JPS64962B2 - - Google Patents
Info
- Publication number
- JPS64962B2 JPS64962B2 JP7344181A JP7344181A JPS64962B2 JP S64962 B2 JPS64962 B2 JP S64962B2 JP 7344181 A JP7344181 A JP 7344181A JP 7344181 A JP7344181 A JP 7344181A JP S64962 B2 JPS64962 B2 JP S64962B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- represented
- titanium
- carbon atoms
- 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.)
- Expired
Links
- 239000010936 titanium Substances 0.000 claims description 54
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 37
- 229910052719 titanium Inorganic materials 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 20
- 239000012265 solid product Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- -1 triisopropylaluminum Chemical compound 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011949 solid catalyst Substances 0.000 description 9
- 239000011343 solid material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer 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
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 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
- 150000005673 monoalkenes Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】
本発明はポリオレフインの製造方法に関し、詳
しくは特定の活性化チタン触媒成分と有機金属化
合物よりなる触媒を用いて、嵩密度が大きくしか
も粒径分布の良好なポリオレフインを効率よく製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefin, and more specifically, a method for producing polyolefin with high bulk density and good particle size distribution using a catalyst comprising a specific activated titanium catalyst component and an organometallic compound. Concerning how to manufacture well.
従来から、マグネシウムとチタンを含有する固
体触媒成分と有機金属化合物からなる触媒を用い
てポリオレフインを製造する方法については知ら
れており、例えば特公昭46−34098号公報、特開
昭52−98076号公報あるいは特開昭53−2580号公
報に開示された方法などがある。 Conventionally, methods for producing polyolefin using a catalyst consisting of a solid catalyst component containing magnesium and titanium and an organometallic compound have been known, for example, Japanese Patent Publication No. 46-34098 and Japanese Patent Application Laid-open No. 52-98076. There are methods disclosed in Japanese Patent Publication No. 53-2580.
しかし、これらはいずれも一長一短があり、特
に、触媒の調製法が複雑である、生成ポリマーの
嵩密度が小さい、粒径分布が不良である、スラリ
ー特性が悪いなど種々の欠点がある。 However, all of these have advantages and disadvantages, and in particular, there are various disadvantages such as a complicated catalyst preparation method, a low bulk density of the resulting polymer, a poor particle size distribution, and poor slurry properties.
本発明はこれら問題点の解消されたポリオレフ
インの製造方法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 method for producing polyolefin in which these problems are solved.
すなわち本発明は、(A)一般式Mg（OR1）2〔式中、
R1は炭素数１〜５のアルキル基を示す。〕で表わ
されるマグネシウムジアルコキシドに、一般式
Ti（OR2）4〔式中、R2は炭素数１〜５のアルキル
基を示す。〕で表わされるテトラアルコキシチタ
ンを反応させ、次いで一般式TiX1 4〔式中、X1は
ハロゲン原子を示す。〕で表わされるテトラハロ
ゲン化チタンを反応させて得られる固体物質およ
び(B)一般式AlR3 3〔式中、R3は炭素数１〜５のアル
キル基を示す。〕で表わされる有機金属化合物を
成分とする触媒を用いて炭素数２〜８のα−オレ
フインを重合することを特徴とするポリオレフイ
ンの製造方法を提供すると共に、触媒の(A)成分と
して上述の固体物質に、さらに一般式TiX2 4〔式
中、X2はハロゲン原子を示す。〕で表わされるテ
トラハロゲン化チタンを反応させて得られる固体
生成物を用い、これと上述の(B)成分を成分とする
触媒を用いて炭素数２〜８のα−オレフインを重
合することを特徴とするポリオレフインの製造方
法をも提供するものである。 That is, the present invention provides (A) general formula Mg(OR 1 ) 2 [wherein,
R 1 represents an alkyl group having 1 to 5 carbon atoms. ] to the magnesium dialkoxide represented by the general formula
Ti( OR2 ) 4 [In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms. ], and then reacted with a tetraalkoxytitanium represented by the general formula TiX 1 4 [wherein, X 1 represents a halogen atom]. ] and (B) a solid substance obtained by reacting titanium tetrahalide represented by the general formula AlR 3 3 [wherein R 3 represents an alkyl group having 1 to 5 carbon atoms]. ] Provided is a method for producing a polyolefin, characterized in that an α-olefin having 2 to 8 carbon atoms is polymerized using a catalyst containing an organometallic compound represented by The solid substance further has the general formula TiX 2 4 [wherein X 2 represents a halogen atom]. ] Using a solid product obtained by reacting titanium tetrahalide represented by the above, and using this and a catalyst containing the above-mentioned component (B), an α-olefin having 2 to 8 carbon atoms is polymerized. The present invention also provides a method for producing the characteristic polyolefin.
本発明に用いるマグネシウムジアルコキシド
は、一般式Mg（OR1）2で表わされるものであり、
ここでR1は前述した如く炭素数１〜５のアルキ
ル基を示す。このマグネシウムジアルコキシドと
しては、マグネシウムジメトキシド、マグネシウ
ムジエトキシド、マグネシウムジプロポキシド、
マグネシウムジブトキシドなどを例示することが
できる。また、これらのマグネシウムジアルコキ
シドは市販のものを使用することができるが、金
属マグネシウムとアルコールの反応により製造し
たものを用いてもよい。 The magnesium dialkoxide used in the present invention is represented by the general formula Mg(OR 1 ) 2 ,
Here, R 1 represents an alkyl group having 1 to 5 carbon atoms as described above. Examples of the magnesium dialkoxide include magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide,
Examples include magnesium dibutoxide. Moreover, although commercially available magnesium dialkoxides can be used, those produced by the reaction of metallic magnesium and alcohol may also be used.
