JPS638124B2 - - Google Patents
Info
- Publication number
- JPS638124B2 JPS638124B2 JP10022379A JP10022379A JPS638124B2 JP S638124 B2 JPS638124 B2 JP S638124B2 JP 10022379 A JP10022379 A JP 10022379A JP 10022379 A JP10022379 A JP 10022379A JP S638124 B2 JPS638124 B2 JP S638124B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- groups
- catalyst component
- general formula
- solid catalyst
- 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
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 29
- 239000011949 solid catalyst Substances 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000011343 solid material Substances 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- -1 ethylene Chemical class 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- 229910052749 magnesium Inorganic materials 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000005484 gravity Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910003902 SiCl 4 Inorganic materials 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- LIBYMBQMJILZPE-UHFFFAOYSA-N oxotitanium;hydrochloride Chemical compound Cl.[Ti]=O LIBYMBQMJILZPE-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 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
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-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
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 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
- 238000005406 washing Methods 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)
Description
本発明はオレフイン類の重合方法に関し、詳し
くは特定の触媒を用いてオレフイン類を効率よく
重合する方法に関する。
従来、エチレン等のオレフイン類の重合法にお
いて、その触媒担体にマグネシウムを含有する化
合物、例えばハロゲン化マグネシウム、マグネシ
ウムアルコキシド等を用い、該物質とハロゲン化
チタンとを反応させて得られる物質が高活性触媒
の成分となることが知られている(特公昭46−
34098号公報、特開昭52−98076号公報、特開昭53
−2580号公報)。しかしながら、上記従来の方法
では触媒活性および得られるポリオレフインの品
質が満足すべきものではなかつた。
上述の如きエチレン等のオレフインの高活性重
合においては、より活性を高めることによつて触
媒除去工程を省略して、製造工程を簡略化し、ま
た担体あたりの生産性を高めることによつて担体
使用量を少なくすることが好ましい。さらにポリ
オレフインの製造上、スラリーのハンドリングの
面から生成ポリマーのかさ比重はできるだけ大き
く、パウダーの粒径も均一化し、微細粒子が少な
いことが望まれている。
本発明者らはかかる観点において、マグネシウ
ムアルコキシドとハロゲン化チタンとの反応生成
物を成分とする触媒を用いてオレフイン類を重合
する方法について鋭意研究を重ねた。その結果、
マグネシウムアルコキシドを複数のハロゲン化物
で特定の処理を行なうことによつて得られる固体
物質を触媒の一成分として用いることにより、目
的とするオレフインの重合が効率よく進行するこ
とを見出し、本発明を完成するに至つた。
すなわち本発明は、(A)チタン含有固体触媒成分
および(B)有機アルミニウム化合物を組み合せてな
る触媒を用いてオレフイン類を重合する方法にお
いて、前記(A)チタン含有固体触媒成分として一般
式Mg(OR1)pX1 2-p(式中、X1はハロゲン原子、
R1は炭素数1〜20個の直鎖状あるいは側鎖状の
アルキル基、アルケニル基、アリール基、シクロ
アルキル基、アリールアルキル基またはアルキル
アリール基を示し、pは1または2を示す。)で
表わされるマグネシウムアルコキシドに対し、一
般式X2 oTi(OR2)4-o(式中、X2はハロゲン原子、
R2は炭素数1〜10個のアルキル基またはアリー
ル基、nは1〜4を示す。)で表わされるハロゲ
ン含有チタン化合物を0.1〜10(モル比)の割合で
反応させ、次いで一般式X3 nSi(OR3)4-n(式中、
X3はハロゲン原子、R3は炭素数1〜10のアルキ
ル基またはアリール基、mは1〜4を示す。)で
表わされるハロゲン含有ケイ素化合物で処理して
得られる固体物質、あるいはこの固体物質をさら
に四塩化チタンで処理したものを用いることを特
徴とするオレフイン類の重合方法を提供するもの
である。
本発明に用いるマグネシウムアルコキシドは一
般式Mg(OR1)X1 2-p(式中、X1はハロゲン原子、
R1は炭素数1〜20個の直鎖状あるいは側鎖状の
アルキル基、アルケニル基、アリール基、シクロ
アルキル基、アリールアルキル基またはアルキル
アリール基を示し、pは1または2を示す。)で
表わされる化合物である。ここでR1は炭素数1
〜20個、好ましくは1〜8個の直鎖状あるいは側
鎖状のアルキル基、アルケニル基、アリール基、
シクロアルキル基、アリールアルキル基、アルキ
ルアリール基などを示す。具体的にはマグネシウ
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、マグネシウムジシクロヘキソキシド、マ
グネシウムジベンゾキシドなどが好適である。ま
た本発明のマグネシウムアルコキシドとしては、
上記のほかにハロゲンを有するモノアルコキシド
(XMgOR1)を用いることもできる。なお、これ
らのマグネシウムアルコキシドは公知の方法によ
り簡単に得ることができる。
