JPH011707A - Catalyst for highly stereoregular polymerization of α-olefins - Google Patents
Catalyst for highly stereoregular polymerization of α-olefinsInfo
- Publication number
- JPH011707A JPH011707A JP62-156604A JP15660487A JPH011707A JP H011707 A JPH011707 A JP H011707A JP 15660487 A JP15660487 A JP 15660487A JP H011707 A JPH011707 A JP H011707A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- polymerization
- titanium tetrachloride
- olefins
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims description 37
- 238000006116 polymerization reaction Methods 0.000 title claims description 29
- 239000004711 α-olefin Substances 0.000 title claims description 9
- 239000000126 substance Substances 0.000 claims description 22
- -1 paramenthane compound Chemical class 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 13
- CFJYNSNXFXLKNS-UHFFFAOYSA-N trans-p-menthane Natural products CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229930004008 p-menthane Natural products 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000005690 diesters Chemical class 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 19
- 239000011949 solid catalyst Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 230000000379 polymerizing effect Effects 0.000 description 7
- 150000003377 silicon compounds Chemical class 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 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 4
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- POXXQVSKWJPZNO-UHFFFAOYSA-N 1-o-ethyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC(C)C POXXQVSKWJPZNO-UHFFFAOYSA-N 0.000 description 1
- JEABIFHLYSDNRJ-UHFFFAOYSA-N 2-o-butyl 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC JEABIFHLYSDNRJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YDFHVOKEEMMIBE-RDJQXTLESA-N M-factor Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CSC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(=O)OC)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](NC(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](NC(=O)[C@@H](N)CC=1C=CC(O)=CC=1)[C@@H](C)O)C(C)C)C1=CC=C(O)C=C1 YDFHVOKEEMMIBE-RDJQXTLESA-N 0.000 description 1
- 101710204204 M-factor Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JANBFCARANRIKJ-UHFFFAOYSA-N bis(3-methylbutyl) benzene-1,2-dicarboxylate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1C(=O)OCCC(C)C JANBFCARANRIKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 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
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 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
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はα−オレフィン項の重合に供した際に、高活性
を維持しつつ、極めて高い立体規則性を有する重合体を
得ることのできる高性能触媒に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention makes it possible to obtain a polymer having extremely high stereoregularity while maintaining high activity when subjected to the polymerization of an α-olefin term. It concerns high performance catalysts.
プロピレンの立体規則性重合用触媒としては、従来周知
の三塩化チタンと有機アルミニウム化合物を組合せた触
媒以外に、新しい型のいわゆる担持型触媒として四塩化
チタンを塩化マグネシウムに電子供与体と共に担持して
、有機アルミニウム化合物および電子供与体と組合せて
用いるものをはじめとする数多くの新型触媒が開発され
提案されている。しかし、これらいずれの触媒において
も生成重合体の立体規則性の点に関して改善の余地を残
しており、高い立体規則性を必要とする場合νこは重合
時に多量の電子供与体を添加使用することが実用上不可
欠とされていた。ところが、斯かる手法をもってしても
極端に高い立体規則性を荷する重汁体は得られず、特に
高活性を維持しつつ、しかも極めて高い立体規則性をも
得ることは全く不可能であった。Catalysts for the stereoregular polymerization of propylene include, in addition to the well-known catalyst combining titanium trichloride and an organoaluminum compound, a new type of supported catalyst in which titanium tetrachloride is supported on magnesium chloride together with an electron donor. A number of new catalysts have been developed and proposed, including those used in combination with organoaluminum compounds and electron donors. However, in all of these catalysts, there is still room for improvement in terms of the stereoregularity of the resulting polymer, and if high stereoregularity is required, a large amount of electron donor should be added during polymerization. was considered indispensable for practical purposes. However, even with such a method, it is not possible to obtain a heavy sucrose with extremely high stereoregularity, and in particular, it is completely impossible to obtain extremely high stereoregularity while maintaining high activity. Ta.
