to the titanium atom in the titanium-containing polyolefin. /Ti (mole ratio) is 10 to 1000, preferably 50 to 500.
さらに、有機ケイ素化合物は、前記−儀式〔！〕で示さ
れる化合物が何ら制限なく採用される。In addition, organosilicon compounds can be used in the above-mentioned rituals [! ] Compounds represented by the following are employed without any restriction.
儀式Ｃ１）中のＲ及びＲ′は、アルキル基、アルケニル
基、アルキニル基及びアリール基等の炭化水素基である
。本発明において好適に用いられる有機ケイ素化合物を
例示すると、次のとおりである。R and R' in formula C1) are hydrocarbon groups such as alkyl, alkenyl, alkynyl and aryl groups. Examples of organosilicon compounds preferably used in the present invention are as follows.
例えば、トリメチルメトキシシラン、トリメチルエトキ
シシラン、ジメチルメトキシシラン、ジメチルジェトキ
シシラン、ジフェニルジメトキシシラン、メチルフエニ
ルジメトキシシラン、ジフェニルジェトキシシラン、エ
チルトリメトキシシラン、メチルトリメトキシシラン、
ビニルトリメトキシシラン、フェニルトリメトキシシラ
ン、メチルトリエトキシシラン、エチルトリエトキシシ
ラン、ビニルトリエトキシシラン、シクロヘキシルメチ
ルジメトキシシラン、プチルトリエトギシシラン、フェ
ニルトリエトキシシラン、６−ドリエトキシシリル２−
ノルボルネンなどである。For example, trimethylmethoxysilane, trimethylethoxysilane, dimethylmethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyljethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane,
Vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, cyclohexylmethyldimethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, 6-driethoxysilyl 2-
Such as norbornene.
重合で用いる有機ケイ素化合物の使用量はチタン含有ポ
リオレフィン中のＴｉ原子に対しＳｉ／Ｔｉ（モル比）
で０．１〜ｔｏｏｏ、好ましくは０．５〜５００である
。The amount of organosilicon compound used in polymerization is Si/Ti (molar ratio) relative to Ti atoms in the titanium-containing polyolefin.
is from 0.1 to too much, preferably from 0.5 to 500.
ケイ酸エチルは、テトラエト：トシシランとも呼ばれる
化合物である。その他のテトラアルコキシシランを用い
ても本発明の効果は得ることができない。ケイ酸エチル
の使用量は、チタン含有ポリオレフィン中のＴｉ原子に
対しＳｉ／Ｔｉ（モル比）で０．１〜１０００、好まし
くは０．５〜５００である。Ethyl silicate is a compound also called tetraeth:tosisilane. Even if other tetraalkoxysilanes are used, the effects of the present invention cannot be obtained. The amount of ethyl silicate used is 0.1 to 1000, preferably 0.5 to 500, in Si/Ti (molar ratio) to Ti atoms in the titanium-containing polyolefin.
本発明では、上記の有機ケイ素化合物とケイ酸エチルと
の組合せにおいて、有機ケイ素化合物の複数個とケイ酸
エチルとを組み合わせてもよい。In the present invention, in the combination of the above organosilicon compound and ethyl silicate, a plurality of organosilicon compounds and ethyl silicate may be combined.
有機ケイ素化合物とケイ酸エチルのモル比は、使用する
有機ケイ素化合物の種類及び目的とする分子量分布、立
体規則性により適宜決定できるが、一般には、有機ケイ
素化合物をケイ酸エチルに対して０．０１〜１０倍モル
、好ましくは０．０５〜５倍モル使用することが好適で
ある。The molar ratio of the organosilicon compound to ethyl silicate can be appropriately determined depending on the type of organosilicon compound used, the desired molecular weight distribution, and the stereoregularity, but generally, the molar ratio of the organosilicon compound to ethyl silicate is 0. It is suitable to use 0.01 to 10 times the mole, preferably 0.05 to 5 times the mole.
