JPH0552323B2 - - Google Patents
Info
- Publication number
- JPH0552323B2 JPH0552323B2 JP58057058A JP5705883A JPH0552323B2 JP H0552323 B2 JPH0552323 B2 JP H0552323B2 JP 58057058 A JP58057058 A JP 58057058A JP 5705883 A JP5705883 A JP 5705883A JP H0552323 B2 JPH0552323 B2 JP H0552323B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- polymerization
- oph
- propylene
- compound
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 28
- 239000011949 solid catalyst Substances 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000002681 magnesium compounds Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 239000000460 chlorine Substances 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 21
- 150000003377 silicon compounds Chemical class 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 14
- 230000037048 polymerization activity Effects 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 description 7
- -1 ethylene, propylene Chemical group 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000005054 phenyltrichlorosilane Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KKNLETZIKBOKKL-UHFFFAOYSA-N ethenyl(diethyl)alumane Chemical compound CC[Al](CC)C=C KKNLETZIKBOKKL-UHFFFAOYSA-N 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- XSXVXSCMWUJXOS-UHFFFAOYSA-N ethyl 2-ethylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1CC XSXVXSCMWUJXOS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QAYQKAPOTVSWLS-UHFFFAOYSA-N methyl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OC QAYQKAPOTVSWLS-UHFFFAOYSA-N 0.000 description 1
- KQQKFHNRMJHXLR-UHFFFAOYSA-N methyl 2-ethylbenzoate Chemical compound CCC1=CC=CC=C1C(=O)OC KQQKFHNRMJHXLR-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-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
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はα−オレフイン重合用固体触媒に関す
る。更に詳しくはエチレン、プロピレン、ブテン
−１，４−メチルペンテン−１等の重合に好まし
く使用される、高重合活性を有する担体付触媒成
分と有機アルミニウム化合物とからなる固体触媒
に関するものである。
従来、担体付触媒で炭素数３以上のα−オレフ
インの立体規則性重合に適した触媒として特開昭
48−16986号、特開昭49−86482号、特開昭50−
108385号、特開昭50−126590号、特開昭51−
28189号等をはじめとしてハロゲン化マグネシウ
ム化合物、好ましくは塩化マグネシウムを担体原
料に用いてチタン含有触媒を製造する方法が数多
く提案されている。
また、本発明で用いる一般式
Mg（OR1）o（OR2）2-o ……〔〕
（式中、R1、R2はアルキル基、アリール基また
はアラルキル基を示し、R1とR2は同一でも異な
つても良い。ｎは２≧ｎ≧０を示す。）
を担体として使用したチタン含有触媒を用いたオ
レフインの重合に関しても特公昭46−34098号、
特公昭47−1768号、特公昭47−42137号等に提案
がなされてはいるが、炭素数３以上のα−オレフ
インの高立体規則性重合に適したものはなかつ
た。一般式〔〕で示される担体を用いて立体規
則性を改良する試みも種々提案され本出願人が先
に提案した特開昭52−98076号をはじめとして特
開昭53−2580号、特開昭53−43094号、特開昭55
−152710号、特開昭56−26904号等が提案されて
はいるが充分に満足出来るものではなかつた。本