一方、本発明に用いるハロゲン有チタン化合物
は、一般式X2nTi(OR2)4-o(X2はハロゲン原子、
R2は炭素数1〜10個のアルキル基またはアリー
ル基、nは1〜4を示す。)で表わされる化合物
であり、具体的にはTiCl4,TiBr4,CH3OTiCl3,
C2H5OTiCl3,C3H7OTiCl3,(C2H5O)2TiCl2
(C2H5O)3TiClなどをあげることができる。
さらに本発明に用いるハロゲン含有ケイ素化合
物は、通常一般式X3nSi(OR3)4-n(X3はハロゲ
ン原子、R3は炭素数1〜10個のアルキル基また
はアリール基、mは1〜4を示す。)で表わされ
る化合物であり、具体的にはSiCl4,CH3OSiCl3,
(CH3O)2SiCl2,(CH3O)3SiCl,C2H5OSiCl3,
(C2H5O)2SiCl2,(C2H5O)3SiCl,C3H7OSiCl3,
(C3H7O)2SiCl2,(C3H7O)3SiCl,C6H5OSiCl3,
(C6H5O)2SiCl2,(C6H5O)3SiCl等をあげること
ができる。
本発明の方法においては、まず上述のマグネシ
ウムアルコキシドとハロゲン含有チタン化合物を
反応させる。この際の反応は、ペンタン、ヘキサ
ン、ヘプタン、シクロヘキサン、ベンゼン、キシ
レン等の不活性溶媒中で行なつてもよく、また無
溶媒下に行なうこともできる。反応温度は0〜
200℃、好ましくは20〜150℃とし、反応時間は5
〜10時間、好ましくは30分〜5時間とする。また
上記マグネシウムアルコキシドとハロゲン含有チ
タン化合物の添加割合は通常はマグネシウムアル
コキシドに対してハロゲン含有チタン化合物を
0.1〜10(モル比)、好ましくは0.5〜5(モル比)
とする。なお、無溶媒下で上述の反応を行なう場
合には、上記両化合物をボールミル等に入れて粉
砕しながら反応を進行させることが望ましい。
本発明においては、上述の反応後、得られた生
成物を充分に洗浄した後、さらに前記のハロゲン
含有ケイ素化合物で処理することとなる。この際
の条件は特に制限はなく適宜選定すればよいが、
通常は上述したものと同じ不活性溶媒中で反応温
度0〜200℃、好ましくは20〜100℃、反応時間5
分〜5時間、好ましくは30分〜4時間とする。ま
た記マグネシウムアルコキシドに対するハロゲン
含有ケイ素化合物の添加割合は通常は0.1〜10(モ
ル比)、好ましくは0.5〜5(モル比)とする。な
お、上記処理は無溶媒下で行なうこともできる
が、この場合にはボールミル等にて粉砕しながら
反応を進行させることが望ましい。
本発明の方法においては上記の処理によつて得
られた固体物質を充分に洗浄して、触媒の一成分
として使用する。
また、本発明の別の態様においては、上記処理
によつて得られた固体物質をさらに四塩化チタン
で処理する。この場合の処理条件は、温度0〜
200℃、好ましくは20〜150℃とし、時間5分〜5
時間、好ましくは30分〜4時間とすべきである。
また、この処理は前述した不活性溶媒中で行なつ
てもよく、あるいは無溶媒下でボールミル等によ
り粉砕しながら行なつてもよい。なお、四塩化チ
タンの添加割合は特に制限はないがマグネシウム
アルコキシドに対して1〜20倍(モル比)程度と
するのが好ましい。
本発明においてはかかる処理によつて得られた
固体物質も、触媒の一成分として使用することが
できる。
本発明の方法においては、上述の処理によつて
得られた固体物質を(A)チタン含有触媒成分とし、
これに有機アルミニウム化合物を(B)成分として加
え、(A),(B)両成分よりなる触媒を用いて行なう。
オレフインを重合するにあたつては、反応系に(A)
成分である上述のチタン含有固体触媒成分の分散
液および(B)成分である有機アルミニウム化合物を
触媒として加え、次いでこの系にオレフインを導
入する。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、チタン含有固
体触媒成分をチタン原子として0.001〜10ミリモ
ル/、好ましくは0.003〜1ミリモル/とし、
一方有機アルミニウム化合物を上記チタン含有固
体触媒成分に対してアルミニウム原子/チタン原
子が1〜1000(原子比)、好ましくは10〜200(原子
比)となるように調節する。また反応系のオレフ
イン圧は種類によつても異なるが、通常は2〜50
気圧の範囲とし、反応温度は0〜200℃、好まし
くは50〜150℃とし、反応時間は10分〜5時間、
好ましくは30分〜3時間とする。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。また上述の(B)成分である有
機アルミニウム化合物の代表例としては、トリメ
チルアルミニウム,トリエチルアルミニウム,ト
リイソプロピルアルミニウム,トリイソブチルア
ルミニウム,トリオクチルアルミニウム等のトリ
アルキルアルミニウム化合物およびジエチルアル
ミニウムモノクロリド,ジイソプロピルアルミニ
ウムモノクロリド,ジイソブチルアルミニウムモ
ノクロリド,ジオクチルアルミニウムモノクロリ
ド等のジアルキルアルミニウムモノハライド等が
あげられる。
上記触媒にて重合できるポリオレフインとして
は、エチレン,プロピレン,1―ブテン,1―ヘ
キセン等のα―オレフインのホモポリマーはもち
ろん、その他これらオレフインと少量の他のα―
オレフインとのコポリマーなどがあげられる。な
お、プロピレンを重合する場合、上述の反応系に
p―トルイル酸メチル、安息香酸エチル等のエス
テルを添加しておくと、得られるポリプロピレン
のアイソタクシテイシーがよくなる。
叙上のように、本発明の方法によつて得られた
チタン含有固体触媒成分を触媒の一成分として用
いてオレフインの重合を行なえば、触媒活性が極
めて高いため、少量の使用で充分な効果が得られ
る。その結果、脱灰工程(触媒除去工程)を省略
することができる。また、ポリオレフインの生産
量あたりの担体使用量および触媒調合回数を従来
法に比べて著しく低減することができる。しかも
得られるポリエチレン,ポリプロピレン等のポリ
オレフインは高かさ比重を有し、粒径分布が良好
であるため、パウダーの取扱いが非常に容易であ
る。
次に本発明の方法を実施例によりさらに詳しく
説明する。
実施例 1
〔固体触媒成分の製造〕
四つ口フラスコに滴下ロート、ガス吹き込み
口、撹拌棒、還流冷却器を取り付けた500ml容四
つ口フラスコに脱水したヘキサン150ml,Mg
(OC2H5)210.0g(88ミリモル)を入れ、20℃で
TiCl4を16.6g(88ミリモル)を滴下した。滴下
終了後、70℃に昇温し、3時間反応を行なつた。
反応後、温度を室温にもどし、上澄液を抜きと
り、新たにヘキサン250mlを加えて洗浄した。こ
の操作を5回繰り返し、固体物質P―1を得た。
P―1のチタン担持量は108mg―Ti/g―担体で
あつた。
次に、P―1のヘキサンスラリーに室温で
SiCl429.9g(176ミリモル)を滴下した。滴下終
了後、70℃に昇温し3時間反応を行なつた。反応
後、温度を室温まで下げ、上澄液を抜きとり、ヘ
キサン250mlを加えて傾斜法により洗浄した。こ
の操作を5回繰り返し、固体触媒成分P−2を得
た。P―2のチタン担持量は55mg―Ti/g―担
体であつた。
次に、P―2のヘキサンスラリーに室温で
TiCl441.6g(220ミリモル)を滴下した。滴下終