また、従来のいわゆる担持型触媒においては触媒中に含
まれるチタン原子に対して圧到的大過剰の有機アルミニ
ウム化合物を用いることが必要であり、これはポリオレ
フィンのコストの上昇につながるばかりでなく、生成重
合体にアルミニウム成分残渣として含まれるたりに、品
質低下の原因ともなっていた。したがって有機アルミニ
ウム化合物の使用量を減少させることは解決すべき技術
的課題であったが、単に有機アルミニウム化合物の使用
量全減少させるのみでは触媒の活性が低下し、本発明者
等の知見によれば生成重合体の嵩比重も低下する。In addition, in conventional supported catalysts, it is necessary to use an extremely large excess of organoaluminum compounds relative to the titanium atoms contained in the catalyst, which not only leads to an increase in the cost of polyolefins, but also It was also included as an aluminum component residue in the produced polymer, causing quality deterioration. Therefore, reducing the amount of organoaluminum compounds used was a technical problem to be solved, but simply reducing the total amount of organoaluminum compounds used will reduce the activity of the catalyst, and according to the findings of the present inventors. In this case, the bulk specific gravity of the produced polymer also decreases.
さらに、通常、前記電子供与体は有機アルミニウム化合
物に対して一定のモル比で用いられるため、従来一般に
行なわれてきた方法では、固体触媒成分に対してかなり
多量に使用することが必要でめった。Furthermore, since the electron donor is usually used in a fixed molar ratio with respect to the organoaluminum compound, in conventional methods, it has been necessary to use it in a considerably large amount relative to the solid catalyst component.
本発明は、かかる従来技術における種々の問題点を解決
し得る新規なα−オレフィン類の高立体規則性重合用触
媒を提供することを目的とするものである。The object of the present invention is to provide a novel catalyst for highly stereoregular polymerization of α-olefins that can solve the various problems in the prior art.
本発明は、
（り ジアルコキシマグネシウム（ａ）ｉ常温で液体
の芳香族炭化水素（ｂ）中に懸濁させ、しかる後に四塩
化チタン（ｃ）および芳香族ジカルボン酸のジエステル
（ｄ）と８０℃ないし１３５℃の温′度域で反応させて
得られた固体物質を分離して、これにさらに四塩化チタ
ン（ｃｌ−反応させて固体生成物を得、該固体生成物に
一般弐ＳＩＲｍ（ＯＨ２）４−ｒｎ（式中Ｒはアルキル
基、シクロアルキル基、ビニル基またはアリール基であ
り、Ｒ′はアルキル基である。Ｒがアルキル基である場
合はそのアルキル基はＲ′と同一であってもよい。ｍは
０≦ｍく４である。）で表わされるケイ素化合物（ｅ）
を接触させ、次いで有機アルミニウム化合物（ｆ） ｌ
接触させることによって得られる固体触媒成分；
（ＩＩ） エポキシパラメンタン化合物および
佃） 有機アルミニウム化合物
よりなることを特徴とするα−オレフィン類の高立体規
則性重合用触媒を提供するものである。The present invention is characterized in that dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon (b) which is liquid at room temperature, and then mixed with titanium tetrachloride (c) and a diester of an aromatic dicarboxylic acid (d). The solid material obtained by the reaction at a temperature range of 135°C to 135°C is separated and further reacted with titanium tetrachloride (Cl-) to obtain a solid product. OH2)4-rn (wherein R is an alkyl group, cycloalkyl group, vinyl group or aryl group, and R' is an alkyl group. When R is an alkyl group, the alkyl group is the same as R') silicon compound (e), where m is 0≦m×4.
and then organic aluminum compound (f) l
The present invention provides a catalyst for highly stereoregular polymerization of α-olefins, which is characterized by comprising a solid catalyst component obtained by contacting: (II) an epoxy paramenthane compound and an organoaluminum compound.
本発明に係るオレフィン類重合用触媒において使用され
る前記（ａ）のジアルコキシマグネシウム（以下単に（
ａ）物質という。）としては、ジェトキシマグネシウム
、ジブトキシマグネシウム、ジフェノキクマグネシウム
、ジグロボキシマグネシウム、ジイソブトキシマグネシ
ウム、ジイソプロポキシマグネシウム等があげられるが
中でもジェトキシマグネシウム、ジグロボキシマグネシ
ウムが好ましい。Dialkoxymagnesium (hereinafter simply referred to as (a)) used in the catalyst for polymerizing olefins according to the present invention
a) It is called a substance. ) include jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, digloboxymagnesium, diisobutoxymagnesium, diisopropoxymagnesium, etc. Among them, jetoxymagnesium and digloboxymagnesium are preferred.