発明者らは、一般式〔〕で示される担体を用い
たチタン含有固体触媒の製法およびその触媒によ
る重合方法について検討した結果本発明に到達し
た。
すなわち本発明は、一般式Mg（OR1）o（OR2）2
−ｏ
（式中、R1、R2はアルキル基、アリール基また
はアラルキル基を示し、R1とR2は同一でも異な
つても良い。ｎは２≧ｎ≧０を示す。）で表わさ
れるマグネシウム化合物を、カルボン酸エステ
ル、ハロゲンとアリールオキシ基を含有するケイ
素化合物および塩素含有４価チタン化合物より成
る３種の化合物で処理することによつて得られる
チタン含有固体触媒成分(a)と、有機アルミニウム
化合物(b)より成る触媒の存在下にオレフインを重
合または共重合させることを特徴とするオレフイ
ン重合体の製造方法である。
先に示したハロゲン含有マグネシウムは吸湿性
または水分と反応する性質があり、ために一般式
〔〕で示される担体を使用することは触媒製造
工程上大きな利点がある。
本発明を詳述すれば、
(A) 一般式〔〕で示されるマグネシウム化合物
を
(B) カルボン酸エステルと
(C) ハロゲンとアリールオキシ基を含有するケイ
素化合物と
(D) 塩素含有４価チタン化合物
より成る３種の化合物で
処理することによつて得られる固体触媒成分(a)
と有機アルミニウム化合物(b)とを必須成分とし、
更に適宜カルボン酸エステル(c)を組合せたチタン
含有触媒を用いてオレフインの重合または共重合
することを特徴とするオレフイン重合体の製造法
である。
本発明で使用する一般式〔〕で示されるマグ
ネシウム化合物Ａを具体的に示すとMg
（OCH3）2、Mg（OC2M5）2、Mg（OC3H7）、Mg
（OC4H9）2、Mg（OC6H5）2、Mg（OCH2C6H5）2、
Mg（OC6H5）（OC4H9）、Mg（OC2H5）（CO6H5）、
Mg（OC4H6CH3）2等のジアルコキシマグネシウ
ム、ジアリールオキシマグネシウム、ジアラルキ
ルオキシマグネシウム、アルキルオキシアリール
オキシマグネシウムを挙げることができる。
カルボン酸エステル(B)としては、酢酸エチル、
プロピオン酸メチル、アクリル酸エチル、オレイ
ン酸エチル、ステアリン酸エチル、フエニル酢酸
エチル、安息香酸メチル、安息香酸エチル、安息
香酸プロピル、安息香酸ブチル、トルイル酸メチ
ル、トルイル酸エチル、トルイル酸プロピル、ト
ルイル酸ブチル、エチル安息香酸メチル、エチル
安息香酸エチル、キシレンカルボン酸エチル、ア
ニス酸メチル、アニス酸エチル、エトキシ安息香
酸メチル、エトキシ安息香酸エチル、ケイ皮酸エ
チル等が挙げられ、それらの中では芳香族カルボ
ン酸エステルが好ましく用いられる。
ハロゲンとアリールオキシ基を含有するケイ素
化合物(C)は、一般式SiRa（OAr）bXc（式中、Ｒ
はアルキル基、アリール基またはアラルキル基を
示し、Arはアリール基を示し、ａ、ｂ、ｃは０
≦ａ＜４、０＜ｂ＜４、０＜ｃ＜４、ａ＋ｂ＋ｃ
＝４である数を示し、Ｘはハロゲンを示す）で表
わされる化合物であるが、具体的には、
PhSi（OPh）2Cl（Phはフエニル基を示す）、PhSi
（OPh）1.5Cl1.5、PhSi（OPh）1Cl2、
PhSi（OPh）0.5Cl2.5、MeSi（OPh）2Cl（Meはメチ
ル基を示す）、MeSi（OPh）1.5cl1.5、MeSi
（OPh）1Cl2、MeSi（OPh）0.5Cl2.5、Si（OPh）3Cl、
Si（OPh）2.5、Cl1.5、Si（OPh）2Cl2、Si（OPh）1.5
Cl2.5、Si（OPh）1Cl3、Si（OPh）0.5Cl3.5等が挙げら
れる。さらにフエニル基が、ハロゲンあるいはア
ルキル基等で置換されていてもよい。これらの
内、好ましくはPhSi（OPh）0.5Cl2.5、PhSi
（OPh）1Cl2、
PhSi（OPh−Cl）0.5Cl2.5、PhSi（OPh−Me）0.5
Cl2.5、PhSi（OPh−Cl）1Cl2、PhSi（OPh−
Me）1Cl2等が挙げられる。
本発明方法において、前記(A)、(B)、(C)、(D)成分
は機械的粉砕手法または炭化水素溶媒の存在また
は不存在下に接触させる方法等の手法をとり得る
が、(A)、(B)、(C)、(D)成分を機械的粉砕混合あるい
は接触させ、不活性炭化水素溶媒で洗浄した後
(B)、(C)、(D)を加えて更に機械的粉砕するかまたは
(B)、(C)、(D)を加熱下に接触混合し不活性炭化水素
溶媒で洗浄する工程を少くとも１回以上繰り返す
方法も好ましくとり得る。
なお、繰り返し処理の際、(C)成分としてハロゲ
ンおよびアリールオキシ含有ケイ素化合物を少く
とも１回用いれば他のハロゲン含有ケイ素化合物
を用いてもよい。
また、触媒製造工程で使用する各成分の１つの
工程での使用量をモル比で表わすと通常次のとお
りである。
Mg（OR1）o（OR2）2-o
カルボン酸エステル10〜0.01、好ましくは１〜
0.1ハロゲンとアリールオキシ基を含有するケイ
素化合物
20〜0.1、好ましくは５〜0.5
塩素含有４価チタン化合物 100〜0.1、好ましく
は40〜１
そして通常生成物中のチタン量が0.1〜10重量
％、好ましくは0.5〜５重量％になるように上記
各成分の使用量を調節する。
上記各方法における機械粉砕は、ポールミル、
衝撃ミル、振動ミル等、従来一般式に採られてい
る方法によればよい。粉砕処理温度は通常室温付
近でよく、加熱、冷却は特に必要としない。粉砕
処理時間は使用する粉砕機の種類にもよるが、通
常、数時間乃至200時間である。
また、不活性炭化水素溶媒の存在または不存在
下での反応は通常室温から200℃、好ましくは80
〜150℃であり、反応時間は0.5〜４時間程度であ
る。
本発明においては上記のようにして得られる反