本発明では上記のマグネシウムジアルコキシド
に、テトラアルコキシチタンを反応させるが、こ
こで用いるテトラアルコキシチタンは、一般式
Ti（OR2）4Tiで表わされる化合物であり、式中の
R2は炭素数１〜５のアルキル基を示す。具体的
には（CH3O）4Ti、（C2H5O）4Ti、（ｎ−
C3H7O）4Ti、（ｎ−C4H9O）4Ti、などをあげるこ
とができる。 In the present invention, the above magnesium dialkoxide is reacted with tetraalkoxytitanium, but the tetraalkoxytitanium used here has the general formula
Ti(OR 2 ) 4 is a compound represented by Ti, and in the formula
R 2 represents an alkyl group having 1 to 5 carbon atoms. Specifically, (CH 3 O) 4 Ti, (C 2 H 5 O) 4 Ti, (n-
Examples include C 3 H 7 O) 4 Ti, (n-C 4 H 9 O) 4 Ti, etc.
上述のマグネシウムジアルコキシドに、テトラ
アルコキシチタンを反応させる際の条件は特に制
限はなく、各種の事情に応じて適宜定めればよ
い。通常は、マグネシウムジアルコキシド１モル
に対して、テトラアルコキシチタン0.5〜50モル、
好ましくは１〜20モルを加え、20〜200℃、好ま
しくは50〜180℃にて５分〜10時間、好ましくは
20分〜５時間の条件で反応を行なえばよい。なお
この反応系にはペンタン、ヘキサン、ヘプタン、
オクタン等の不活性炭化水素を溶媒として加える
こともできる。 The conditions for reacting the above-mentioned magnesium dialkoxide with tetraalkoxytitanium are not particularly limited, and may be appropriately determined depending on various circumstances. Usually, 0.5 to 50 moles of tetraalkoxytitanium per 1 mole of magnesium dialkoxide,
Preferably 1 to 20 mol is added and the mixture is heated at 20 to 200°C, preferably 50 to 180°C for 5 minutes to 10 hours, preferably
The reaction may be carried out for 20 minutes to 5 hours. Note that this reaction system contains pentane, hexane, heptane,
Inert hydrocarbons such as octane can also be added as solvents.
次に本発明においては、上述の反応生成物であ
る均一溶液に、テトラハロゲン化チタンを反応さ
せる。このテトラハロゲン化チタンは、前述した
如く一般式TiX1 4で表わされるものであり、ここ
でX1は塩素原子、臭素原子、沃素原子などのハ
ロゲン原子を示す。具体的にはTiCl4，TiBr4，
TiI4などを例示することができる。これらは単独
でも混合物として用いてもよい。これらのうち特
に四塩化チタン（TiCl4）を用いるのが好まし
い。 Next, in the present invention, the homogeneous solution which is the above-mentioned reaction product is reacted with titanium tetrahalide. As described above, this titanium tetrahalide is represented by the general formula TiX 1 4 , where X 1 represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. Specifically, TiCl 4 , TiBr 4 ,
An example is TiI 4 . These may be used alone or as a mixture. Among these, it is particularly preferable to use titanium tetrachloride (TiCl 4 ).
上述の反応生成物を、上記のテトラハロゲン化
チタンと反応させる際の条件は特に制限はない
が、通常は前述のマグネシウムジアルコキシド１
モルに対して、テトラハロゲン化チタンを0.1〜
20モル、好ましくは１〜10モルの範囲で加え、10
〜200℃、好ましくは30〜150℃にて５分〜10時
間、好ましくは30分〜５時間反応させる。この反
応は必要に応じてペンタン、ヘキサン、ヘプタン
等の不活性溶媒を用いることも可能である。 The conditions for reacting the above-mentioned reaction product with the above-mentioned titanium tetrahalide are not particularly limited, but usually the above-mentioned magnesium dialkoxide 1
0.1 to 1 mole of titanium tetrahalide
20 mol, preferably in the range of 1 to 10 mol, 10
The reaction is carried out at ~200°C, preferably 30~150°C for 5 minutes to 10 hours, preferably 30 minutes to 5 hours. This reaction can also be carried out using an inert solvent such as pentane, hexane, heptane, etc., if necessary.
上述の反応終了後、反応液から固体状の生成物
を分離し、得られた生成物を必要に応じてヘプタ
ン等の不活性溶媒で洗浄して、目的とする固体物
質を得る。 After the above-mentioned reaction is completed, the solid product is separated from the reaction solution, and the obtained product is washed with an inert solvent such as heptane as necessary to obtain the desired solid substance.
本発明ではこのようにして得られた固体物質
を、ポリオレフインの製造用触媒の(A)成分（固体
触媒成分）として用いる。 In the present invention, the solid substance thus obtained is used as component (A) (solid catalyst component) of a catalyst for producing polyolefin.