これらの触媒成分の添加順序は特に限定されず、有機ケ
イ素化合物とケイ酸エチルを同時に混合供給しても、ま
たは別々に供給してもよい。またこれらは、予め有機ア
ルミニウム化合物と接触、或いは混合させた後に供給す
ることもできる。The order of addition of these catalyst components is not particularly limited, and the organosilicon compound and ethyl silicate may be mixed and fed simultaneously or separately. Moreover, these can also be supplied after being brought into contact with or mixed with the organoaluminum compound in advance.
その他の重合条件は、本発明の効果が認められる限り、
特に制限はされないが一般には次の条件が好ましい。重
合温度は、２０〜２００℃、好ましくは５０〜１５０℃
であり、分子量調節剤として水素を共存させることもで
きる。また、重合は、スラリー重合、無溶媒重合、及び
気相重合等が適用でき、回分式、半回分式、連続式の何
れの方法でもよく、更に重合を条件の異なる２段以上に
分けて行うこともできる。重合を行うオレフィン類とし
ては、エチレン、プロピレン、ブテン−１、ペンテン−
１，ヘキセン−１，４−メチクペンテンー１などであり
、これらの七ツマ−を単独で、又は２種以上を混合して
用いることができる。、２種以上のオレフィンを用いる
場合は、特定の一種を９０モル％以上用いることが得ら
れるポリオレフィンの立体規則性の向上の点から好まし
い。Other polymerization conditions are as long as the effects of the present invention are recognized.
Although not particularly limited, the following conditions are generally preferred. Polymerization temperature is 20-200°C, preferably 50-150°C
and hydrogen can also be present as a molecular weight regulator. In addition, slurry polymerization, solvent-free polymerization, gas phase polymerization, etc. can be applied to the polymerization, and any method such as a batch method, a semi-batch method, or a continuous method may be used, and the polymerization is further divided into two or more stages with different conditions. You can also do that. Olefins to be polymerized include ethylene, propylene, butene-1, and pentene-1.
1,hexene-1,4-methicpentene-1, etc., and these hexamers can be used alone or in combination of two or more. When two or more types of olefins are used, it is preferable to use 90 mol % or more of the specific type from the viewpoint of improving the stereoregularity of the resulting polyolefin.
（効果）
本発明の方法を採用することにより、立体規則性が良く
且つ分子量分布の広いポリオレフィンが得られる。従っ
て、得られたポリオレフィンは流動性、剛性に優れ、射
出成形やフィルム成形に好適な材料である。(Effects) By employing the method of the present invention, a polyolefin with good stereoregularity and a wide molecular weight distribution can be obtained. Therefore, the obtained polyolefin has excellent fluidity and rigidity, and is a material suitable for injection molding and film molding.
本発明のオレフィン重合方法に於いて、特定の触媒系を
用いて得られるポリオレフィンの分子量分布の広がる理
由は未だ明らかではないが、本発明者らは以下のように
考えている。すなわち、本発明者らは、−儀式（１）で
表される有機ケイ素化合物を単独で用いた場合に高分子
量成分が生成し、一方、ケイ酸エチルを単独で用いた場
合に低分子量成分が生成するという興味ある事実を見い
だし、この２種を同時に用いることで同一系内に２種の
異なる活性点が生成し分子量分布が広くなることに成功
したと推定している。同時に本発明では有機ケイ素化合
物とケイ酸エチルに起因する２種の活性点が、いずれも
アイツタクチイックなものであり、このことが広分子量
分布化と高立体規則性化の同時達成につながったと考え
ている。In the olefin polymerization method of the present invention, the reason why the molecular weight distribution of the polyolefin obtained using a specific catalyst system is broadened is not yet clear, but the present inventors think as follows. That is, the present inventors have found that when the organosilicon compound represented by formula (1) is used alone, a high molecular weight component is generated, whereas when ethyl silicate is used alone, a low molecular weight component is generated. They found the interesting fact that these two types of active sites are generated, and believe that by using these two types at the same time, two different types of active sites are generated in the same system, resulting in a broader molecular weight distribution. At the same time, in the present invention, the two types of active sites originating from the organosilicon compound and ethyl silicate are both highly active, and this is believed to have led to the simultaneous achievement of a wide molecular weight distribution and high stereoregularity. thinking.