応生成物を次いで不活性炭化水素溶媒で洗浄し、
溶媒への可溶成分を除去する。そしてかくして得
られる触媒成分(a)と有機アルミニウム化合物(b)、
更に必要に応じてカルボン酸エステル(c)を混合し
てなる触媒系を用いて、オレフインの重合または
共重合を行なつてポリオレフインを製造するので
ある。この際(a)、(b)、(c)各成分の添加順序には特
に制限はない。
次にこの触媒系で用いられる有機アルミニウム
化合物〔(b)成分〕としては、好ましくは一般式
AlR2 oX3-oで表わされる化合物が挙げられる。上
式においてR2は炭素数１〜20個の炭化水素基、
特に脂肪族炭化水素基であり、Ｘはハロゲン、ｎ
は２〜３の数を示す。この有機アルミニウム化合
物の具体例としては、トリエチルアルミニウム、
トリプロピルアルミニウム、トリイソブチルアル
ミニウム、トリヘキシルアルミニウム、トリオク
チルアルミニウム、モノビニルジエチルアルミニ
ウム、ジエチルアルミニウムモノクライド等が挙
げられるが、好ましくはトリアルキルアルミニウ
ム単独およびジアルキルアルミニウムモノハライ
ドとの混合物が用いられる。
また、触媒系成分(c)は前述の固体触媒成分(a)製
造時に用いた(B)成分が用いられるが、好ましくは
芳香族カルボン酸エステルである。
触媒各成分の使用割合は、触媒成分(a)中のチタ
ン対(b)成分のアルミニウム化合物対(c)成分のカル
ボン酸エステルのモル比が１：３〜500：０〜100
好ましくは１：20〜200：３〜50になるように選
ばれる。
オレフインとしては、エチレン、プロピレン、
ブテン−１，３−メチルブテン−１，４−メチル
ペンテン−１等が挙げられ、好ましくは炭素数３
以上のα−オレフイン、特にプロピレンが挙げら
れる。また重合は単独重合のほかランダムまたは
ブロツク共重合体にも適用できる。
重合反応は不活性炭化水素、例えばヘキサン、
ヘプタン、シクロヘキサン、ベンゼン、トルエ
ン、ペンタン、ブタン或いはこれらの混合物、ま
たは重合を受けるα−オレフインの液化物を溶媒
といてスラリー重合方式で実施するのが好ましい
が、気相中で重合を行なうこともできる。温度は
50〜100℃、好ましくは60〜90℃であり、圧力は
特に制限されないが、通常大気圧〜100気圧の範
囲内から選ばれる。
また重合系内に分子量調節剤として水素を存在
させることもでき、これによりメルトフローイン
デツクス（MFI、ASTM−D1238で測定）で50
〜0.1のポリマーを容易に製造することができる。
その他それぞれのα−オレフインの重合、共重合
に当つて通常採られる手段を本発明方法に適用す
ることもできる。例えば前記触媒３成分(a)、(b)、
(c)または(a)、(b)２成分を用いてα−オレフインで
前処理する手法等である。
次に実施例によつて本発明を更に具体的に説明
するが、本発明はその要旨を逸脱しない限りこれ
ら実施例によつて制約を受けるものでない。
なお、第１図は本発明に含まれる技術内容の理
解を助けるためのフローチヤート図であり、本発
明はその要旨を超えない限りフローチヤート図に
よつて何ら制約を受けるものではない。
なお実施例において、重合活性（Ｋとして示
す）は１時間につきα−オレフイン圧１Kg／cm2当
り、チタン１ｇ当りのポリマー生成量(g)であり、
触媒効率（CEとして示す）は触媒成分のチタン
１ｇ当りのポリマーの生成量(g)である。アイソタ
クチツクインデツクス（として示す）は改良型
ソツクスレー抽出器で沸騰ｎ−ヘプタンにより６
時間抽出した場合の残量（重量％）である。非結
晶性ポリマーは沸騰ｎ−ヘプタンに可溶であるか
らは結晶性ポリマーの収率を示す。嵩密度（ρB
として示す。単位はｇ／c.c.）はJIS−Ｋ−6721に
従つて測定した。メルトフローインデツクス
（MFIとして示す）はASTM−Ｄ−1238に従つて
測定した。
実施例 １
(A) 触媒の製造
撹拌機、温度計を備えた300mlフラスコに精
製N2シール下市販Mg（OC2H5）2を５(g)ｒ採取
し、組成C6H5Si（OC6H5）0.5Cl2.5で示されるケ
イ素化合物10.5(g)ｒ、安息香酸エチル1.3(g)ｒ、
TiCl483(g)ｒをN2シール下に添加し、撹拌下
徐々に昇温した。
130℃に昇温後、同温度で１時間保持した後、
精製ｎ−ヘプタンで充分洗浄して上澄液を分離
後乾燥し、固体生成物を得た。
次いでC6H5Si（OC6H5）0.5Cl2.5のケイ素化合
物10.5(g)ｒ、安息香酸エチル1.3(g)ｒ、TiCl483
(g)ｒを添加し、130℃において１時間、固体生
成物を処理した。その後精製ｎ−ヘプタンで充
分洗浄し、上澄液を分離後乾燥し、固体触媒を
得た。担持Ti量は2.5重量％であつた。
(B) プロピレンの重合
精製N2で充分に置換した２の誘導撹拌式
オートクレープに、N2シール下室温でトリエ
チルアルミニウム1.3ミリモル、パラメチル安
息香酸メチル0.46ミリモルを添加し、更に室温
でH2を1.8Kg／cm2になるように加え、液体プロ
ピレンを700(g)ｒ添加した。撹拌下で昇温し、
70℃で上記固体触媒25mgを添加し、重合開始と
した。
70℃で１時間保持した後、余剰のプロピレン
をパージし、全てのアタクチツクポリプロピレ
ンを含め、白色粉末ポリプロピレン400(g)ｒを
得た。触媒効率CEは640Kg−PP／ｇ−Ti、重
合活性Ｋは21300であつた。
ρBは0.43ｇ／c.c.でありは96.1％、MFIは8.9で
あつた。
実施例 ２
実施例１の(A)において、ケイ素化合物として
C6H5Si（OC6H5）Cl211.8(g)ｒを用いた以外は、実
施例１(A)と同様にして固体触媒を得た。担持Ti
量は2.6重量％であつた。実施例１の(B)と同様に
してプロピレンの重合を行つたところ、触媒効率
