JPS6411649B2 - - Google Patents
Info
- Publication number
- JPS6411649B2 JPS6411649B2 JP3724081A JP3724081A JPS6411649B2 JP S6411649 B2 JPS6411649 B2 JP S6411649B2 JP 3724081 A JP3724081 A JP 3724081A JP 3724081 A JP3724081 A JP 3724081A JP S6411649 B2 JPS6411649 B2 JP S6411649B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- titanium trichloride
- weight
- polymerization
- trichloride composition
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 37
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 alkyl aluminum compound Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011949 solid catalyst Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 6
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 6
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- ICEQTWAHBIDMIH-UHFFFAOYSA-N bis(2-methylpropyl)alumanylium;2-methylpropan-1-olate Chemical compound CC(C)C[O-].CC(C)C[Al+]CC(C)C ICEQTWAHBIDMIH-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- PPQUYYAZSOKTQD-UHFFFAOYSA-M diethylalumanylium;iodide Chemical compound CC[Al](I)CC PPQUYYAZSOKTQD-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- 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、嵩密度及び粒度分布の良好なポリオ
レフインを連続して製造する方法に関する。
更に詳しくは、これらの品質優秀なポリオレフ
インを固体触媒成分を含む触媒系含有物をポンプ
循環する操作を伴う方法によりながら連続且つ安
定して製造する方法に関する。
三塩化チタンもしくは三塩化チタン組成物と有
機アルミニウム化合物とからなる触媒、あるいは
チタン化合物を但持もしくは、化学結合させた担
体触媒成分と有機アルミニウム化合物とからなる
触媒系を用いて、一種または二種以上のオレフイ
ンを重合することは公知である。
一方、四塩化チタンを有機アルミニウム化合物
により環元して得られる三塩化チタン組成物、ま
たはこの三塩化チタン組成物を錯化剤で処理した
後、更に四塩化チタンで処理した三塩化組成物を
用いると粒度分布のそろつたポリオレフインが得
られることも公知である。
ところでポリオレフインの製造工程では触媒成
分含有スラリーをポンプで循環して連続的に重合
槽に供給したり、また重合槽での除熱を強化する
ためポンプを使用して重合体スラリーの一部を外
部循環する方法を採用する場合がある。
しかし、これらに於いてポンプを使用すること
により、前述した粒度分布のそろつたポリオレフ
インが得られる触媒を用いても固体粒子がくずれ
て重合物の粒度分布が広くなり、微粉が増加す
る。またその他の触媒系の場合でも得られるポリ
マーの微粉が増大し、粒度分布が微粒を多く含む
ようになる。そして、これらの現象に伴い嵩密度
も小さくなる傾向にある。
以上の現象は乾燥工程で微粒がロスとなる等の
問題を生ずる外、特に粒度分布のそろつた触媒を
使用する場合のメリツトがなくなるなどの理由か
ら製造上好ましくない。
そこで本発明者らは鋭意検討した結果、予め固
体触媒成分当り0.01〜１ｇ予備重合を行なつた
後、一種または二種以上のオレフインの重合を行
なうことにより、これらの現象が防止できること
を見出し、本発明に到達した。
即ち、本発明は、(A)三塩化チタンもしくは、三
塩化チタン組成物または(B)チタン化合物を担持も
しくは化学結合させた担体触媒成分のいずれか一
種の固体触媒成分と(C)有機アルミニウム化合物と
からなる触媒系を用いて、ポリオレフインを製造
するに際し、
前記触媒系により一種または二種以上のオレ
フインを(A)または(B)の固体触媒成分１ｇ当り0.01
〜１ｇになるように予備重合し、次いで該予備
重合物を含む触媒系１重量部に、一種または二種
以上のオレフインを100重量部以上使用し、これ
らに溶剤及び必要に応じて(C)有機アルミニウム化
合物を追加して連続重合する際に、重合反応器の
内容物100重量部に対し、１分間に１重量部以上
90重量部未満をポンプ循環させ連続重合すること
を特徴とするポリオレフインの連続製造方法であ
る。