（実施例）
以下実施例及び比較例を掲げて本発明を説明するが、本
発明はこれら実施例に限定されるものではない。(Examples) The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
以下の実施例において測定方法について説明する。The measurement method will be explained in the following examples.
（１） ｐ−キシレン可溶分
ポリマー１ｇをｐ−キシレン１００ｃｃに加え攪はんし
ながら、１２０℃まで昇温した後、更に３０分撹はんを
続け、ポリマーを完全に溶かした後、ｐ−キシレン溶液
を２３℃、２４時間放置した。(1) Add 1 g of p-xylene soluble polymer to 100 cc of p-xylene, raise the temperature to 120°C while stirring, continue stirring for another 30 minutes, completely dissolve the polymer, and add p-xylene to 100 cc of p-xylene. -The xylene solution was left at 23°C for 24 hours.
析出物は濾別し、ｐ−キシレン溶液を完全に濃縮するこ
とで可溶分をえた。The precipitate was separated by filtration, and the p-xylene solution was completely concentrated to obtain a soluble component.
室温ｐ−キシレン可溶分（％）＝ （ｐ−キシレン可溶
分（ｇ）／ポリマー１ｇ）Ｘ１００で表される。Room temperature p-xylene soluble content (%) = (p-xylene soluble content (g)/1 g of polymer) x 100.
（２）メルトインデックス（以下、Ｍ＋と略す）ＡＳＴ
Ｍ ０７９０に準拠
（３）曲げ弾性率（以下、Ｆｍと略す）日本製鋼所 Ｊ
Ｉ２０ＳＡｎ型射出成形機により６３．６ ａｍ Ｘ
１２．７ ａｍ Ｘ Ｏ，３１＋ｎの試験片を作成し、
ＡＳＴＭ：Ｄ−７９０に準じて行った。(2) Melt index (hereinafter abbreviated as M+) AST
Based on M 0790 (3) Flexural modulus (hereinafter abbreviated as Fm) Japan Steel Works J
63.6 am X by I20SAn type injection molding machine
12.7 am X O, create a 31+n test piece,
It was performed according to ASTM:D-790.
（４）分子量分布（以下、ｐＪ ｗ ／ ｐＪｉ ｎと
略す）重量平均分子量（Ｍｗ）と数平均分子ｌ（Ｍｎ）
の比でＧＰｃ（ゲルバーミニ、−ジョンクロマトグラフ
ィー）法により測定した。ウォーターズ社製ＧＰＣ−１
５０ＣによりＯ−ジクロルベンゼンを溶媒とし、１３５
℃で行った。(4) Molecular weight distribution (hereinafter abbreviated as pJ w / pJin) Weight average molecular weight (Mw) and number average molecular l (Mn)
The ratio was measured by GPc (Gelvermini-John Chromatography) method. Waters GPC-1
50C using O-dichlorobenzene as a solvent, 135
It was carried out at ℃.
（５）スパイラルフロー
スパイラル金型を取り付けた８オンス射出成形機により
２３０℃で射出成型を行い、金型冷却後、ウェルド部か
らの樹脂長を測定した。(5) Injection molding was performed at 230° C. using an 8-ounce injection molding machine equipped with a spiral flow spiral mold, and after cooling the mold, the resin length from the weld portion was measured.