CE＝600Kg−PP／ｇ−Ti、重合活性Ｋ＝20000で
あつた。ρBは0.42ｇ／c.c.で、は95.9％、MFIは
9.8であつた。
実施例 ３
実施例１の(A)において、ケイ素化合物として
C6H5Si（OC6H4−CH3）0.5Cl2.510.8(g)ｒを用いた以
外は実施例１(A)と同様にして固体触媒を得た。担
持Ti量は2.3重量％であつた。実施例１(B)と同様
にしてプロピレンの重合を行つたところ、触媒効
率CE＝580Kg−PP／ｇ−Ti、重合活性Ｋ＝
19300、ρB＝0.42ｇ／c.c.、＝95.8％、MFI＝8.8
の結果であつた。
実施例 ４
実施例１の(A)において、ケイ素化合物として
C6H5Si（OC6H4−CH3）Cl212.4(g)ｒを用いた以外
は実施例１(A)と同様にして固体触媒を得た。担持
Ti量は2.4重量％であつた。実施例１(B)と同様の
操作でプロピレンの重合を行つたところ、触媒効
率CE＝550Kg−PP／ｇ−Ti、重合活性Ｋ＝18300
であつた。ρB＝0.41ｇ／c.c.、＝95.4％、MFI＝
11.0であつた。
実施例 ５
実施例１の(A)においてケイ素化合物として
C6H5Si（OC6H4−Cl）0.5Cl2.511.3gr用いた以外は実
施例１(A)と同様にして固体触媒を得た。担持Ti
量は2.5重量％であつた。実施例１(B)と同様にし
てプロピレンの重合を行い、触媒効率CE＝540Kg
−PP／ｇ−Ti、重合活性Ｋ＝18000、ρB＝0.42
ｇ／c.c.、＝95.5％、MFI＝9.2の結果を得た。
実施例 ６
実施例１(A)において、ケイ素化合物として
C6H5Si（OC6H4−Cl）Cl213.3(g)ｒを用いた以外は
実施例１(A)と同様にして固体触媒を得た。実施例
１(B)と同様にしてプロピレンの重合を行つたとこ
ろ、触媒効率をCE＝530Kg−PP／ｇ−Ti、重合
活性Ｋ＝17700であり、ρB＝0.41ｇ／c.c.、＝95.3
％、MFI＝10.0であつた。
比較例 １
(A) 触媒の製造
実施例１の(A)において、ケイ素化合物として
フエニルトリクロルシラン9.2(g)ｒを用いた他
は、実施例１(A)と同様な操作を行つて固体触媒
を得た。担持Ti量は2.1重量％であつた。
(B) プロピレンの重合
上記(A)で得た固体触媒25.0mgを使用して、実
施例１(B)と同様な操作でプロピレンの重合を行
つたところ、触媒効率CE＝400Kg−PP／ｇ−
Tiで重合活性Ｋ＝13300であつた。ρBは0.40
ｇ／c.c.、＝94.4％、MFI＝10.0であつた。
比較例 ２
実施例１(A)においてケイ素化合物を使用しない
こと以外は、実施例１と同様にして固体触媒を合
成し、実施例１(B)と同様にしてプロピレンの重合
を行つた。その結果、触媒効率CE＝280Kg−
PP／ｇ−Ti、重合活性Ｋ＝9300、ρB＝0.38ｇ／
c.c.、＝91.0％、MFI＝5.3であつた。
実施例７、８、比較例３、４
実施例７、８では実施例１の触媒を、比較例
３、４では比較例１の触媒を用いてプロピレン重
合時に添加するパラメチル安息香酸メチルの量を
表−１に示すように変更し重合を実施した。
結果を表−１に示す。
The present invention relates to a solid catalyst for α-olefin polymerization. More specifically, the present invention relates to a solid catalyst preferably used for the polymerization of ethylene, propylene, butene-1,4-methylpentene-1, etc., which is composed of a supported catalyst component having high polymerization activity and an organoaluminum compound. Conventionally, JP-A-Sho has proposed a supported catalyst suitable for the stereoregular polymerization of α-olefins having 3 or more carbon atoms.
No. 48-16986, JP-A No. 49-86482, JP-A No. 50-
No. 108385, Japanese Patent Application Publication No. 126590, Japanese Patent Application Publication No. 1973-
Many methods have been proposed, including No. 28189, for producing a titanium-containing catalyst using a halogenated magnesium compound, preferably magnesium chloride, as a carrier raw material. Furthermore, the general formula used in the present invention is Mg(OR 1 ) o (OR 2 ) 2-o ...[] (wherein, R 1 and R 2 represent an alkyl group, an aryl group, or an aralkyl group, and R 1 and R 2 may be the same or different; n indicates 2≧n≧0.