また本発明の他の態様では、上記のの固体物質
に、さらにテトラハロゲン化チタンを反応させ、
得られた固体生成物を触媒の(A)成分として用い
る。ここでテトラハロゲン化チタンは一般式
TiX2 4〔式中、X2はハロゲン原子を示す。〕で表わ
されるものであつて、前述の一般式TiX1 4で表わ
されるテトラハロゲン化チタンと同じものであつ
てもよく、また異なるものであつてもよい。なお
X2は塩素原子、臭素原子、沃素原子などのハロ
ゲン原子であり、これらテトラハロゲン化チタン
としては例えばTiCl4，TiBr4，TiI4などが挙げ
られる。これらは単独でもそられの混合物として
用いてもよい。これらのうち特に四塩化チタン
（TiCl4）を用いるのが好ましい。 In another aspect of the present invention, the solid material described above is further reacted with titanium tetrahalide,
The solid product obtained is used as component (A) of the catalyst. Here, titanium tetrahalide has the general formula
TiX 2 4 [In the formula, X 2 represents a halogen atom. ], and may be the same as or different from the titanium tetrahalide represented by the general formula TiX 14 described above. In addition
X 2 is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and examples of these titanium tetrahalides include TiCl 4 , TiBr 4 , and TiI 4 . These may be used alone or as a mixture thereof. Among these, it is particularly preferable to use titanium tetrachloride (TiCl 4 ).
上述の固体物質を上記一般式TiX2 4で表わされ
るテトラハロゲン化チタンと反応させる際の条件
は特に制限はないが、通常は前述のマグネシウム
ジアルコキシド１モルに対して、テトラハロゲン
化チタンを0.1〜20モル、好ましくは１〜10モル
の範囲で加え、10〜200℃、好ましくは30〜150℃
にて５分〜10時間、好ましくは30分〜５時間反応
させる。この反応は必要に応じてペンタン、ヘキ
サン、ヘプタン等の不活性溶媒を用いることも可
能である。 There are no particular restrictions on the conditions for reacting the above-mentioned solid substance with the titanium tetrahalide represented by the general formula TiX 2 4 , but usually 0.1 titanium tetrahalide is reacted with 1 mol of the above-mentioned magnesium dialkoxide. ~20 mol, preferably 1 to 10 mol, added at 10 to 200°C, preferably 30 to 150°C
The reaction is carried out for 5 minutes to 10 hours, preferably for 30 minutes to 5 hours. This reaction can also be carried out using an inert solvent such as pentane, hexane, heptane, etc., if necessary.
上述の反応終了後、反応液から固体生成物を分
離し、十分に洗浄して、これを触媒の(A)成分とし
て用いる。 After the above reaction is completed, the solid product is separated from the reaction solution, thoroughly washed, and used as the component (A) of the catalyst.
本発明によれば、上記の固体物質あるいは該固
体物質をテトラハロゲン化チタンと反応させて得
られる固体生成物を(A)成分とし、また有機金属化
合物を(B)成分とした、(A)，(B)両成分よりなる触媒
を用いて炭素数の２〜８のα−オレフインを重合
し、ポリオレフインを製造する。 According to the present invention, the solid substance or the solid product obtained by reacting the solid substance with titanium tetrahalide is the component (A), and the organometallic compound is the component (B). , (B) An α-olefin having 2 to 8 carbon atoms is polymerized using a catalyst comprising both components to produce a polyolefin.
ポリオレフインの製造にあたつては、反応系に
(A)成分である前記の固体物質あるいは固体生成物
の分散液および(B)成分である有機金属化合物を加
え、次いでこの系に原料オレフインを導入する。 When producing polyolefin, the reaction system
A dispersion of the solid substance or solid product as component (A) and an organometallic compound as component (B) are added, and then the raw material olefin is introduced into the system.
重合方法ならびに条件等は特に制限はなく、溶
液重合、懸濁重合、気相重合等のいずれも可能で
あり、また連続重合、非連続重合のどちらも可能
である。触媒成分の添加量は、溶液重合あるいは
懸濁重合の場合を例にとれば、(A)成分をチタン原
子に換算して0.001〜1.0ミリモル／、好ましく
は0.005〜0.5ミリモル／とし、(B)成分を(A)成分
中のチタン原子に対して１〜1000（モル比）、好ま
しくは10〜500（モル比）とする。また反応系の原
料オレフイン圧は常圧〜50Kg／cm2が好ましく反応
温度は30〜200℃、好ましくは50〜150℃とする。
重合に際しての分子量調節は公知の手段、例えば
水素等により行なうことができる。なお反応時間
は10分〜10時間、好ましくは30分〜５時間の間で
適宜選定すればよい。 The polymerization method and conditions are not particularly limited, and any of solution polymerization, suspension polymerization, gas phase polymerization, etc. is possible, and both continuous polymerization and discontinuous polymerization are possible. Taking the case of solution polymerization or suspension polymerization as an example, the amount of the catalyst component added is 0.001 to 1.0 mmol/, preferably 0.005 to 0.5 mmol/in terms of titanium atoms of component (A), and (B) The amount of the component is 1 to 1000 (molar ratio), preferably 10 to 500 (molar ratio) to the titanium atoms in component (A). Further, the pressure of the raw material olefin in the reaction system is preferably normal pressure to 50 kg/cm 2 , and the reaction temperature is 30 to 200°C, preferably 50 to 150°C.
Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen. The reaction time may be appropriately selected from 10 minutes to 10 hours, preferably from 30 minutes to 5 hours.
本発明の方法においては触媒の(B)成分として一
般式AlR3 3で表わされる有機金属化合物を用いる。
式中、R3は前述した如く炭素数１〜５のアルキ
ル基である。具体的に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等の
トリアルキルアルミニウムが挙げられ、またこれ
らの混合物も好適なものとしてあげられる。 In the method of the present invention, an organometallic compound represented by the general formula AlR 3 3 is used as component (B) of the catalyst.
In the formula, R 3 is an alkyl group having 1 to 5 carbon atoms as described above. Specific examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, and triisobutylaluminum, and mixtures thereof are also suitable.
また本発明の方法においては、重合反応の際
に、エステル等の電子供与性化合物を加えると、
特にプロピレンの重合の場合には、立体規則性の
よりすぐれたポリマーを得ることができる。 Furthermore, in the method of the present invention, when an electron-donating compound such as an ester is added during the polymerization reaction,
Particularly in the case of propylene polymerization, polymers with better stereoregularity can be obtained.
本発明の方法では上記の如き触媒を用いて炭素
数２〜８のα−オレフインを重合すする。このα
−オレフインは一般式R4−CH＝CH2〔式中、R4
は水素または炭素数１〜６のアルキル基を示す。〕
で表わされるもの、例えばエチレン、プロピレ
ン、ブテン−１，ヘキセン−１，オクテン−１等
の直鎖モノオレフイン類をはじめ、４−メチル−
ペンテン−１等の分岐モノオレフイン類、ブタジ
エン等のジエン類その他各種のものがあげられ、
本発明は、これらの単独重合、あるいは各種α−
オレフイン相互の共重合に有効に利用できる。 In the method of the present invention, an α-olefin having 2 to 8 carbon atoms is polymerized using the catalyst as described above. This α
-Olefin has the general formula R 4 -CH=CH 2 [wherein R 4
represents hydrogen or an alkyl group having 1 to 6 carbon atoms. ]
4-methyl-
Examples include branched monoolefins such as pentene-1, dienes such as butadiene, and various others.
The present invention deals with these homopolymerizations or various α-
It can be effectively used for copolymerization of olefins.
本発明の方法によれば、用いる触媒の活性が極
めて高いため触媒の除去工程（いわゆる脱灰工
程）を省略することが可能である。また得られる
ポリオレフインが高嵩密度のものであるため、生
産効率が高く、しかも粒径分布がシヤープである
ため乾燥操作が容易であつて消費エネルギーを節
約できると共に取扱いが非常に容易である。 According to the method of the present invention, since the activity of the catalyst used is extremely high, it is possible to omit the catalyst removal step (so-called deashing step). Furthermore, since the polyolefin obtained has a high bulk density, production efficiency is high, and the particle size distribution is sharp, making drying easy, saving energy consumption, and being extremely easy to handle.
次に本発明の実施例を比較例と共に示す。なお
以下の実施例および比較例における操作はすべて
アルゴン気流下にて行なつた。 Next, examples of the present invention will be shown together with comparative examples. All operations in the following Examples and Comparative Examples were performed under an argon stream.
実施例 １
(1) 固体触媒成分の製造
300mlの三つ口フラスコにマグネシウムジエト
キシド３ｇ（26ミリモル）とテトラ−ｎ−ブトキ
シチタン17ｇ（52ミリモル）を加えた後、昇温し
140℃で２時間反応を行なつた。反応終了後60℃
に冷却し、ｎ−ヘキサン100mlを加えた。次いで
この系に四塩化チタン19ｇ（100ミリモル）を30
分にわたつて滴下した。この滴下開始と同時に白
色固体の析出がみられた。滴下終了後、還流下で
３時間反応を行なつた。反応終了後、室温にもど
し、静置して上澄液を抜き取り、新たにｎ−ヘキ
サン100mlを加え、撹拌、静置、液抜きを行なつ
た。静置、上澄液の抜き取り、ｎ−ヘキサンの添
加、撹拌、静置、液抜きの操作を５回繰り返し、
その結果、固体物質を得た。この固体物質につい
て、比色法にて測定したところチタン担持量は
158mg−Ti／ｇ−担体であつた。Example 1 (1) Production of solid catalyst component After adding 3 g (26 mmol) of magnesium diethoxide and 17 g (52 mmol) of tetra-n-butoxytitanium to a 300 ml three-necked flask, the temperature was raised.
The reaction was carried out at 140°C for 2 hours. 60℃ after completion of reaction
The mixture was cooled to 100 mL, and 100 ml of n-hexane was added. Next, 19 g (100 mmol) of titanium tetrachloride was added to this system for 30 minutes.
It was dripped over several minutes. At the same time as this dropwise addition was started, white solid was observed to precipitate. After the dropwise addition was completed, the reaction was carried out under reflux for 3 hours. After the reaction was completed, the temperature was returned to room temperature, the mixture was allowed to stand still, and the supernatant liquid was extracted, and 100 ml of n-hexane was newly added, followed by stirring, standing, and draining. Repeat the operations of standing still, removing the supernatant liquid, adding n-hexane, stirring, standing still, and removing the liquid 5 times.