本発明に係るオレフィン類重合用触媒で用いられる前記
（ｂ）の常温で液体の芳香族炭化水素（以下単に（ｂ）
物質という。）としてはトルエン、キシレン、エチルベ
ンゼン、フロビルベンゼン、ブチルベンゼンなどがあげ
られる。The above (b) aromatic hydrocarbon that is liquid at room temperature (hereinafter simply referred to as (b)) used in the catalyst for polymerizing olefins according to the present invention
It is called substance. ) include toluene, xylene, ethylbenzene, flobylbenzene, butylbenzene, etc.
本発明に係るオレフィン類重合用触媒で用いられる前記
（ｄ）の芳香族ジカルボン酸のジエステル（以下単に（
ａ）物質という。）としては、フタル酸のジエステルが
好ましく、例えば、ジメチルフタレート、ジエチルフタ
レート、ジプロピルフタレート、ジイソプロピルフタレ
ート、ジブチルツクｖ−１−、ジイソプロピルフタレー
ト、シアミルフタレート、ジイソアミルフタレート、エ
チルブチルフタレート、エチルイソブチルフタレート、
エチルプロピル７タレートなどがあげられる。The diester of the aromatic dicarboxylic acid (d) used in the catalyst for polymerizing olefins according to the present invention (hereinafter simply (
a) It is called a substance. ) is preferably a diester of phthalic acid, such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisopropyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate. ,
Examples include ethylpropyl 7-talate.
本発明に係るオレフィン類重合用触媒において使用され
る前記（ｅ）のケイ素化合物（以下単に（６）物質とい
う。）としてはアルコキシシラン、フェニルアルコキシ
シラ／、アルキルアルコキンシラン、ビニルアルコキシ
シラン、シクロアルキルアルコキシシラン、シクロアル
キルアルキルアルコキシシランなどがめげられるが具体
的例としてテトラメトキシシラン、テトラエトキシシラ
ン、フェニルトリメトキシシラン、フェニルトリエトキ
シシラン、フェニルトリプロポキシシラン、フェニルト
リイソプロポキシシラン、ジフェニルジメトキシシラン
、ジフェニルジェトキシシラン、メチルトリメトキシシ
ラン、メチルトリメトキシシラン、メチルトリエトキシ
クラン、エチルトリエトキシシラン、エチルトリイソプ
ロポキシシラン、ビニルトリメトキシシラン、ビニルト
リエトキシシランなどをあげることができる、
本発明に係るオレフィン類重合用触媒において用いられ
る前記（ＩＩ）のエポキシパラメンタン化合物としては
１．８−エポキシパラメンタンないしはそれにアルキル
基やノーロゲンなどの置換基の結合のものの中から選択
して用いることができる。Examples of the silicon compound (e) (hereinafter simply referred to as substance (6)) used in the catalyst for polymerizing olefins according to the present invention include alkoxysilane, phenylalkoxysila/, alkylalcoquine silane, vinylalkoxysilane, cyclo Specific examples include alkyl alkoxysilane, cycloalkylalkyl alkoxysilane, etc., but specific examples include tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, and diphenyldimethoxysilane. , diphenyljethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxyclane, ethyltriethoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. The epoxy paramenthane compound (II) used in the catalyst for polymerizing olefins may be selected from 1,8-epoxy paramenthane or those bound to substituents such as alkyl groups and norogens. can.
本発明に係るオレフィン類重合用触媒において用いられ
る前記（ｆ）または（２））の有機アルミニウム化合物
としては、トリアル中ルアルミニウム、ジアルキルアル
ミニウムハライド、アルキルアルミニウムシバライド、
アルキルアルミニウムセスキハライドおよびこれらの混
合物があげられる。Examples of the organoaluminum compound (f) or (2)) used in the catalyst for polymerizing olefins according to the present invention include aluminum in trial, dialkylaluminum halide, alkylaluminum civalide,
Mention may be made of alkyl aluminum sesquihalides and mixtures thereof.
前述の固体生成物を得る際の第１の好ましい態様として
は、（ａ）物質を（ｂ）物質中に懸濁させ、しかる後に
四塩化チタンを加え、８０℃以上に昇温した後（ｄ）物
質を添加して８０℃ないし１３５℃の温度域で反応さ・
Ｃる方法があげられる。また、第２の好ましい態様とし
ては、四塩化チタンと（、ｉ）物質を室温で添加した後
、８０℃ないし１５５℃の温度域で反応させる方法があ
げられる。なお、上述の四塩化チタンは、これを常温で
液体の芳香族炭化水素で希釈して用いることができる。A first preferred embodiment for obtaining the above-mentioned solid product is to suspend (a) the substance in the (b) substance, then add titanium tetrachloride, raise the temperature to 80°C or higher, and then (d) ) is added and reacted at a temperature range of 80℃ to 135℃.