Although proposals have been made in Japanese Patent Publications No. 47-1768 and Japanese Patent Publication No. 47-42137, none have been found suitable for highly stereoregular polymerization of α-olefins having 3 or more carbon atoms. Various attempts have been made to improve the stereoregularity using a carrier represented by the general formula [], including JP-A No. 52-98076, which was previously proposed by the present applicant, as well as JP-A No. 53-2580, JP-A No. No. 1983-43094, Japanese Patent Application Publication No. 1983
-152710, JP-A-56-26904, etc. have been proposed, but these have not been fully satisfactory. The present inventors have arrived at the present invention as a result of studying a method for producing a titanium-containing solid catalyst using a carrier represented by the general formula [] and a polymerization method using the catalyst. That is, the present invention is based on the general formula Mg(OR 1 ) o (OR 2 ) 2
-o (In the formula, R 1 and R 2 represent an alkyl group, an aryl group, or an aralkyl group, and R 1 and R 2 may be the same or different. n represents 2≧n≧0.) A titanium-containing solid catalyst component (a) obtained by treating a magnesium compound with three types of compounds consisting of a carboxylic acid ester, a silicon compound containing a halogen and an aryloxy group, and a chlorine-containing tetravalent titanium compound; This is a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound (b). The above-mentioned halogen-containing magnesium has a property of being hygroscopic or reacting with moisture, and therefore, the use of a support represented by the general formula [] has a great advantage in the catalyst manufacturing process. To explain the present invention in detail, (A) a magnesium compound represented by the general formula [ ], (B) a carboxylic acid ester, (C) a silicon compound containing a halogen and an aryloxy group, and (D) a chlorine-containing tetravalent titanium Solid catalyst component (a) obtained by treatment with three types of compounds consisting of
and an organoaluminum compound (b) as essential components,
This method of producing an olefin polymer is characterized in that the olefin is polymerized or copolymerized using a titanium-containing catalyst in combination with an appropriate carboxylic acid ester (c). Specifically, the magnesium compound A represented by the general formula [] used in the present invention is Mg
( OCH3 ) 2 , Mg( OC2M5 ) 2 , Mg( OC3H7 ), Mg
(OC 4 H 9 ) 2 , Mg (OC 6 H 5 ) 2 , Mg (OCH 2 C 6 H 5 ) 2 ,
Mg( OC6H5 ) ( OC4H9 ) , Mg( OC2H5 ) ( CO6H5 ) ,
Examples include dialkoxymagnesium, diaryloxymagnesium, dialkyloxymagnesium, and alkyloxyaryloxymagnesium such as Mg(OC 4 H 6 CH 3 ) 2 . As the carboxylic acid ester (B), ethyl acetate,
Methyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, toluic acid Examples include butyl, methyl ethylbenzoate, ethyl ethylbenzoate, ethyl xylenecarboxylate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, etc. Among them, aromatic Carboxylic acid esters are preferably used. The silicon compound (C) containing a halogen and an aryloxy group has the general formula SiRa(OAr)bXc (wherein R
represents an alkyl group, an aryl group, or an aralkyl group, Ar represents an aryl group, and a, b, and c are 0
≦a<4, 0<b<4, 0<c<4, a+b+c
= 4, and X represents a halogen), specifically, PhSi(OPh) 2 Cl (Ph represents a phenyl group), PhSi
(OPh) 1.5 Cl 1.5 , PhSi (OPh) 1 Cl 2 , PhSi (OPh) 0.5 Cl 2.5 , MeSi (OPh) 2 Cl (Me represents a methyl group), MeSi (OPh) 1.5 cl 1.5 , MeSi
(OPh) 1 Cl 2 , MeSi(OPh) 0.5 Cl 2.5 , Si(OPh) 3 Cl,
Si (OPh) 2.5 , Cl 1.5 , Si (OPh) 2 Cl 2 , Si (OPh) 1.5
Examples include Cl 2.5 , Si(OPh) 1 Cl 3 , Si(OPh) 0.5 Cl 3.5 and the like. Furthermore, the phenyl group may be substituted with a halogen or an alkyl group. Among these, PhSi(OPh) 0.5 Cl 2.5 , PhSi
(OPh) 1 Cl 2 , PhSi(OPh−Cl) 0.5 Cl 2.5 , PhSi(OPh−Me) 0.5
Cl 2.5 , PhSi(OPh−Cl) 1 Cl 2 , PhSi(OPh−
Me) 1 Cl 2 etc. In the method of the present invention, the components (A), (B), (C), and (D) may be treated by mechanical pulverization or by contacting them in the presence or absence of a hydrocarbon solvent. After mechanically grinding, mixing or contacting components A), (B), (C), and (D) and washing with an inert hydrocarbon solvent.
Add (B), (C), and (D) and further mechanically crush or
A method of repeating the steps of contact-mixing (B), (C), and (D) under heating and washing with an inert hydrocarbon solvent at least once can also be preferably used. In addition, in the repeated treatment, as long as the halogen- and aryloxy-containing silicon compound is used at least once as component (C), other halogen-containing silicon compounds may be used. Furthermore, the amounts of each component used in the catalyst manufacturing process in one process are usually expressed in molar ratios as follows. Mg (OR 1 ) o (OR 2 ) 2-o carboxylic acid ester 10 to 0.01, preferably 1 to
Silicon compound containing 0.1 halogen and aryloxy group 20-0.1, preferably 5-0.5 Chlorine-containing tetravalent titanium compound 100-0.1, preferably 40-1 and usually the amount of titanium in the product is 0.1-10% by weight, The amount of each of the above components used is preferably adjusted to 0.5 to 5% by weight. Mechanical pulverization in each of the above methods is performed using a pole mill,
Any conventional method such as an impact mill or a vibration mill may be used. The pulverization temperature may normally be around room temperature, and heating and cooling are not particularly required. The pulverization time depends on the type of pulverizer used, but is usually from several hours to 200 hours. In addition, the reaction in the presence or absence of an inert hydrocarbon solvent is usually carried out at room temperature to 200°C, preferably at 80°C.