了後、温度を70℃に昇温し、3時間反応を行なつ
た。反応後、室温にもどして上澄液を抜きとり、
新たにヘキサン250mlを加え、傾斜法により洗浄
した。この操作を5回繰り返し、固体触媒成分P
―3を得た。P―3のチタン担持量は303mg―
Ti/g−担体であつた。
〔エチレンの重合〕
1のオートクレーブに、ヘキサン400ml,ト
リエチルアルミニウム2ミリモル,固体触媒成分
P―2をTiとして0.01ミリモル加え、80℃にし
た。水素を3Kg/cm2加え、エチレンを5Kg/cm2加
え、全圧を9.3Kg/cm2にエチレンを維持して1時
間重合を行なつた。その結果、白色のポリエチレ
ン98.4gが得られた。得られたものの触媒活性は
チタン原子1g,1時間当たり205Kgでメルトイ
ンデツクスは1.5g/10分、ポリマーのかさ比重
は0.26,105μ以下の微粉は3.0%であつた。
実施例 2〜4
実施例1において、SiCl4の使用量を変えて固
体触媒成分(P―2)を製造し、それらを触媒と
してエチレンの重合を行なつた結果を下表に示
す。
The present invention relates to a method for polymerizing olefins, and more particularly to a method for efficiently polymerizing olefins using a specific catalyst. Conventionally, in the polymerization method of olefins such as ethylene, a compound containing magnesium, such as magnesium halide, magnesium alkoxide, etc., is used as a catalyst carrier, and a substance obtained by reacting the substance with titanium halide has a high activity. It is known to be a component of catalysts (Special Publication No. 1973-
Publication No. 34098, Japanese Patent Application Laid-Open No. 1982-98076, Japanese Patent Application Publication No. 1983
-2580). However, in the above-mentioned conventional method, the catalyst activity and the quality of the obtained polyolefin were not satisfactory. In the highly active polymerization of olefins such as ethylene as described above, by increasing the activity, the catalyst removal step can be omitted, simplifying the manufacturing process, and by increasing the productivity per carrier, the use of a carrier can be improved. It is preferable to reduce the amount. Furthermore, in the production of polyolefin, it is desired that the bulk specific gravity of the resulting polymer be as high as possible from the viewpoint of slurry handling, that the particle size of the powder be uniform, and that the number of fine particles be small. From this point of view, the present inventors have conducted intensive research on a method for polymerizing olefins using a catalyst containing a reaction product of magnesium alkoxide and titanium halide. the result,
The present invention was completed by discovering that the polymerization of the target olefin can proceed efficiently by using a solid material obtained by treating magnesium alkoxide with multiple halides as a component of the catalyst. I came to the conclusion. That is, the present invention provides a method for polymerizing olefins using a catalyst formed by combining (A) a titanium-containing solid catalyst component and (B) an organoaluminum compound, in which (A) the titanium-containing solid catalyst component has the general formula Mg ( OR 1 ) p X 1 2-p (wherein, X 1 is a halogen atom,
R 1 represents a linear or side-chain alkyl group, alkenyl group, aryl group, cycloalkyl group, arylalkyl group or alkylaryl group having 1 to 20 carbon atoms; p represents 1 or 2; ) with the general formula X 2 o Ti(OR 2 ) 4-o (wherein, X 2 is a halogen atom,
R2 represents an alkyl group or an aryl group having 1 to 10 carbon atoms, and n represents 1 to 4. ) is reacted with a halogen-containing titanium compound represented by the formula X 3 n Si (OR 3 ) 4-n (in the formula,