There are ways to do C. A second preferred embodiment is a method in which titanium tetrachloride and the substance (i) are added at room temperature and then reacted in a temperature range of 80°C to 155°C. Note that the above-mentioned titanium tetrachloride can be used by diluting it with an aromatic hydrocarbon that is liquid at room temperature.
前述の固体触媒成分の調製における各物質の使用割合は
通常（ａ） ＊質１ｔに対し、（ｄ）物質はα０１〜２
ｆ、好ましくはα１〜１ｆの範囲であり、四塩化チタン
は１１を以上、好ましくは１２以上の範囲である。また
、（ｂ）物質は、任意の割合で用いられるが、懸濁液を
形成し得る量であることが必要である。The ratio of each substance used in the preparation of the above-mentioned solid catalyst component is usually (a) *1 ton of substance, and (d) substance α01~2
f is preferably in the range of α1 to 1f, and titanium tetrachloride is in the range of 11 or more, preferably 12 or more. Further, the substance (b) may be used in any proportion, but it is necessary that the amount is such that a suspension can be formed.
さらに、各原料物質の反応および接触は通常０℃から用
いられるチタンハロゲン化物の沸点までの温度で１００
時間以下、好ましくＦｉｌＯ時間以下の範囲で行なわれ
る。Furthermore, the reaction and contact of each raw material is usually carried out at a temperature ranging from 0°C to the boiling point of the titanium halide used for 100°C.
It is carried out within a range of less than 1 hour, preferably less than FilO time.
以上の如くして得られた固体生成物に（ｅ）物質を接触
させ、次−で有機アルミニウム化合物（ｂ）を接触させ
て固体触媒成分を得るがこの際通常該固体生成物１ｔに
対し、（ｅ）物質は１１〜Ｓ？。The solid product obtained as described above is brought into contact with the substance (e), and then brought into contact with the organoaluminum compound (b) to obtain a solid catalyst component. (e) Is the substance 11-S? .
有機アルミニウム化合物（ｆ）はα１〜１０？の範囲で
用いられる。上記の（ｅ）物質との接触あるいは有機ア
ルミニウム化合物（ｆ）との接触はいずれも１００℃以
下の温度で１００時間以下、好ましくは１０時間以内行
なわれる。Is the organoaluminum compound (f) α1-10? Used within the range of The contact with the above-mentioned substance (e) or the contact with the organic aluminum compound (f) is carried out at a temperature of 100° C. or less for 100 hours or less, preferably 10 hours or less.
前記の固体生成物は（ｅ）物質との接触に先だち適当な
有機溶媒を用いて洗浄される。(e) The solid product is washed with a suitable organic solvent prior to contact with the substance.
また、上記の（ａ）物質、（ｂ）物質、四塩化チタンお
よび（ａ）物質より得られる固体物質および上記の固体
触媒成分はいずれも必要に応じて適時適当な有機溶媒を
用いて洗浄することが好ましい。In addition, the above (a) substance, (b) substance, titanium tetrachloride, the solid substance obtained from the (a) substance, and the above solid catalyst component are all washed with an appropriate organic solvent as needed. It is preferable.
上述の操作は酸素および水分等の不存在下に行なわれる
ことが好ましい。The above operations are preferably carried out in the absence of oxygen, moisture, and the like.
以上の如くして製造された固体触媒成分は、前述のエポ
キシパラメンタン化合物および有機アルミニウム化合物
と組合せてオレフィン類重合用触媒を形成する。使用さ
れる有機アルミニウム化合物の量は特に限定されるもの
ではないが前述の如き理由で少ない方が好ましく、通常
触媒成分中のチタン原子のモル当りモル比で１〜５０の
範囲で用いられる。念だし、十分な性能を得られる範囲
であれば、概略上記モル比を満足していればよい、また
、該エポキシパラメンタン化合物は有機アルミニウム化
合物のモル当りモル比で１以下の範囲で用いられる。The solid catalyst component produced as described above is combined with the above-mentioned epoxy paramenthane compound and organoaluminum compound to form a catalyst for polymerizing olefins. Although the amount of the organoaluminum compound used is not particularly limited, it is preferably small for the reasons mentioned above, and is usually used in a molar ratio of 1 to 50 per mole of titanium atoms in the catalyst component. As a reminder, as long as sufficient performance can be obtained, it is sufficient to approximately satisfy the above molar ratio, and the epoxy paramenthane compound is used at a molar ratio of 1 or less per mole of the organoaluminum compound. .