As a result, a solid material was obtained. When this solid material was measured using a colorimetric method, the amount of titanium supported was
It was 158 mg-Ti/g-carrier.
(2) エチレンの重合
１のステンレス製オートクレープにｎ−ヘキ
サン400ml、トリイソブチルアルミニウム
（TIBA）２ミリモルおよび上記(1)で得られた固
体物質をチタンとして0.04ミリモル加え80℃に昇
温した。次いで水素３Kg／cm2加えるとともに、エ
チレン５Kg／cm2加え、全圧を9.3Kg／cm2−Ｇとし、
さらにこの全圧を維持するようにエチレンを導入
しながら１時間重合を行なつた。その結果、白色
のポリエチレン170ｇが得られた。このポリエチ
レンの嵩密度は0.31ｇ／cm3、メルトインデツクス
（MI）は2.6ｇ／10分であつた。また、ここで用
いた触媒の活性は、チタン１ｇ、１時間あたり89
Kgであつた。(2) Polymerization of ethylene 400 ml of n-hexane, 2 mmol of triisobutylaluminum (TIBA), and 0.04 mmol of the solid material obtained in (1) above as titanium were added to the stainless steel autoclave prepared in 1, and the temperature was raised to 80°C. Next, 3 kg/cm 2 of hydrogen and 5 kg/cm 2 of ethylene were added to make the total pressure 9.3 kg/cm 2 -G.
Furthermore, polymerization was carried out for 1 hour while introducing ethylene to maintain this total pressure. As a result, 170 g of white polyethylene was obtained. This polyethylene had a bulk density of 0.31 g/cm 3 and a melt index (MI) of 2.6 g/10 minutes. In addition, the activity of the catalyst used here is 89% per gram of titanium per hour.
It was Kg.
実施例
(1) 固体触媒成分の製造
実施例１(1)で得られた固体物質に、四塩化チタ
ンを、前述のマグネシウムジエトキシド３ｇ中の
マグネシウム１モルに対して、チタン５モルに相
当する量を60℃に加え、還流下で３時間反応を行
なつた。反応終了後、実施例１(1)と同様にｎ−ヘ
キサン洗浄を行ない、固体生成物を得た。この固
体生成物について、比色法にて測定したところチ
タン担持量は53mg−Ti／ｇ−担体であつた。Example (1) Production of solid catalyst component Titanium tetrachloride was added to the solid material obtained in Example 1 (1) in an amount equivalent to 5 moles of titanium per 1 mole of magnesium in 3 g of the above-mentioned magnesium diethoxide. This amount was added to 60°C, and the reaction was carried out under reflux for 3 hours. After the reaction was completed, washing with n-hexane was performed in the same manner as in Example 1(1) to obtain a solid product. When this solid product was measured by a colorimetric method, the amount of titanium supported was 53 mg-Ti/g-support.
(2) エチレンの重合
実施例１(2)において固体物質の代わりに、上記
実施例２(1)において得られた固体生成物をチタン
として0.01ミリモル加えたこと以外は、実施例１
(2)と同様の操作にて重合を行なつた。その結果、
白色のポリエチレン167ｇが得られた。このポリ
エチレンの嵩密度は0.26ｇ／cm3、MIは3.0ｇ／10
分であつた。また、ここで用いた触媒の活性は、
チタン１ｇ、１時間あたり349Kgであつた。(2) Polymerization of ethylene Example 1 except that 0.01 mmol of the solid product obtained in Example 2 (1) above was added as titanium instead of the solid substance in Example 1 (2).
Polymerization was carried out in the same manner as in (2). the result,
167 g of white polyethylene was obtained. The bulk density of this polyethylene is 0.26g/cm 3 and the MI is 3.0g/10
It was hot in minutes. In addition, the activity of the catalyst used here is
1g of titanium was 349Kg per hour.
比較例 １
(1) 固体触媒成分の製造
実施例１(1)においてテトラ−ｎ−ブトキシチタ
ンを加えなかつたこと以外は実施例１(1)と同様の
処理を行なつて固体物質を得た。このもののチタ
ン担持量は120mg−Ti／ｇ−担体であつた。Comparative Example 1 (1) Production of solid catalyst component A solid substance was obtained by carrying out the same treatment as in Example 1 (1) except that tetra-n-butoxytitanium was not added in Example 1 (1). . The amount of titanium supported on this product was 120 mg-Ti/g-support.
(2) エチレンの重合
実施例１(2)において、実施例１(1)で得られた固
体物質の代わりに上記比較例１(1)で得られた固体
物質を用いたこと以外は、実施例１(2)と同様の操
作にて重合を行なつた。その結果、白色のポリエ
チレン83ｇが得られた。このポリエチレンの嵩密
度は0.20ｇ／cm3、MIは2.5ｇ／10分であつた。(2) Polymerization of ethylene In Example 1 (2), the solid substance obtained in Comparative Example 1 (1) above was used instead of the solid substance obtained in Example 1 (1). Polymerization was carried out in the same manner as in Example 1 (2). As a result, 83 g of white polyethylene was obtained. This polyethylene had a bulk density of 0.20 g/cm 3 and an MI of 2.5 g/10 min.