X 3 is a halogen atom, R 3 is an alkyl group or aryl group having 1 to 10 carbon atoms, and m is 1 to 4. The present invention provides a method for polymerizing olefins, which is characterized in that it uses a solid material obtained by treatment with a halogen-containing silicon compound represented by (1), or a solid material obtained by further treating this solid material with titanium tetrachloride. The magnesium alkoxide used in the present invention has the general formula Mg(OR 1 )X 1 2-p (wherein, X 1 is a halogen atom,
R 1 represents a linear or side-chain alkyl group, alkenyl group, aryl group, cycloalkyl group, arylalkyl group or alkylaryl group having 1 to 20 carbon atoms; p represents 1 or 2; ) is a compound represented by Here R 1 is carbon number 1
~20, preferably 1 to 8 linear or side chain alkyl groups, alkenyl groups, aryl groups,
Indicates a cycloalkyl group, an arylalkyl group, an alkylaryl group, etc. Specifically, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium dicyclohexoxide, magnesium dibenzoxide, and the like are preferred. Furthermore, the magnesium alkoxide of the present invention includes:
In addition to the above, monoalkoxides containing halogen (XMgOR 1 ) can also be used. Note that these magnesium alkoxides can be easily obtained by known methods. On the other hand, the halogenated titanium compound used in the present invention has the general formula X 2 nTi(OR 2 ) 4-o (X 2 is a halogen atom,
R2 represents an alkyl group or an aryl group having 1 to 10 carbon atoms, and n represents 1 to 4. ), specifically TiCl 4 , TiBr 4 , CH 3 OTiCl 3 ,
C 2 H 5 OTiCl 3 , C 3 H 7 OTiCl 3 , (C 2 H 5 O) 2 TiCl 2
Examples include (C 2 H 5 O) 3 TiCl. Furthermore , the halogen - containing silicon compound used in the present invention usually has the general formula : 4), specifically SiCl 4 , CH 3 OSiCl 3 ,
( CH3O ) 2SiCl2 , ( CH3O ) 3SiCl , C2H5OSiCl3 ,
(C 2 H 5 O) 2 SiCl 2 , (C 2 H 5 O) 3 SiCl, C 3 H 7 OSiCl 3 ,
(C 3 H 7 O) 2 SiCl 2 , (C 3 H 7 O) 3 SiCl, C 6 H 5 OSiCl 3 ,
Examples include (C 6 H 5 O) 2 SiCl 2 and (C 6 H 5 O) 3 SiCl. In the method of the present invention, first, the above-mentioned magnesium alkoxide and a halogen-containing titanium compound are reacted. This reaction may be carried out in an inert solvent such as pentane, hexane, heptane, cyclohexane, benzene, xylene, etc., or may be carried out without a solvent. The reaction temperature is 0~
200℃, preferably 20-150℃, reaction time 5
~10 hours, preferably 30 minutes to 5 hours. In addition, the ratio of the above magnesium alkoxide and halogen-containing titanium compound is usually such that the halogen-containing titanium compound is added to the magnesium alkoxide.
0.1-10 (molar ratio), preferably 0.5-5 (molar ratio)
shall be. In addition, when carrying out the above-mentioned reaction in the absence of a solvent, it is desirable to proceed with the reaction while placing both the above-mentioned compounds in a ball mill or the like and pulverizing them. In the present invention, after the above-mentioned reaction, the obtained product is sufficiently washed and then further treated with the halogen-containing silicon compound. The conditions at this time are not particularly limited and can be selected as appropriate.