重合は有機溶媒の存在下でも或いは不存在下でも行なう
ことができ、またオレフィン単量体は気体および液体の
いずれの状四でも用いることができる。重合温度！−！
２００℃以下好ましくは１００℃以下であり゛、重合圧
力は１００ゆ／ｃＷ１２・Ｇ以下、好ましくは５０ ｋ
ｌ／ｃｍ” −Ｇ以下である。Polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gaseous or liquid form. Polymerization temperature! -!
The temperature is 200℃ or less, preferably 100℃ or less, and the polymerization pressure is 100Y/cW12・G or less, preferably 50K.
l/cm"-G or less.
本発明に係る触媒を用いて単独重合または共重合される
α−オレフィン類はプロピレン、１−プテン等である。α-olefins that are homopolymerized or copolymerized using the catalyst according to the present invention include propylene, 1-butene, and the like.
本発明に係る触媒によれば従来実用上全く得られなかっ
たような高い立体規則性を持つ重合体を得ることができ
、しかも触媒の活性も高度に維持することができる。According to the catalyst of the present invention, it is possible to obtain a polymer having a high degree of stereoregularity, which has never been practically obtained in the past, and the activity of the catalyst can also be maintained at a high level.
本発明の触媒によれば従来の技術と比較して、重合時の
有機アルミニウム化合物やケイ素化合物の使用Ｊｔｅ著
しく減少させることができる。According to the catalyst of the present invention, the use of organoaluminum compounds and silicon compounds during polymerization can be significantly reduced compared to conventional techniques.
しかも触媒活性や生成重合体の嵩比重の低下が起らない
という効果があり、このことはポリオレフィンの製造コ
ストを低減できるという大きな利点をも次らし、また、
有機アルミニウム化合物やケイ素化合物に起因する生成
重合体中の残渣を少なくできるという利点をもたらす。Moreover, it has the effect of not causing a decrease in the catalyst activity or the bulk specific gravity of the produced polymer, which has the great advantage of reducing the manufacturing cost of polyolefin.
This has the advantage that the amount of residue in the produced polymer due to organoaluminum compounds and silicon compounds can be reduced.
また、本発明の触媒によれば重合時に用いるケイ素化合
物ｔ’を大幅に減少することができるため生成重合体に
おける臭気の問題を実質上解決することができ、このこ
とは、特にバルク重合や気相重合においてより大きな利
点となる。Furthermore, according to the catalyst of the present invention, the amount of silicon compound t' used during polymerization can be significantly reduced, so that the problem of odor in the resulting polymer can be substantially solved. This is a greater advantage in phase polymerization.
さらに、従来、触媒の単位時間当りの活性が、重合の経
過に伴なづて大幅に低下するという、いわゆる高活性担
持型触媒における共通の欠点が存在したが、本発明に係
る触媒においては、重合時間の経過に伴なう活性の低下
が、従来公知の触媒に比較し、極めて小さいため、共重
合等重合時間をより長くする場合にも有用である。Furthermore, conventionally, there has been a common drawback in so-called high-activity supported catalysts in that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, Since the decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, it is also useful in cases where the polymerization time is longer, such as in copolymerization.
さらに付言すると、工業的なオレフィン重合、体の製造
においては重合時に水素を共存させることがＭ工制御な
どの点から一般的とされているが、従来の塩化マグネシ
ウムを担体とし、有機カルボン酸エステルを用いた触媒
は水素共存下では活性および立体規則性が大幅に低下す
るという欠点を有していた。しかし、本発明に係る触媒
を用いて水素共存下にオレフィンの重合を行なった場合
、特に生成重合体のＭ工が極めて高い場合においても、
活性および立体規則性ｕ低下ｔ、ない。工業的なポリオ
レフィンの製造においては重合装置の能力、後処理工程
の能力などの点で生成重合体の嵩比重が非常に大きな問
題となるが、本発明に係る触媒は、この点においても、
極めて優れた特性に有している。Furthermore, in industrial olefin polymerization and olefin production, it is common practice to coexist hydrogen during polymerization from the viewpoint of M process control. Catalysts using this catalyst had the disadvantage that their activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when olefin polymerization is carried out in the coexistence of hydrogen using the catalyst according to the present invention, even when the resulting polymer has an extremely high M-factor,
Activity and stereoregularity decrease, no. In the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem in terms of the capacity of the polymerization equipment, the capacity of the post-treatment process, etc., but the catalyst according to the present invention also has the following problems in this respect:
It has extremely excellent properties.