実施例１
〔チタン化合物の調製〕
チタン成分の調製方法は、特開昭５８−８３００６号公
報の実施例１の方法に準じて行った。すなわち無水塩化
マグネシウム０．９５ ｇ （１０ｍｍｏｌ） 、デカ
ン１０ｄ、及び２−エチルヘキシルアルコール４、７
ｄ （３０５ｓｏｌ）を１２５℃で２時間加熱攪はんし
た後、この溶液中に無水フタル酸０．５５ｇ（３，７５
ｍｍｏｌ）を添加し、１２５℃にてさらに１時間攪はん
混合を行い、均一？霧液とした。室温まで冷却した後、
−２０℃に保持された四塩化チタン４０ ｄ （０，３
６ｓｕ＋＋ｏｌ）中に１時間にわたって全量滴下装入し
た。装入終了後、この混合液の温度を２時間かけて１１
０℃に昇温し、１１０℃に達したところでジイソブチル
フタレート０．５４ｄ（２，５ｍｍｏｌ）を添加し、こ
れより２時間、同温度にて攪はん下保持した。２時間の
反応終了後熱濾過にて固体部を採取し、この固体部２０
０ｄのＴｉ Ｃ１，４にて再懸濁させた後、再び１１０
℃で２時間、加熱反応を行なった。反応終了後、再び熱
濾過にて固体部を採取し、デカン及びヘキサンにて、洗
液中に遊離のチタン化合物が検出されな（なる迄、充分
洗浄した。以上の製造方法にて調製された固体Ｔｉ触媒
成分は、ヘプタンスラリーとして保存した。固体Ｔｉ触
媒成分の組成はチタン２．１重量％、塩素５７重量％、
マグネシウム１８．０重量％、及びジイソブチルフタレ
ート２１．９重量％であった。Example 1 [Preparation of titanium compound] The titanium component was prepared according to the method of Example 1 of JP-A-58-83006. That is, 0.95 g (10 mmol) of anhydrous magnesium chloride, 10 d of decane, and 4,7 ml of 2-ethylhexyl alcohol.
After heating and stirring d (305 sol) at 125°C for 2 hours, 0.55 g of phthalic anhydride (3,75 sol) was added to this solution.
mmol) and stirred and mixed at 125°C for an additional hour until the mixture was homogeneous. It was made into a liquid mist. After cooling to room temperature,
Titanium tetrachloride 40 d (0,3
6su++ol) over 1 hour. After charging, the temperature of this mixture was increased to 11% over 2 hours.
The temperature was raised to 0°C, and when the temperature reached 110°C, 0.54 d (2.5 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, a solid portion was collected by hot filtration, and this solid portion 20
After resuspending in 0 d of Ti C1,4, again at 110
The heating reaction was carried out at ℃ for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration and thoroughly washed with decane and hexane until no free titanium compound was detected in the washing solution. The solid Ti catalyst component was stored as a heptane slurry.The composition of the solid Ti catalyst component was 2.1% by weight of titanium, 57% by weight of chlorine,
Magnesium was 18.0% by weight, and diisobutyl phthalate was 21.9% by weight.
Ｎ２置換を施した１ｚオートクレーブ中に精製へブタン
２００ｄ、トリエチルアルミニウム１５ｎｉｍｏｌ、固
体Ｔｉ触媒成分をＴｉ原子換算で５ｆｌＩｍｏｌ装入し
た後、プロピレンを全体でチタン成分１ｇに対し１０ｇ
となるように１時間連続的に反応器に導入した。なおこ
の間の温度は１５℃に保持した。After charging 200 d of purified hebutane, 15 nmol of triethylaluminum, and 5 flImol of solid Ti catalyst component in terms of Ti atom into a 1z autoclave subjected to N2 substitution, a total of 10 g of propylene was added per 1 g of titanium component.
The mixture was continuously introduced into the reactor for 1 hour. Note that the temperature during this time was maintained at 15°C.
１時間後プロピレンの導入を停止し、反応器内をＮ２で
充分に置換した。得られたスラリーの固体部分を精製へ
ブタンで６回洗浄し、チタン含有ポリオレフィンを得た
。After 1 hour, the introduction of propylene was stopped, and the inside of the reactor was sufficiently purged with N2. The solid portion of the obtained slurry was washed six times with purified hemobutane to obtain a titanium-containing polyolefin.