Usually in the same inert solvent as mentioned above, reaction temperature 0-200°C, preferably 20-100°C, reaction time 5.
The time period is from minutes to 5 hours, preferably from 30 minutes to 4 hours. The ratio of the halogen-containing silicon compound to the magnesium alkoxide is usually 0.1 to 10 (molar ratio), preferably 0.5 to 5 (molar ratio). Note that the above treatment can be carried out without a solvent, but in this case, it is desirable to proceed with the reaction while pulverizing with a ball mill or the like. In the method of the present invention, the solid material obtained by the above treatment is thoroughly washed and used as a component of the catalyst. In another embodiment of the invention, the solid material obtained by the above treatment is further treated with titanium tetrachloride. In this case, the processing conditions are as follows:
200℃, preferably 20~150℃, time 5 minutes~5
The time should preferably be between 30 minutes and 4 hours.
Further, this treatment may be carried out in the above-mentioned inert solvent, or may be carried out without a solvent while being pulverized using a ball mill or the like. The proportion of titanium tetrachloride to be added is not particularly limited, but it is preferably about 1 to 20 times (molar ratio) to that of magnesium alkoxide. In the present invention, the solid material obtained by such treatment can also be used as a component of the catalyst. In the method of the present invention, the solid material obtained by the above treatment is used as (A) a titanium-containing catalyst component,
An organoaluminum compound is added as component (B) to this, and a catalyst consisting of both components (A) and (B) is used.
When polymerizing olefin, (A) is added to the reaction system.
A dispersion of the titanium-containing solid catalyst component described above as a component and an organoaluminum compound as a component (B) are added as a catalyst, and then an olefin is introduced into the system. 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 10 mmol/, preferably 0.003 to 1 mmol/in terms of titanium atoms of the titanium-containing solid catalyst component,
On the other hand, the organoaluminum compound is adjusted to have an aluminum atom/titanium atom ratio of 1 to 1000 (atomic ratio), preferably 10 to 200 (atomic ratio), relative to the titanium-containing solid catalyst component. In addition, the olefin pressure in the reaction system varies depending on the type, but is usually 2 to 50
The atmospheric pressure is in the range of 0 to 200°C, preferably 50 to 150°C, and the reaction time is 10 minutes to 5 hours.
Preferably it is 30 minutes to 3 hours. Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen. Typical examples of organoaluminum compounds that are component (B) mentioned above include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, and trioctylaluminum, and diethylaluminum monochloride and diisopropylaluminum monochloride. Examples include dialkylaluminum monohalides such as chloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride. Polyolefins that can be polymerized using the above catalyst include homopolymers of α-olefins such as ethylene, propylene, 1-butene, and 1-hexene, as well as other α-olefins containing these olefins and small amounts of other α-olefins.
Examples include copolymers with olefins. In addition, when polymerizing propylene, adding an ester such as methyl p-toluate or ethyl benzoate to the above-mentioned reaction system improves the isotacticity of the resulting polypropylene. As mentioned above, if the titanium-containing solid catalyst component obtained by the method of the present invention is used as a catalyst component to polymerize olefins, the catalyst activity is extremely high, so that a sufficient effect can be obtained even with a small amount of use. is obtained. As a result, the deashing step (catalyst removal step) can be omitted. Furthermore, the amount of carrier used and the number of catalyst preparations per production amount of polyolefin can be significantly reduced compared to conventional methods. Furthermore, the resulting polyolefins such as polyethylene and polypropylene have a high bulk specific gravity and a good particle size distribution, making the powder very easy to handle. Next, the method of the present invention will be explained in more detail with reference to Examples. Example 1 [Production of solid catalyst component] 150 ml of dehydrated hexane, Mg was placed in a 500 ml four-necked flask equipped with a dropping funnel, a gas inlet, a stirring rod, and a reflux condenser.
Add 10.0g (88 mmol) of (OC 2 H 5 ) 2 and heat at 20℃.
16.6 g (88 mmol) of TiCl 4 was added dropwise. After the dropwise addition was completed, the temperature was raised to 70°C and reaction was carried out for 3 hours.
After the reaction, the temperature was returned to room temperature, the supernatant was removed, and 250 ml of hexane was added for washing. This operation was repeated five times to obtain solid substance P-1.
The amount of titanium supported on P-1 was 108 mg-Ti/g-support. Next, add the hexane slurry of P-1 at room temperature.
29.9 g (176 mmol) of SiCl 4 was added dropwise. After the dropwise addition was completed, the temperature was raised to 70°C and the reaction was carried out for 3 hours. After the reaction, the temperature was lowered to room temperature, the supernatant liquid was taken out, 250 ml of hexane was added, and the mixture was washed by a decanting method. This operation was repeated five times to obtain solid catalyst component P-2. The amount of titanium supported in P-2 was 55 mg-Ti/g-support. Next, add the hexane slurry of P-2 at room temperature.