以下に、本発明を実施例および比較し！Ｉ ＶＣよりさ
らに具体的に説明する。Examples and comparisons of the present invention are given below! This will be explained more specifically than IVC.
実ｒ１Ｅ２リ １
〈固体触媒成分の調製〉
窒素ガスで充分に置換され、撹拌機を具備した容Ｒ２０
０−の丸底フラスコにジェトキシマグネシウム１０２お
よびトルエン８０ｇＲｔｉ装入して懸濁状態とした。次
いでこの懸濁液ｒこＴｉ０６゜２０−を加え１００１：
：に昇温してジブチルフタレート２．５−を加えた。次
いで１１５℃に昇温して２時間攪拌しながら反応させ固
体物質を得た。該固体物質を６０℃のトルエン１００−
で３回洗浄し、新たにトルエン８Ｏ−１Ｔ ｉ Ｏｔ４
２０ｔｄｆｒ：加えて１１５℃で２時間攪拌しながら反
応させた。Actual R1E2 Li 1 <Preparation of solid catalyst component> A volume R20 sufficiently purged with nitrogen gas and equipped with a stirrer.
102 g of jetoxymagnesium and 80 g Rti of toluene were placed in a round bottom flask to form a suspension. Next, this suspension was added with Ti06°20-1001:
: The temperature was raised to 2.5-dibutyl phthalate was added. Next, the temperature was raised to 115°C, and the mixture was reacted with stirring for 2 hours to obtain a solid substance. The solid material was immersed in toluene at 60°C.
Wash 3 times with toluene 8O-1T i Ot4
20 tdfr: In addition, the mixture was reacted at 115°C for 2 hours with stirring.
反応終了後４０℃のｎ−ヘプタン２００ｄによる洗浄を
１０回行ない固体生成物を得た。この際、該固体生成物
中のチタン含有率を測定したところ２．８２重量うでめ
った。次に該固体生成物３２を内容積３００−の撹拌装
置付丸底フラスコにとり、ｎ−ヘプタン１０ローおよび
ジフェニルジメトキシシラン１．０＋ｄ’！（加えて充
分に攪拌しな後、トリイソブチルアルミニウム１、ロー
およびジエチルアルミニウムクロライド［１２ｍを加え
て室温で２時間攪拌下に反応させた。反応終了後室温の
ｎ−へブタン１００−で５回洗浄し固体触媒成分とした
。なお、この際固体触媒成分中のチタン含有率を測定し
たところ２．５６重ｉｉ−優であった。After completion of the reaction, washing with 200 d of n-heptane at 40°C was performed 10 times to obtain a solid product. At this time, the titanium content in the solid product was measured and found to be 2.82 weight. The solid product 32 was then placed in a 300-liter round bottom flask equipped with a stirrer, and 10 rho of n-heptane and 1.0+d' of diphenyldimethoxysilane were added. (After addition and sufficient stirring, triisobutylaluminum 1, rho and diethylaluminum chloride [12m] were added and reacted at room temperature with stirring for 2 hours. After the reaction was completed, n-hebutane 100-100% at room temperature was added 5 times. It was washed to obtain a solid catalyst component. At this time, the titanium content in the solid catalyst component was measured and was found to be 2.56% by weight.