（重合〕
ＮｚＭ換を施した内容量４００ ／のオートクレーブに
、プロピレン２００Ｉｌを装入し、トリエチルアルミニ
ウム２１９ｍｍｏＬジフェニルジメトキシシラン６．６
１１ｍｏｌ、ケイ酸エチル２６．３ ｍｍｏｌ、更に、
水素２．０ Ｎ １を装入した後、オートクレーブの内
湯を６５℃に昇温し、チタン含有ポリオレフィンをチタ
ン原子で０．８８５ｕａｏｌ装入し、続いてオートクレ
ーブの内湯を７０℃まで昇温し、３時間のプロピレンの
重合を行った。重合圧力３１ｋｇ／ｄ、この間の温度は
７０℃に保持し、水素濃度をガスクロマトグラフで確認
しながらＱ、２ｍｏｌχに保持した。３時間後未反応の
プロピレンをパージし、白色顆粒状の重合体を得た。続
いて得られた重合体は、２００１のへブタンで６０℃、
３０分間洗浄し、十分に乾燥を行った。(Polymerization) 200 Il of propylene was charged into an autoclave with an internal capacity of 400 μl that had been subjected to NzM conversion, and 219 mmol of triethylaluminum and 6.6 mmol of diphenyldimethoxysilane were added.
11 mol, ethyl silicate 26.3 mmol, and
After charging 2.0 N 1 of hydrogen, the temperature of the inner hot water of the autoclave was raised to 65 ° C., 0.885 uaol of titanium-containing polyolefin was charged with titanium atoms, and then the inner hot water of the autoclave was heated to 70 ° C. Polymerization of propylene was carried out for 3 hours. The polymerization pressure was 31 kg/d, the temperature was maintained at 70° C., and the hydrogen concentration was maintained at Q and 2 molχ while checking with a gas chromatograph. After 3 hours, unreacted propylene was purged to obtain a white granular polymer. The resulting polymer was then heated with 2001 hebutane at 60°C.
It was washed for 30 minutes and thoroughly dried.
全重合体の収量は、３２ｋｇであり、この時の活性は１
６０００ ｇ ｐｐ／ｇ ｃａｔ ・３ｈｒであ
った。The total polymer yield was 32 kg, and the activity was 1
It was 6000 g pp/g cat ・3 hr.
上記重合体に酸化防止剤を添加し十分に混合したのち造
粒機によりベレット状とした。After adding an antioxidant to the above polymer and thoroughly mixing it, it was formed into pellets using a granulator.
Ｍｌ、ｐ−キシレン可溶分、Ｍｗ／Ｍｎ、Ｆｍ。Ml, p-xylene soluble content, Mw/Mn, Fm.
スパイラルフロー長の結果を表１に示す。Table 1 shows the results of spiral flow length.
実施例２
実施例１の重合に於いて、ジフェニルジメトキシシラン
の代わりにシクロヘキシルメチルジメトキシシラン、メ
チルフエニルジメトキシシラン、ジメチルジメトキシシ
ランを用いた以外は実施例１と同様の操作を行った。結
果を表１に示す。Example 2 The same procedure as in Example 1 was performed except that cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, and dimethyldimethoxysilane were used in place of diphenyldimethoxysilane. The results are shown in Table 1.
実施例３
実施例１の重合に於いて、ジフェニルジメトキシシラン
とケイ酸エチルのモル比を表１の割合で用いた以外は実
施例１と同様の操作を行った。結果を表１に示す。Example 3 In the polymerization of Example 1, the same operations as in Example 1 were performed except that the molar ratios of diphenyldimethoxysilane and ethyl silicate were used as shown in Table 1. The results are shown in Table 1.
実施例４
実施例１の予備重合に於いてチタン成分を添加する前に
ヨウ素５＋＋ｉｏｌを添加した以外は実施例１と同様の
操作を行った。結果を表１に示す。Example 4 The same operation as in Example 1 was performed except that 5++ iol of iodine was added before adding the titanium component in the prepolymerization of Example 1. The results are shown in Table 1.