41.6 g (220 mmol) of TiCl 4 was added dropwise. After the dropwise addition was completed, the temperature was raised to 70°C and reaction was carried out for 3 hours. After the reaction, return to room temperature and remove the supernatant.
Another 250 ml of hexane was added and the mixture was washed by the decanting method. Repeat this operation 5 times, solid catalyst component P
- got 3. The amount of titanium supported on P-3 is 303 mg.
It was Ti/g-support. [Polymerization of ethylene] 400 ml of hexane, 2 mmol of triethylaluminum, and 0.01 mmol of solid catalyst component P-2 as Ti were added to the autoclave No. 1, and the temperature was heated to 80°C. Hydrogen was added at 3 kg/cm 2 and ethylene at 5 kg/cm 2 , and polymerization was carried out for 1 hour while maintaining the ethylene at a total pressure of 9.3 kg/cm 2 . As a result, 98.4 g of white polyethylene was obtained. The catalyst activity of the product obtained was 205 kg per hour per gram of titanium atom, the melt index was 1.5 g/10 minutes, the bulk specific gravity of the polymer was 0.26, and the content of fine powder of 105 μm or less was 3.0%. Examples 2 to 4 In Example 1, solid catalyst components (P-2) were produced by varying the amount of SiCl 4 used, and ethylene was polymerized using these as catalysts. The results are shown in the table below.
実施例1において、SiCl4の代りにSi
(OC2H5)2Cl2を73.6g(352ミリモル)使用した
こと以外は実施例1と同様の操作を行なつて固体
触媒成分P―2を製造した。P―2のチタン担持
量は72mg―Ti/g―担体であつた。
〔エチレンの重合〕
上記の固体触媒成分P―2を用いたこと以外
は、実施例1と同様な条件でエチレンの重合を行
なつた。その結果、ポリエチレン75gが得られ、
触媒活性はチタン原子1g、1時間あたりのポリ
エチレン収量156Kgであつた。また得られたポリ
エチレンのメルトインデツクスは1.7、かさ比重
は0.24であり、105μ未満の微粉は5.5重量%であ
つた。
実施例 6
〔固体触媒成分の製造〕
エチルマグネシウムクロリド(C2H5MgCl)の
テトラヒドロフラン溶液にマグネシウムと等モル
のエタノールを反応させ、減圧乾燥してMg
(OC2H5)Cl10g(95.7ミリモル)を製造し、こ
れをヘキサン150mlに懸濁して、この懸濁液に
TiCl4を18.1g(95.7ミリモル)滴下し、適下終
了後70℃で3時間反応させた。次に、さらに
SiCl4を20℃で36.4g(191ミリモル)滴下し、70
℃に昇温して3時間反応させた。反応後、温度を
下げ室温において上澄液を抜き取り、新たにヘキ
サン250mlを加えて、傾斜法により洗浄した。こ
の操作を5回繰り返し、固体触媒成分P―2を得
た。このP―2のチタン担持量は35mg―Ti/g
―担体であつた。
〔エチレンの重合〕
上記の固体触媒成分P―2を用いたこと以外
は、実施例1と同様の条件でエチレンの重合を行
なつた。その結果、ポリエチレン82.3gが得ら
れ、触媒活性はチタン原子1g、1時間あたりの
ポリエチレン収量171Kgであつた。また得られた
ポリエチレンのメルトインデツクスは1.1、かさ
比重は0.27であり、105μ未満の微粉は7.3重量%
であつた。
実施例 7
〔プロピレンの重合〕
1のオートクレーブにn―ヘプタン400ml、
トリエチルアルミニウム2ミリモルおよび実施例
1で得られた固体触媒成分P―2とTiとして0.04
ミリモル加え、70℃に昇温した。この反応系にプ
ロピレンを7Kg/cm2に保持するよう連続的に供給
して2時間重合した。終了後、温度を下げ未反応
ガスをパージしポリマーを回収した。ポリプロピ
レンの収量は78gであり、沸とうn―ヘプタン不
溶分は55.3%であつた。
比較例 1
実施例1で得られた固体物質P―1をTiとし
て0.05ミリモルを使用し、他は実施例1と同じ条
件でエチレンの重合を行なつた。その結果、ポリ
エチレン63.1gが得られ、触媒活性はチタン原子
1g、1時間あたりのポリエチレン収量26Kgであ
つた。また得られたポリエチレンのメルトインデ
ツクスは2.3、かさ比重0.19であり、105μ未満の
微粉は1.3重量%であつた。
実施例 8
実施例1で得られた固体触媒成分P―3をTi
として0.01ミリモル使用する以外は、実施例1と
同様な条件でエチレンの重合を行なつた。その結
果、ポリエチレン132gが得られ、触媒活性はチ
タン原子1g,1時間あたりのポリエチレン収量
275Kgであつた。また得られたポリエチレンのメ
ルトインデツクスは1.2、かさ比重0.32であつた。
実施例 9〜11
実施例2〜4で得られた固体触媒成分P―2を
さらに過剰のTiCl4で処理して固体触媒成分P―
3を製造し、それらを触媒としてエチレンの重合
を行なつた結果を下表に示す。
In Example 1, SiCl 4 was replaced with Si
Solid catalyst component P-2 was produced in the same manner as in Example 1 except that 73.6 g (352 mmol) of (OC 2 H 5 ) 2 Cl 2 was used. The amount of titanium supported in P-2 was 72 mg-Ti/g-support. [Polymerization of ethylene] Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the solid catalyst component P-2 was used. As a result, 75g of polyethylene was obtained,
The catalyst activity was 1 g of titanium atom, and the polyethylene yield was 156 kg per hour. The melt index of the obtained polyethylene was 1.7, the bulk specific gravity was 0.24, and the content of fine powder less than 105μ was 5.5% by weight. Example 6 [Production of solid catalyst component] A solution of ethylmagnesium chloride (C 2 H 5 MgCl) in tetrahydrofuran is reacted with ethanol in an equimolar amount of magnesium, and dried under reduced pressure to produce Mg
Prepare 10 g (95.7 mmol) of (OC 2 H 5 )Cl, suspend it in 150 ml of hexane, and add it to this suspension.