The temperature is ~150°C, and the reaction time is about 0.5 to 4 hours. In the present invention, the reaction product obtained as described above is then washed with an inert hydrocarbon solvent,
Remove components soluble in the solvent. and the thus obtained catalyst component (a) and organoaluminum compound (b),
Further, if necessary, a catalyst system containing a carboxylic acid ester (c) is used to carry out polymerization or copolymerization of the olefin to produce a polyolefin. At this time, there is no particular restriction on the order in which the components (a), (b), and (c) are added. Next, the organoaluminum compound [component (b)] used in this catalyst system preferably has the general formula
Examples include compounds represented by AlR 2 o X 3-o . In the above formula, R 2 is a hydrocarbon group having 1 to 20 carbon atoms,
In particular, it is an aliphatic hydrocarbon group, where X is a halogen, n
indicates a number of 2 to 3. Specific examples of this organoaluminum compound include triethylaluminum,
Examples include tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, monovinyl diethylaluminium, diethylaluminium monoclide, and preferably trialkyl aluminum alone or a mixture with dialkyl aluminum monohalide is used. Further, as the catalyst system component (c), the component (B) used in the production of the solid catalyst component (a) described above is used, but aromatic carboxylic acid ester is preferable. The ratio of catalyst components to be used is such that the molar ratio of titanium in catalyst component (a) to aluminum compound in component (b) to carboxylic acid ester in component (c) is 1:3 to 500:0 to 100.
Preferably, the ratio is selected to be 1:20 to 200:3 to 50. Olefins include ethylene, propylene,
Examples include butene-1,3-methylbutene-1,4-methylpentene-1, preferably 3 carbon atoms.
The above-mentioned α-olefins, especially propylene, can be mentioned. In addition to homopolymerization, the polymerization can also be applied to random or block copolymers. The polymerization reaction is carried out using an inert hydrocarbon, such as hexane,
Slurry polymerization is preferably carried out using heptane, cyclohexane, benzene, toluene, pentane, butane, or a mixture thereof, or a liquefied product of α-olefin to be polymerized as a solvent, but polymerization may also be carried out in a gas phase. can. The temperature is
The temperature is 50 to 100°C, preferably 60 to 90°C, and the pressure is not particularly limited, but is usually selected from within the range of atmospheric pressure to 100 atm. Hydrogen can also be present as a molecular weight regulator in the polymerization system, which results in a melt flow index (MFI, measured by ASTM-D1238) of 50
~0.1 polymers can be easily produced.
Other methods commonly used for the polymerization and copolymerization of α-olefins can also be applied to the method of the present invention. For example, the three catalyst components (a), (b),
(c) or a method of pretreating with α-olefin using two components (a) and (b). Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples unless it deviates from the gist thereof. It should be noted that FIG. 1 is a flowchart diagram to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not exceed the gist thereof. In the examples, the polymerization activity (denoted as K) is the amount of polymer produced (g) per 1 g of titanium per 1 kg/cm 2 of α-olefin pressure per hour,
Catalytic efficiency (expressed as CE) is the amount of polymer produced (g) per gram of titanium in the catalyst component. The isotactic index (denoted as
This is the remaining amount (% by weight) when extracted over time. Since the amorphous polymer is soluble in boiling n-heptane, it indicates the yield of crystalline polymer. Bulk density (ρ B
Shown as The unit (g/cc) was measured according to JIS-K-6721. Melt flow index (denoted as MFI) was determined according to ASTM-D-1238. Example 1 (A) Production of catalyst 5 (g) of commercially available Mg(OC 2 H 5 ) 2 was collected under a purified N 2 seal in a 300 ml flask equipped with a stirrer and a thermometer, and the composition was C 6 H 5 Si ( OC 6 H 5 ) 0.5 Cl 2.5 silicon compound 10.5 (g) r, ethyl benzoate 1.3 (g) r,
83 (g) r of TiCl 4 was added under a N 2 blanket and the temperature was gradually increased with stirring. After raising the temperature to 130℃ and keeping it at the same temperature for 1 hour,
The supernatant was thoroughly washed with purified n-heptane and the supernatant was separated and dried to obtain a solid product. Then 10.5 (g) r of silicon compound of C 6 H 5 Si (OC 6 H 5 ) 0.5 Cl 2.5 , 1.3 (g) r of ethyl benzoate, TiCl 4 83