実施例５
実施例１の予備重合に於いてチタン成分を添加する前に
ヨウ化エチル５１０１を添加した以外は実施例１と同様
の操作を行った。結果を表１に示す。Example 5 The same operation as in Example 1 was performed except that ethyl iodide 5101 was added before adding the titanium component in the prepolymerization of Example 1. The results are shown in Table 1.
比較例１
実施例１の重合に於いて、ケイ酸エチルを用いなかった
以外は実施例１と同様の操作を行った。Comparative Example 1 In the polymerization of Example 1, the same operation as in Example 1 was performed except that ethyl silicate was not used.
結果を表２に示す。The results are shown in Table 2.
比較例２
実施例１の重合に於いて、ジフェニルジメトキシシラン
を用いなかった以外は実施例１と同様の操作を行った。Comparative Example 2 In the polymerization of Example 1, the same operation as in Example 1 was performed except that diphenyldimethoxysilane was not used.
結果を表２に示す。The results are shown in Table 2.
比較例３
実施例１に於いて、予備重合を施さなかった以外は実施
例１と同様の操作を行った。結果を表２に示す。Comparative Example 3 The same operation as in Example 1 was performed except that preliminary polymerization was not performed. The results are shown in Table 2.
比較例４
実施例１の重合に於いて、ケイ酸エチルの代わりにメチ
ルトリエトキシシラン、ケイ酸メチル、ケイ酸イソプロ
ピル、ケイ酸ブチルを用いた以外は実施例１と同様の操
作を行った。結果を表２に示す。Comparative Example 4 In the polymerization of Example 1, the same operation as in Example 1 was performed except that methyltriethoxysilane, methyl silicate, isopropyl silicate, and butyl silicate were used instead of ethyl silicate. The results are shown in Table 2.
手続補正書Procedural amendment
Claims (1)
ン Ｂ 有機アルミニウム化合物 Ｃ 一般式 Ｒ＿ｎＳｉ（ＯＲ′）＿４＿−＿ｎ 〔但し、ＲおよびＲ′は、同種又は異種 の炭化水素基であり、ｎは１〜３の整数 である。〕 で示される有機ケイ素化合物 Ｄ ケイ酸エチル の存在下にオレフィンを重合することを特徴とするポリ
オレフィンの製造方法。(1) A Titanium-containing polyolefin obtained by prepolymerization B Organoaluminum compound C General formula R_nSi(OR')_4_-_n [However, R and R' are the same or different hydrocarbon groups, and n is 1 It is an integer of ~3. ] Organosilicon compound D represented by: A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of ethyl silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32362288A JPH0747604B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32362288A JPH0747604B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02170803A true JPH02170803A (en) | 1990-07-02 |
| JPH0747604B2 JPH0747604B2 (en) | 1995-05-24 |
Family
ID=18156792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32362288A Expired - Fee Related JPH0747604B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0747604B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7244794B2 (en) | 2005-03-29 | 2007-07-17 | Samsung Total Petrochemicals Co., Ltd. | Method for producing propylene polymer having a very high melt-flowability |
| US7619048B2 (en) | 2005-09-30 | 2009-11-17 | Samsung Total Petrochemicals Co., Ltd. | Method for producing propylene polymer using alkoxysilane compound containing trialkysilyl group in molecular structure |
-
1988
- 1988-12-23 JP JP32362288A patent/JPH0747604B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7244794B2 (en) | 2005-03-29 | 2007-07-17 | Samsung Total Petrochemicals Co., Ltd. | Method for producing propylene polymer having a very high melt-flowability |
| US7619048B2 (en) | 2005-09-30 | 2009-11-17 | Samsung Total Petrochemicals Co., Ltd. | Method for producing propylene polymer using alkoxysilane compound containing trialkysilyl group in molecular structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0747604B2 (en) | 1995-05-24 |
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