18.1 g (95.7 mmol) of TiCl 4 was added dropwise, and after the addition, the reaction was carried out at 70° C. for 3 hours. Then further
36.4 g (191 mmol) of SiCl 4 was added dropwise at 20°C, and 70
The temperature was raised to 0.degree. C., and the mixture was reacted for 3 hours. After the reaction, the temperature was lowered and the supernatant liquid was taken out at room temperature, 250 ml of hexane was added, and the mixture was washed by a decanting method. This operation was repeated five times to obtain solid catalyst component P-2. The amount of titanium supported in this P-2 is 35mg-Ti/g
-It was a carrier. [Polymerization of ethylene] Polymerization of ethylene was carried out under the same conditions as in Example 1, except that the above-mentioned solid catalyst component P-2 was used. As a result, 82.3 g of polyethylene was obtained, the catalyst activity was 1 g of titanium atom, and the polyethylene yield per hour was 171 kg. The melt index of the obtained polyethylene was 1.1, the bulk specific gravity was 0.27, and the fine powder less than 105μ was 7.3% by weight.
It was hot. Example 7 [Polymerization of propylene] 400 ml of n-heptane in autoclave 1,
2 mmol of triethylaluminum, solid catalyst component P-2 obtained in Example 1 and 0.04 as Ti
mmol was added and the temperature was raised to 70°C. Propylene was continuously supplied to the reaction system to maintain a concentration of 7 kg/cm 2 and polymerization was carried out for 2 hours. After completion, the temperature was lowered, unreacted gas was purged, and the polymer was recovered. The yield of polypropylene was 78 g, and the boiling n-heptane insoluble content was 55.3%. Comparative Example 1 Ethylene polymerization was carried out under the same conditions as in Example 1 except that 0.05 mmol of Ti was used in the solid substance P-1 obtained in Example 1. As a result, 63.1 g of polyethylene was obtained, the catalyst activity was 1 g of titanium atom, and the yield of polyethylene per hour was 26 kg. The melt index of the obtained polyethylene was 2.3, the bulk specific gravity was 0.19, and the amount of fine powder less than 105μ was 1.3% by weight. Example 8 The solid catalyst component P-3 obtained in Example 1 was
Ethylene polymerization was carried out under the same conditions as in Example 1, except that 0.01 mmol of ethylene was used. As a result, 132 g of polyethylene was obtained, and the catalyst activity was 1 g of titanium atom, polyethylene yield per hour.
It weighed 275Kg. The polyethylene obtained had a melt index of 1.2 and a bulk specific gravity of 0.32. Examples 9 to 11 Solid catalyst component P-2 obtained in Examples 2 to 4 was further treated with excess TiCl 4 to obtain solid catalyst component P-
The following table shows the results of producing 3 and polymerizing ethylene using them as catalysts.
実施例7においてP―2に代えて実施例1のP
―3を固体触媒成分として使用したこと以外は実
施例7と同じ条件でプロピレンの重合を行なつ
た。ポリプロピレン123gが得られ、沸とうn―
ヘプタン不溶分は60.1%であつた。
In Example 7, P-2 in Example 1 was replaced with P-2.
Polymerization of propylene was carried out under the same conditions as in Example 7 except that -3 was used as the solid catalyst component. 123g of polypropylene was obtained and boiled n-
The heptane insoluble content was 60.1%.