く重 合〉
窒素ガスで完全に置換された内容積２．０ｔの攪拌装置
付オートクレーブに、ｎ−へブタン７００ｄｆｔ装入し
、窒素ガス雰囲気を保ちつつトリエチルアルミニウム５
０１９，１．８−エポキシパラメンタン２０ｑ１次いで
前記固体触媒成分１９５ｑを装入した。その後水素ガス
１５〇−を装入し７０℃に昇温してプロピレンガスを導
入しつつ６に９／ｅｔｙｒ”・Ｇの圧力を維持して２時
間の重合を行なった。重合終了後得られた固体重合体を
Ｆ別し、８０℃に加温して減圧乾燥した。一方、Ｆ液を
凝縮して重合溶媒に溶存する重合体の量を仏）とし、固
体重合体の量金山）とする。また得られた固体重合体を
沸騰ｎ−へブタンで６時間抽出しｎ−へブタンに不溶解
の重合体を得、この量ｋ （ｃ）とする。Polymerization> 700 dft of n-hebutane was charged into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which was completely purged with nitrogen gas, and 5 dft of triethylaluminum was added while maintaining the nitrogen gas atmosphere.
20q1 of 019,1.8-epoxy paramenthane and then 195q of the solid catalyst component were charged. Thereafter, hydrogen gas (150°C) was charged, the temperature was raised to 70°C, and propylene gas was introduced while maintaining a pressure of 6 to 9/etyr"·G and polymerization was carried out for 2 hours. After the polymerization was completed, the obtained The solid polymer obtained was separated into F, heated to 80°C and dried under reduced pressure.Meanwhile, the amount of polymer dissolved in the polymerization solvent by condensing the F solution was defined as the amount of solid polymer. Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was defined as k (c).
固体触媒成分当りの重合活性ノ）ヲ式 また結晶性重合体の収率■）を式 で表わし、全結晶性重合体の収率伊）ヲ式より求めた。Polymerization activity per solid catalyst component In addition, the yield of crystalline polymer (■) is expressed by the formula The yield of the total crystalline polymer was determined from the formula.
また生成重合体中の残留塩素を（Ｇ）、生成重合体のＭ
Ｉを市）、嵩比ｆｆ ｅ （ｂ）で表わす。In addition, residual chlorine in the produced polymer (G), M of the produced polymer
I is expressed as city) and bulk ratio ff e (b).
得られた結果は第１表に示す通りである。The results obtained are shown in Table 1.
実施例２
ジフェニルジメトキシシランの代りに７エニルトリエト
キシシランを用いた以外は実施例１と同様にして実験を
行なった。なお、この際の固体触媒成分中のチタン含有
率は２．５１重ｆｆｉ憾であった。重合に際しては固体
触媒成分１ρ９ｑを用いた以外は実施例１と同様にして
実験を行った。得られた結果は、第１表に示す通りであ
る。Example 2 An experiment was carried out in the same manner as in Example 1 except that 7enyltriethoxysilane was used instead of diphenyldimethoxysilane. Incidentally, the titanium content in the solid catalyst component at this time was 2.51 parts ffi. An experiment was conducted in the same manner as in Example 1, except that 1ρ9q of solid catalyst components were used during the polymerization. The results obtained are shown in Table 1.
実施例３
ジフェニルジメトキシシランのｆｌ を１５ｍとした以
外は実施例１と同様にして実験を行なった。なお、この
際の固体触媒成分中のチタン含有率は２．６０重量憾で
あった。重合に際しては固体触媒成分１９．２５９’に
用いた以外は、実施例１と同様にして実験を行なった。Example 3 An experiment was conducted in the same manner as in Example 1 except that the fl of diphenyldimethoxysilane was changed to 15 m. Incidentally, the titanium content in the solid catalyst component at this time was 2.60% by weight. An experiment was carried out in the same manner as in Example 1, except that solid catalyst component 19.259' was used for polymerization.
得られた結果は第１表に示す通りである。The results obtained are shown in Table 1.
比較例１
重合時［１，８−エポキシパラメンタンを使用すること
なく、他は、実施例１と同様にして実験を行なった。得
られた結果は第１表に示す通りである。Comparative Example 1 An experiment was conducted in the same manner as in Example 1, except that 1,8-epoxy paramenthane was not used during polymerization. The results obtained are shown in Table 1.
第１表Table 1
【図面の簡単な説明】
第１図は本発明の理解を助けるための模式的図面である
。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic drawing to help understand the present invention.