(g)r was added and the solid product was treated at 130°C for 1 hour. Thereafter, it was thoroughly washed with purified n-heptane, and the supernatant liquid was separated and dried to obtain a solid catalyst. The amount of Ti supported was 2.5% by weight. (B) Polymerization of propylene 1.3 mmol of triethylaluminum and 0.46 mmol of methyl p-methylbenzoate were added to the induction stirring autoclave ( 2) which had been sufficiently purged with purified N2 at room temperature under a N2 seal, and then H2 was added at room temperature. 700(g)r of liquid propylene was added to the mixture so that the amount was 1.8Kg/cm 2 . Raise the temperature while stirring,
25 mg of the above solid catalyst was added at 70°C to initiate polymerization. After being held at 70° C. for 1 hour, excess propylene was purged to obtain 400 (g) r of white powder polypropylene, including all the atactic polypropylene. The catalyst efficiency CE was 640 Kg-PP/g-Ti, and the polymerization activity K was 21,300. ρ B was 0.43 g/cc, 96.1%, and MFI was 8.9. Example 2 In (A) of Example 1, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 11.8 (g)r of C 6 H 5 Si(OC 6 H 5 )Cl 2 was used. Supported Ti
The amount was 2.6% by weight. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency was
CE=600Kg-PP/g-Ti, polymerization activity K=20000. ρ B is 0.42g/cc, is 95.9%, and MFI is
It was 9.8. Example 3 In (A) of Example 1, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that C6H5Si ( OC6H4 - CH3 ) 0.5Cl2.510.8 ( g ) r was used. The amount of Ti supported was 2.3% by weight. When propylene was polymerized in the same manner as in Example 1 (B), catalyst efficiency CE=580Kg-PP/g-Ti, polymerization activity K=
19300, ρ B =0.42g/cc, =95.8%, MFI=8.8
The result was Example 4 In (A) of Example 1, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 12.4(g ) r of C6H5Si ( OC6H4 - CH3 )Cl2 was used. carrying
The amount of Ti was 2.4% by weight. When propylene was polymerized in the same manner as in Example 1 (B), catalyst efficiency CE = 550 Kg-PP/g-Ti, polymerization activity K = 18300
It was hot. ρ B =0.41g/cc, =95.4%, MFI=
It was 11.0. Example 5 As a silicon compound in Example 1 (A)
A solid catalyst was obtained in the same manner as in Example 1(A) except that 11.3gr of C6H5Si ( OC6H4 - Cl ) 0.5Cl2.5 was used. Supported Ti
The amount was 2.5% by weight. Polymerization of propylene was carried out in the same manner as in Example 1 (B), and the catalyst efficiency was CE = 540 Kg.
-PP/g-Ti, polymerization activity K=18000, ρ B =0.42
Results of g/cc = 95.5% and MFI = 9.2 were obtained. Example 6 In Example 1(A), as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 13.3 (g)r of C6H5Si ( OC6H4 - Cl ) Cl2 was used. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency was CE = 530 Kg-PP/g-Ti, polymerization activity K = 17700, ρ B = 0.41 g/cc, = 95.3
%, MFI=10.0. Comparative Example 1 (A) Production of catalyst In (A) of Example 1, a solid was prepared by performing the same operation as in Example 1 (A) except that phenyltrichlorosilane 9.2 (g) r was used as the silicon compound. I got a catalyst. The amount of Ti supported was 2.1% by weight. (B) Polymerization of propylene Using 25.0 mg of the solid catalyst obtained in (A) above, propylene polymerization was carried out in the same manner as in Example 1 (B). Catalytic efficiency CE = 400 Kg - PP/g −
The polymerization activity K for Ti was 13,300. ρ B is 0.40
g/cc = 94.4%, MFI = 10.0. Comparative Example 2 A solid catalyst was synthesized in the same manner as in Example 1, except that no silicon compound was used in Example 1(A), and propylene was polymerized in the same manner as in Example 1(B). As a result, the catalyst efficiency CE = 280Kg−
PP/g-Ti, polymerization activity K=9300, ρ B =0.38g/
cc, = 91.0%, MFI = 5.3. Examples 7 and 8, Comparative Examples 3 and 4 In Examples 7 and 8, the catalyst of Example 1 was used, and in Comparative Examples 3 and 4, the catalyst of Comparative Example 1 was used, and the amount of methyl para-methylbenzoate added during propylene polymerization was Polymerization was carried out with the changes shown in Table 1. The results are shown in Table-1.
【表】
実施例 ９
(A) 触媒の製造
撹拌機、温度計を備えた300mlフラスコにN2
シール下、Mg（OC2H5）５ｇを採取し、フエ
ニルトリクロルシラン9.2ｇ、安息香酸エチル
1.3ｇ、TiCl483ｇを添加した。撹拌下徐々に昇
温し、130℃に昇温後同温度で１時間保持した。
その後、精製ヘプタンで充分洗浄して、上澄液
を分離し乾燥して固体生成物を得た。
次いで得られた固体性生物に、ケイ素化合物
としてC6H5Si（OC6H5）Cl2を11.8ｇ、安息香酸
エチル1.3ｇ、TiCl483ｇを添加し、130℃にお
いて１時間処理した。その後ｎ−ヘプタンで充
分に洗浄し、上澄液を分離乾燥し、固体触媒を
得た。担持Ti量は2.7重量％であつた。
(B) プロピレンの重合
上記(A)で得られた固体触媒25.0mgを用いて、
実施例１(C)と同様にしてプロピレンの重合を行
つた。その結果、触媒効率EC＝580Kg−PP／
ｇ−Ti、重合活性Ｋ＝19300、ρB＝0.43ｇ／c.c.、
＝95.8％、MFI＝9.5であつた。
比較例 ５
実施例のＡにおいて、ケイ素化合物として
C6H5SiCOC6H5）Cl211.8ｇを用いて、安息香酸
エチルを添加しなかつた以外は、実施例１(A)と同
様にして、固体触媒を得た。担持Ti量は6.9重量
％であつた。実施例１の(B)と同様にしてプロピレ
ンの重合を行つたところ、触媒効率CE＝150Kg−
PP／ｇ−Ti、重合活性Ｋ＝5000であつた。は
67.1％、MFIは50であり、ρBは測定不能であつ
た。
上記の値を安息香酸エチルを添加した実施例２
の値と比較する。[Table] Example 9 (A) Production of catalyst N2 was added to a 300 ml flask equipped with a stirrer and a thermometer.