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)
ミニウム化合物を組み合せてなる触媒を用いてオ
レフイン類を重合する方法において、前記(A)チタ
ン含有固体触媒成分として一般式Mg(OR1)p
X1 2-p(式中、X1はハロゲン原子、R1は炭素数1
〜20個の直鎖状あるいは側鎖状のアルキル基、ア
ルケニル基、アリール基、シクロアルキル基、ア
リールアルキル基またはアルキルアリール基を示
し、pは1または2を示す。)で表わされるマグ
ネシウムアルコキシドに対し、一般式X2 oTi
(OR2)4-o(式中、X2はハロゲン原子、R2は炭素
数1〜10個のアルキル基またはアリール基、nは
1〜4を示す。)で表わされるハロゲン含有チタ
ン化合物を0.1〜10(モル比)の割合で反応させ、
次いで一般式X3 nSi(OR3)4-n(式中、X3はハロ
ゲン原子、R3は炭素数1〜10のアルキル基また
はアリール基、mは1〜4を示す。)で表わされ
るハロゲン含有ケイ素化合物で処理して得られる
固体物質を用いることを特徴とするオレフイン類
の重合方法。 2 (A)チタン含有固体触媒成分および(B)有機アル
ミニウム化合物を組み合せてなる触媒を用いてオ
レフイン類を重合する方法において、前記(A)チタ
ン含有固体触媒成分として一般式Mg(OR1)p
X1 2-p(式中、X1はハロゲン原子、R1は炭素数1
〜20個の直鎖状あるいは側鎖状のアルキル基、ア
ルケニル基、アリール基、シクロアルキル基、ア
リールアルキル基またはアルキルアリール基を示
し、pは1または2を示す。)で表わされるマグ
ネシウムアルコキシドに対し、一般式X2 oTi
(OR2)4-o(式中、X2はハロゲン原子、R2は炭素
数1〜10個のアルキル基またはアリール基、nは
1〜4を示す。)で表わされるハロゲン含有チタ
ン化合物を0.1〜10(モル比)の割合で反応させ、
次いで一般式X3 nSi(OR3)4-n(式中、X3はハロ
ゲン原子、R3は炭素数1〜10のアルキル基また
はアリール基、mは1〜4を示す。)で表わされ
るハロゲン含有ケイ素化合物で処理し、さらに四
塩化チタンで処理して得られる固体物質を用いる
ことを特徴とするオレフイン類の重合方法。[Scope of Claims] 1. In a method for polymerizing olefins using a catalyst comprising a combination of (A) a titanium-containing solid catalyst component and (B) an organoaluminum compound, the titanium-containing solid catalyst component (A) has the general formula Mg( OR1 ) p
X 1 2-p (In the formula, X 1 is a halogen atom, R 1 is a carbon number of 1
~20 straight-chain or side-chain alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, arylalkyl groups, or alkylaryl groups, and p represents 1 or 2. ), the general formula X 2 o Ti
(OR 2 ) 4-o (wherein, X 2 is a halogen atom, R 2 is an alkyl group or aryl group having 1 to 10 carbon atoms, and n is 1 to 4). React at a ratio of 0.1 to 10 (molar ratio),
Then , it is represented by the general formula A method for polymerizing olefins, characterized by using a solid material obtained by treatment with a halogen-containing silicon compound. 2. In a method for polymerizing olefins using a catalyst comprising a combination of (A) a titanium-containing solid catalyst component and (B) an organoaluminum compound, the general formula Mg(OR 1 ) p is used as the titanium-containing solid catalyst component (A).
X 1 2-p (In the formula, X 1 is a halogen atom, R 1 is a carbon number of 1
~20 straight-chain or side-chain alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, arylalkyl groups, or alkylaryl groups, and p represents 1 or 2. ), the general formula X 2 o Ti
(OR 2 ) 4-o (wherein, X 2 is a halogen atom, R 2 is an alkyl group or aryl group having 1 to 10 carbon atoms, and n is 1 to 4). React at a ratio of 0.1 to 10 (molar ratio),
Then , it is represented by the general formula 1. A method for polymerizing olefins, which comprises using a solid material obtained by treating with a halogen-containing silicon compound and further treating with titanium tetrachloride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10022379A JPS5624408A (en) | 1979-08-08 | 1979-08-08 | Polymerization of olefin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10022379A JPS5624408A (en) | 1979-08-08 | 1979-08-08 | Polymerization of olefin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5624408A JPS5624408A (en) | 1981-03-09 |
JPS638124B2 true JPS638124B2 (en) | 1988-02-20 |
Family
ID=14268286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10022379A Granted JPS5624408A (en) | 1979-08-08 | 1979-08-08 | Polymerization of olefin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5624408A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59182806A (en) * | 1983-04-01 | 1984-10-17 | Mitsubishi Chem Ind Ltd | Production of olefinic polymer |
CN100532402C (en) * | 2001-11-01 | 2009-08-26 | 出光兴产株式会社 | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
TW200300144A (en) | 2001-11-01 | 2003-05-16 | Idemitsu Petrochemical Co | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
-
1979
- 1979-08-08 JP JP10022379A patent/JPS5624408A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5624408A (en) | 1981-03-09 |
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