Claims (1)
液体の芳香族炭化水素（ｂ）中に懸濁させ、しかる後に
、四塩化チタン（ｃ）および芳香族ジカルボン酸のジエ
ステル（ｄ）と８０℃ないし１３５℃の温度域で反応さ
せて得られた固 体物質を分離して、これにさらに四塩化チ タン（ｃ）を反応させて固体生成物を得、該固体生成物
に一般式ＳｉＲ＿ｍ（ＯＲ′）＿４＿−＿ｍ（式中Ｒは
アルキル基、シクロアルキル基、ビニル 基またはアリール基であり、Ｒ′はアルキル基である。 Ｒがアルキル基である場合はそ のアルキル基はＲ′と同一であつてもよい。 ｍは０≦ｍ＜４である。）で表わされるケ イ素化合物（ｅ）を接触させ、次いで有機アルミニウム
化合物（ｆ）を接触させることによつて得られる固体触
媒成分； （II）エポキシパラメンタン化合物 および （III）有機アルミニウム化合物 よりなることを特徴とするα−オレフィン類の高立体規
則性重合用触媒。 ２）上記の固体物質を得る際、ジアルコキシマグネシウ
ム（ａ）を常温で液体の芳香族炭化水素（ｂ）中に懸濁
させ、しかる後に四塩化チタン（ｃ）を加え、８０℃以
上に昇温した後芳香族ジカルボン酸のジエステル（ｄ）
を添加して８０℃ないし１３５℃の温度域で反応させる
ことよりなる特許請求の範囲第１項記載のα−オレフィ
ン類の高立体規則性重合用触媒。 ３）前記の固体物質を得る際、四塩化チタン（ｃ）と芳
香族ジカルボン酸のジエステル（ｄ）を室温で添加した
後、８０℃ないし１３５℃の温度域で反応させることよ
りなる特許請求の範囲第１項記載のα−オレフィン類の
高立体規則性重合用触媒。 ４）前記の四塩化チタン（ｃ）を常温で液体の芳香族炭
化水素で希釈して用いる特許請求の範囲第１項ないし第
３項のいずれかに記載のα−オレフィン類の高立体規則
性重合用触媒。[Claims] 1) (I) Dialkoxymagnesium (a) is suspended in a liquid aromatic hydrocarbon (b) at room temperature, and then titanium tetrachloride (c) and an aromatic dicarboxylic acid are suspended in a liquid aromatic hydrocarbon (b). A solid material obtained by reacting with diester (d) at a temperature range of 80° C. to 135° C. is separated, and this is further reacted with titanium tetrachloride (c) to obtain a solid product, and the solid product is has the general formula SiR_m(OR')_4_-_m (wherein R is an alkyl group, cycloalkyl group, vinyl group, or aryl group, and R' is an alkyl group. When R is an alkyl group, the alkyl group may be the same as R'; m is 0≦m<4.) and then an organoaluminum compound (f). A catalyst for highly stereoregular polymerization of α-olefins, comprising: (II) an epoxy paramenthane compound; and (III) an organoaluminum compound. 2) When obtaining the above solid substance, dialkoxymagnesium (a) is suspended in liquid aromatic hydrocarbon (b) at room temperature, then titanium tetrachloride (c) is added, and the temperature is raised to 80°C or higher. Diesters of aromatic dicarboxylic acids (d) after warming
The catalyst for highly stereoregular polymerization of α-olefins according to claim 1, which comprises adding and reacting at a temperature range of 80°C to 135°C. 3) When obtaining the solid substance, titanium tetrachloride (c) and diester of aromatic dicarboxylic acid (d) are added at room temperature and then reacted at a temperature range of 80°C to 135°C. A catalyst for highly stereoregular polymerization of α-olefins according to Item 1. 4) High stereoregularity of α-olefins according to any one of claims 1 to 3, in which the titanium tetrachloride (c) is diluted with an aromatic hydrocarbon that is liquid at room temperature. Polymerization catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15660487A JP2514035B2 (en) | 1987-06-25 | 1987-06-25 | Catalyst for highly stereoregular polymerization of α-olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15660487A JP2514035B2 (en) | 1987-06-25 | 1987-06-25 | Catalyst for highly stereoregular polymerization of α-olefins |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPS641707A JPS641707A (en) | 1989-01-06 |
| JPH011707A true JPH011707A (en) | 1989-01-06 |
| JP2514035B2 JP2514035B2 (en) | 1996-07-10 |
Family
ID=15631372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15660487A Expired - Lifetime JP2514035B2 (en) | 1987-06-25 | 1987-06-25 | Catalyst for highly stereoregular polymerization of α-olefins |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2514035B2 (en) |
-
1987
- 1987-06-25 JP JP15660487A patent/JP2514035B2/en not_active Expired - Lifetime
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