比較例 ２
(1) 固体触媒成分の製造
実施例２(1)において、実施例１(1)で得られた固
体物質の代わりに、上記比較例１(1)で得られた固
体物質を用いたこと以外は、実施例２(1)と同様の
操作を行ない、固体生成物を得た。このもののチ
タン担持量は85mg−Ti／ｇ−担体であつた。Comparative Example 2 (1) Production of solid catalyst component In Example 2 (1), the solid material obtained in Comparative Example 1 (1) above was used instead of the solid material obtained in Example 1 (1). A solid product was obtained by carrying out the same operation as in Example 2 (1) except for the following. The amount of titanium supported on this product was 85 mg-Ti/g-support.
(2) エチレンの重合
実施例１(2)において、実施例１(1)で得られた固
体物質の代わりに、上記比較例２(1)で得られた固
体生成物を用いたこと以外は、実施例１(2)と同様
の操作にて重合を行なつた。その結果、白色のポ
リエチレン78ｇが得られた。このポリエチレンの
嵩密度は0.26ｇ／cm3、MIは1.9ｇ／10分であつた。(2) Polymerization of ethylene In Example 1 (2), the solid product obtained in Comparative Example 2 (1) above was used instead of the solid substance obtained in Example 1 (1). Polymerization was carried out in the same manner as in Example 1 (2). As a result, 78 g of white polyethylene was obtained. This polyethylene had a bulk density of 0.26 g/cm 3 and an MI of 1.9 g/10 min.
実施例 ３
(1) 固体触媒成分の製造
実施例１(1)においてテトラ−ｎ−ブトキシチタ
ンの代わりにテトライソプロポキシチタンを用い
たこと以外は、実施例１(1)と同様の操作を行ない
固体物質（チタン担持量143mg−Ti／ｇ−担体）
を得た。さらにこの固体物質を用いて実施例２(1)
と同様の操作を行ない、固体生成物を得た。この
もののチタン担持量は58mg−Ti／ｇ−担体であ
つた。Example 3 (1) Production of solid catalyst component The same operation as in Example 1(1) was performed except that tetraisopropoxytitanium was used instead of tetra-n-butoxytitanium in Example 1(1). Solid material (titanium supported amount 143mg-Ti/g-support)
I got it. Furthermore, using this solid substance, Example 2 (1)
A solid product was obtained by performing the same operation as above. The amount of titanium supported on this product was 58 mg-Ti/g-support.
(2) エチレンの重合
１のステンレス製オートクレープにｎ−ヘキ
サン400ml、トリエチルアルミニウム2.0ミリモル
および上記(1)で得られた固体生成物をチタンとし
て0.01ミリモル加え、80℃に昇温した。次いで水
素３Kg／cm2、エチレン５Kg／cm2を加え、全圧を
9.3Kg／cm2−Ｇとし、さらにこの全圧を維持する
ようにエチレンを導入しながら80℃にて１時間重
合を行なつた。その結果、白色のポリエチレン
178ｇが得られた。このポリエチレンの嵩密度は
0.29ｇ／cm3、MIは2.7ｇ／10分であつた。また、
ここで用いた触媒の活性はチタン１ｇ、１時間あ
たり371Kgであつた。(2) Polymerization of ethylene 400 ml of n-hexane, 2.0 mmol of triethylaluminum, and 0.01 mmol of the solid product obtained in (1) above as titanium were added to the stainless steel autoclave prepared in 1, and the temperature was raised to 80°C. Next, add 3 kg/cm 2 of hydrogen and 5 kg/cm 2 of ethylene to reduce the total pressure.
The pressure was 9.3 Kg/cm 2 -G, and polymerization was carried out at 80° C. for 1 hour while introducing ethylene to maintain this total pressure. As a result, white polyethylene
178g was obtained. The bulk density of this polyethylene is
0.29 g/cm 3 and MI was 2.7 g/10 minutes. Also,
The activity of the catalyst used here was 371 kg per hour for 1 g of titanium.
実施例 ４
(1) 固体触媒成分の製造
実施例１(1)においてテトラ−ｎ−ブトキシチタ
ンを34ｇ（104ミリモル）、四塩化チタンを35ｇ
（185ミリモル）加えたこと以外は、実施例１(1)と
同様の操作を行ない、固体物質（チタン担持量
137mg−Ti／ｇ−担体）を得た。さらにこの固体
物質を用いて実施例２(1)と同様の操作を行ない固
体生成物を得た。このもののチタン担持量は50mg
−Ti／ｇ−担体であつた。Example 4 (1) Production of solid catalyst component In Example 1 (1), 34 g (104 mmol) of tetra-n-butoxytitanium and 35 g of titanium tetrachloride were used.
The same operation as in Example 1 (1) was carried out except for adding (185 mmol) of the solid substance (titanium supported amount).
137 mg-Ti/g-carrier) was obtained. Further, using this solid substance, the same operation as in Example 2(1) was carried out to obtain a solid product. The amount of titanium supported by this product is 50mg
-Ti/g- carrier.
(2) エチレンの重合
実施例１(2)において固体物質の代わりに、上記
実施例４(1)で得られた固体生成物を用いたこと以
外は、実施例１(2)と同様の操作にて重合を行なつ
た。その結果、白色のポリエチレン147ｇが得ら
れた。このポリエチレンの嵩密度は0.27ｇ／cm3、
MIは3.2ｇ／10分であつた。(2) Polymerization of ethylene The same procedure as in Example 1(2) was performed, except that the solid product obtained in Example 4(1) above was used instead of the solid substance in Example 1(2). Polymerization was carried out at As a result, 147 g of white polyethylene was obtained. The bulk density of this polyethylene is 0.27g/cm 3 ,
MI was 3.2 g/10 minutes.