Under a seal, 5 g of Mg (OC 2 H 5 ) was collected, and 9.2 g of phenyltrichlorosilane and ethyl benzoate were collected.
1.3 g and 83 g of TiCl 4 were added. While stirring, the temperature was gradually raised to 130°C, and then maintained at the same temperature for 1 hour.
Thereafter, the mixture was thoroughly washed with purified heptane, and the supernatant liquid was separated and dried to obtain a solid product. Next, 11.8 g of C 6 H 5 Si (OC 6 H 5 ) Cl 2 as silicon compounds, 1.3 g of ethyl benzoate, and 83 g of TiCl 4 were added to the obtained solid organism, and the mixture was treated at 130° C. for 1 hour. Thereafter, it was thoroughly washed with n-heptane, and the supernatant liquid was separated and dried to obtain a solid catalyst. The amount of Ti supported was 2.7% by weight. (B) Polymerization of propylene Using 25.0 mg of the solid catalyst obtained in (A) above,
Polymerization of propylene was carried out in the same manner as in Example 1(C). As a result, catalyst efficiency EC=580Kg−PP/
g-Ti, polymerization activity K=19300, ρ B =0.43g/cc,
= 95.8%, MFI = 9.5. Comparative Example 5 In Example A, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 11.8 g of C 6 H 5 SiCOC 6 H 5 )Cl 2 was used and ethyl benzoate was not added. The amount of Ti supported was 6.9% by weight. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency CE = 150Kg-
PP/g-Ti, polymerization activity K=5000. teeth
67.1%, MFI was 50, and ρ B was not measurable. Example 2 in which ethyl benzoate was added to the above values
Compare with the value of
【表】
以上のように、電子供与性化合物の添加によつ
て、重合活性および立体規則性が飛躍的に向上し
ており、電子供与性化合物の添加効果は明白であ
る。[Table] As shown above, the polymerization activity and stereoregularity were dramatically improved by the addition of the electron donating compound, and the effect of the addition of the electron donating compound is obvious.
第１図は本発明の一態様を示すフローチヤート
図である。
FIG. 1 is a flowchart showing one embodiment of the present invention.
Claims (1)
はアラルキル基を示し、R1とR2は同一でも異な
つても良い。ｎは２≧ｎ≧０を示す。）で表わさ
れるマグネシウム化合物を、カルボン酸エステ
ル、ハロゲンとアリールオキシ基を含有するケイ
素化合物および塩素含有４価チタン化合物より成
る３種の化合物で処理することによつて得られる
チタン含有固体触媒成分(a)と、有機アルミニウム
化合物(b)より成る触媒の存在下にオレフインを重
合または共重合させることを特徴とするオレフイ
ン重合体の製造方法。 ２ カルボン酸エステル(c)の共存下にオレフイン
を重合または共重合させることを特徴とする特許
請求の範囲第１項記載の方法。[Claims] 1 General formula Mg (OR 1 ) o (OR 2 ) 2-o (wherein R 1 and R 2 represent an alkyl group, an aryl group, or an aralkyl group, and R 1 and R 2 are the same (n indicates 2≧n≧0.) Magnesium compounds represented by Production of an olefin polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst consisting of a titanium-containing solid catalyst component (a) obtained by treatment with a compound and an organoaluminum compound (b) Method. 2. The method according to claim 1, wherein the olefin is polymerized or copolymerized in the coexistence of the carboxylic acid ester (c).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5705883A JPS59182806A (en) | 1983-04-01 | 1983-04-01 | Production of olefinic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5705883A JPS59182806A (en) | 1983-04-01 | 1983-04-01 | Production of olefinic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59182806A JPS59182806A (en) | 1984-10-17 |
| JPH0552323B2 true JPH0552323B2 (en) | 1993-08-05 |
Family
ID=13044838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5705883A Granted JPS59182806A (en) | 1983-04-01 | 1983-04-01 | Production of olefinic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59182806A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06815B2 (en) * | 1985-02-07 | 1994-01-05 | 三菱化成株式会社 | Method for producing propylene polymer |
| DE3767762D1 (en) * | 1986-05-21 | 1991-03-07 | Mitsubishi Chem Ind | METHOD FOR PRODUCING AN OLEFIN POLYMER. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624408A (en) * | 1979-08-08 | 1981-03-09 | Idemitsu Kosan Co Ltd | Polymerization of olefin |
-
1983
- 1983-04-01 JP JP5705883A patent/JPS59182806A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624408A (en) * | 1979-08-08 | 1981-03-09 | Idemitsu Kosan Co Ltd | Polymerization of olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59182806A (en) | 1984-10-17 |
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