実施例５ （プロピレンの重合）
１のステンレス製オートクレープに乾燥した
ｎ−ヘプタン400ml、トリエチルアルミニウム2.0
ミリモル、ｐ−トルイル酸メチル0.6ミリモルお
よび実施例２(1)で得られた固体生成物をチタンと
して0.02ミリモル加え、70℃に昇温した。次に水
素0.2Kg／cm2を加え、さらにプロピレンで全圧を
７Kg／cm2−Ｇに維持しながら２時間重合を行なつ
た。重合反応終了後、生成物を70℃において濾過
して溶媒を除き、乾燥して172ｇのポリプロピレ
ンを得た。このポリプロピレンの沸騰ｎ−ヘプタ
ン抽出残量は83.5％であり、一方、重合溶媒より
可溶性ポリマー13.5ｇが回収された。また、ここ
で用いた触媒の活性は、チタン１ｇ、２時間あた
り179Kgであつた。Example 5 (Polymerization of propylene) 400 ml of dried n-heptane and 2.0 ml of triethylaluminum were placed in a stainless steel autoclave.
0.6 mmol of methyl p-toluate and 0.02 mmol of the solid product obtained in Example 2 (1) as titanium were added, and the temperature was raised to 70°C. Next, 0.2 kg/cm 2 of hydrogen was added, and polymerization was carried out for 2 hours while maintaining the total pressure at 7 kg/cm 2 -G with propylene. After the polymerization reaction was completed, the product was filtered at 70°C to remove the solvent and dried to obtain 172 g of polypropylene. The residual amount of this polypropylene extracted with boiling n-heptane was 83.5%, and on the other hand, 13.5 g of soluble polymer was recovered from the polymerization solvent. Furthermore, the activity of the catalyst used here was 179 kg per 1 g of titanium and 2 hours.
比較例 ３
(1) 固体触媒成分の製造
300mlの三つ口フラスコに、マグネシウムジエ
トキシド３ｇ（26ミリモル）、テトラ−ｎ−ブト
キシチタン17ｇ（52ミリモル）およびジクロルジ
ブトキシチタン17.9ｇ（52ミリモル）を同時に加
え、さらに沸点範囲130〜160℃の石油留分100ml
を加えて、７時間還流下で反応させた。反応終了
後得られた沈澱物を傾瀉ならびに100mlのｎ−ヘ
キサンによる洗浄を５回繰り返して固体生成物を
得た。この固体生成物のチタン担持量は140mg−
Ti／ｇ−担体であつた。Comparative Example 3 (1) Production of solid catalyst component In a 300 ml three-necked flask, 3 g (26 mmol) of magnesium diethoxide, 17 g (52 mmol) of tetra-n-butoxytitanium, and 17.9 g (52 mmol) of dichlorodibutoxytitanium were added. ) and 100ml of petroleum distillate with a boiling point range of 130~160℃.
was added, and the mixture was reacted under reflux for 7 hours. After the reaction was completed, the resulting precipitate was decanted and washed five times with 100 ml of n-hexane to obtain a solid product. The amount of titanium supported in this solid product is 140mg−
It was Ti/g-support.
(2) エチレンの重合
実施例１(2)において、固体物質の代わりに上記
比較例３(1)で得られた固体生成物を用いたこと以
外は、実施例１(2)と同様の操作にて重合を行なつ
た。その結果、白色のポリエチレン20mgが得られ
た。このポリエチレンの嵩密度は0.15ｇ／cm3であ
つた。またここで用いた触媒の活性は、チタン１
ｇ、１時間あたり10.4Kgであつた。(2) Polymerization of ethylene In Example 1 (2), the same operation as in Example 1 (2) was performed except that the solid product obtained in Comparative Example 3 (1) above was used instead of the solid substance. Polymerization was carried out at As a result, 20 mg of white polyethylene was obtained. The bulk density of this polyethylene was 0.15 g/cm 3 . In addition, the activity of the catalyst used here is titanium 1
g, 10.4Kg per hour.
第１図は本発明の方法で用いる触媒の調製工程
を表わした図面である。
FIG. 1 is a drawing showing the steps for preparing a catalyst used in the method of the present invention.
Claims (1)
５のアルキル基を示す。〕で表わされるマグネシ
ウムジアルコキシドに、一般式Ti（OR2）4〔式中、
R2は炭素数１〜５のアルキル基を示す。〕で表わ
されるテトラアルコキシチタンを反応させ、次い
で一般式TiX1 4〔式中、X1はハロゲン原子を示
す。〕で表わされるテトラハロゲン化チタンを反
応させて得られる固体物質および(B)一般式AlR3 3
〔式中、R3は炭素数１〜５のアルキル基を示す。〕
で表わされる有機金属化合物を成分とする触媒を
用いて炭素数２〜８のα−オレフインを重合する
ことを特徴とするポリオレフインの製造方法。 ２ (A)一般式Mg（OR1）2〔式中、R1は炭素数１〜
５のアルキル基を示す。〕で表わされるマグネシ
ウムジアルコキシドに、一般式Ti（OR2）4〔式中、
R2は炭素数１〜５のアルキル基を示す。〕で表わ
されるテトラアルコキシチタンを反応させ、次い
で一般式TiX1 4〔式中、X1はハロゲン原子を示
す。〕で表わされるテトラハロゲン化チタンを反
応させ、さらに得られる固体物質に、一般式
TiX2 4〔式中X2はハロゲン原子を示す。〕で表わさ
れるテトラハロゲン化チタンを反応させて得られ
る固体生成物および(B)一般式AlR3 3〔式中、R3は炭
素数１〜５のアルキル基を示す。〕で表わされる
有機金属化合物を成分とする触媒を用いて炭素数
２〜８のα−オレフインを重合することを特徴と
するポリオレフインの製造方法。[Claims] 1 (A) General formula Mg(OR 1 ) 2 [In the formula, R 1 is a carbon number of 1 to
5 shows the alkyl group. ] to the magnesium dialkoxide represented by the general formula Ti(OR 2 ) 4 [wherein,
R 2 represents an alkyl group having 1 to 5 carbon atoms. ], and then reacted with a tetraalkoxytitanium represented by the general formula TiX 1 4 [wherein, X 1 represents a halogen atom]. ] and (B) a solid substance obtained by reacting titanium tetrahalide represented by the general formula AlR 3 3
[In the formula, R 3 represents an alkyl group having 1 to 5 carbon atoms. ]
A method for producing a polyolefin, which comprises polymerizing an α-olefin having 2 to 8 carbon atoms using a catalyst containing an organometallic compound represented by the formula. 2 (A) General formula Mg (OR 1 ) 2 [In the formula, R 1 is a carbon number of 1 to
5 shows the alkyl group. ] to the magnesium dialkoxide represented by the general formula Ti(OR 2 ) 4 [wherein,
R 2 represents an alkyl group having 1 to 5 carbon atoms. ], and then reacted with a tetraalkoxytitanium represented by the general formula TiX 1 4 [wherein, X 1 represents a halogen atom]. ] is reacted with titanium tetrahalide represented by the general formula
TiX 2 4 [In the formula, X 2 represents a halogen atom. ] and (B) a solid product obtained by reacting titanium tetrahalide represented by the general formula AlR 3 3 [wherein R 3 represents an alkyl group having 1 to 5 carbon atoms]. A method for producing a polyolefin, which comprises polymerizing an α-olefin having 2 to 8 carbon atoms using a catalyst containing an organometallic compound represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7344181A JPS57190004A (en) | 1981-05-18 | 1981-05-18 | Preparation of polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7344181A JPS57190004A (en) | 1981-05-18 | 1981-05-18 | Preparation of polyolefin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32388289A Division JPH02269104A (en) | 1989-12-15 | 1989-12-15 | Production of polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57190004A JPS57190004A (en) | 1982-11-22 |
| JPS64962B2 true JPS64962B2 (en) | 1989-01-10 |
Family
ID=13518324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7344181A Granted JPS57190004A (en) | 1981-05-18 | 1981-05-18 | Preparation of polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57190004A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59176307A (en) * | 1983-03-28 | 1984-10-05 | Idemitsu Kosan Co Ltd | Production of polypropylene |
| WO2010006756A1 (en) * | 2008-07-18 | 2010-01-21 | Saudi Basic Industries Corporation | Process for the production of polyethylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2752577A1 (en) * | 1977-11-25 | 1979-06-07 | Hoechst Ag | METHOD FOR PRODUCING A MIXED CATALYST |
-
1981
- 1981-05-18 JP JP7344181A patent/JPS57190004A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57190004A (en) | 1982-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS64407B2 (en) | ||
| JP4519231B2 (en) | Styrene-butadiene block copolymer | |
| EP1830954A2 (en) | Soluble magnesium complexes useful for the production of polyolefin catalysts and catalysts prepared therewith | |
| JP3913814B2 (en) | Polymerization method of ethylene | |
| JPH0315644B2 (en) | ||
| JPS64962B2 (en) | ||
| JPS6356248B2 (en) | ||
| JPS6250481B2 (en) | ||
| JPS5812889B2 (en) | Polyethylene material | |
| JP3253650B2 (en) | Method for producing ethylene (co) polymer | |
| JPH0725833B2 (en) | Method for producing propylene homopolymer and copolymer | |
| JPH06811B2 (en) | Method for producing polyolefin | |
| KR100393169B1 (en) | A Metallocene Catalyst Containing Biphenyl-substituted Cyclopentadienyl Group and A Method for Polymerizing Olefins Using the Same | |
| JPS64964B2 (en) | ||
| JPS642121B2 (en) | ||
| JPS642125B2 (en) | ||
| JPS6410529B2 (en) | ||
| JPS64405B2 (en) | ||
| JPS64965B2 (en) | ||
| JP2637137B2 (en) | Method for producing isotactic poly-α-olefin | |
| JPS638124B2 (en) | ||
| JPH0240088B2 (en) | ||
| JP2536527B2 (en) | Method for producing polyethylene | |
| KR810001467B1 (en) | Process for polymerization of -oleffins | |
| JPS584930B2 (en) | Polyethylene manufacturing method |