本発明に係る触媒系に使用される三塩化チタン
もしくは三塩化チタン組成物とはオレフインの重
合に使用される公知のものであれば特に制限はな
い。例えば、四塩化チタンを水素で環元して得ら
れる三塩化チタン、四塩化チタンを金属で還元し
て得られる三塩化チタンと金属ハライドとの共晶
体、および四塩化チタンを有機アルミニウム化合
物で還元して得られる三塩化チタン組成物または
三塩化チタンを錯化剤で処理した後、更に四塩化
チタンで接触処理した三塩化チタン組成物、ある
いは更にこれらに粉砕、洗浄、その他種々の前処
理を施したもの等があげられる。
本発明におけるチタン化合物を但持または化学
結合させた担体触媒成分とはオレフインの重合に
使用されるものであれば、特に制限はない。例え
ば、シリカ、アルミナ、酸化硼素、マグネシウム
化合物（マグネシウムハライド、マグネシウムヒ
ドロキシハライド、水酸化マグネシウム、炭酸マ
グネシウム、酸化マグネシウムなど）等をそのま
ま、あるいは必要により前処理した物に、四塩化
チタン、三塩化チタンあるいは、三塩化チタン組
成物を但持または化学結合させたもの等があげら
れる。また担体として使用するマグネシウムハラ
イドは、例えば、有機マグネシウム化合物とハロ
ゲン化シランとの反応により合成したもの、ある
いはマグネシウムハライドを一旦アルコールなど
に溶解させたのち、析出させたものでもかまわな
い。
これらの固体触媒成分については、四塩化チタ
ンを有機アルミニウム化合物で還元して得られる
三塩化チタン組成物、またはこの三塩化チタン組
成物を錯化剤で処理した後、更に四塩化チタンで
処理した三塩化チタン組成物、あるいは有機マグ
ネシウム化合物とハロゲン化シランとの反応によ
り合成したマグネシウムハライドまたは、マグネ
シウムハライドを一旦アルコールなどに溶解させ
た後、析出させたマグネシウムハライドに四塩化
チタンを但持したものなど、一般にオレフインを
重合した際、生成したポリオレフインの粒度分布
が狭く、また球状あるいはそれに近いポリオレフ
インを製造しうる固体触媒成分を使用する際、本
発明の方法で重合すれば生成するポリオレフイン
の形状が製造工程の間にくずれることなく製造で
きる点で特に顕著な効果がある。
とりわけ、四塩化チタンを有機アルミニウム化
合物で還元して得られる三塩化チタン組成物、ま
たはこの三塩化チタンを錯化剤で処理した後、更
に四塩化チタンで処理した三塩化チタン組成物を
触媒として使用した場合、本発明の方法で重合す
れば、得られるポリオレフインの粒度分布は10メ
ツシユ〜100メツシユが95％以上である。
本発明における有機アルミニウム化合物として
は、例えば、トリエチルアルミニウム、トリイソ
ブチルアルミニウム、トリ−ｎ−プロピルアルミ
ニウム、ジエチルアルミニウムモノクロライド、
ジエチルアルミニウムモノブロマイド、ジエチル
アルミニウムモノアイオダイド、ジエチルアルミ
ニウムモノエトキサイド、ジイソブチルアルミニ
ウムモノイソブトキサイド、ジエチルアルミニウ
ムモノハイドライド、ジイソブチルアルミニウム
モノハイドライド、エチルアルミニウムセスキク
ロライドなどがあげられ、これらの一種または二
種以上を用いることができる。
本発明に係る触媒系は、前記(A)三塩化チタンも
しくは三塩化チタン組成物、または(B)チタン化合
物を担持もしくは化学結合させた担体触媒成分の
いずれか一種の固体触媒成分と(C)有機アルミニウ
ム化合物の２成分を用いることが必須であるが、
これらの成分以外に必要に応じて第３成分を添加
してもかまわない。この第３成分は一般に電子供
与体と称されるエーテル類、アルコール類、エス
テル類、アミン類、有機リン化合物などであり、
これらの一種または二種以上を用いるものであ
る。
触媒系として(A)または(B)成分と(C)成分の重量比
は特に制限はないが、通常１：0.2〜15である。
本発明において四塩化チタンをアルキルアルミ
ニウム化合物で還元して得た三塩化チタン組成物
の処理に使用される錯化剤は、エーテル、チオエ
ーテルチオール、ホスフイン、アミン、アミド、
ケトン、エステルなどを挙げることができる。
本発明の方法によつて重合または共重合しうる
オレフインとはエチレン、プロピレン、ブテン−
１、ヘキセン−１、４−メチルペンテン−１、ス
チレンなどおよびこれらの混合物が挙げられる。
本発明においては一種または二種以上のオレフ
インを固体触媒成分１ｇ当り0.01〜１ｇになるよ
うに予備重合する。予備重合量が上記範囲より少
ない場合には前記目的を十分に達成することが困
難であり、また予備重合量が上記範囲より多くな
ると、固体触媒の粒度が大きくなり、そのため予
備重合槽底部に沈降付着、配管曲管部付着が生じ
やすく、また触媒供給のダイヤフラムポンプのチ
エツク弁閉塞を生じやすく好ましくない。また上
記範囲中で得られるポリオレフインの性状は良好
であるため、それ以上の効果は無く、無意味であ
る。また予備重合は以下の条件で行なうと良い。
重合温度は90℃以下であれば特に制限はないが、
通常、常温〜50℃の範囲である。重合圧力も特に
制限はないが、通常１〜６Kg／cm2−absである。
本発明は(A)三塩化チタンもしくは、三塩化チタ
ン組成物または(B)チタン化合物を担持もしくは化
学結合させた担体触媒成分のいずれかの固体触媒
成分１ｇ当り、一種または二種以上のオレフイン
を0.1〜１ｇ予備重合を行い、次いでこの予備重
合を含む触媒系１重量部あたり一種または二種以
上のオレフイン100重量部以上を使用し、これ等
に溶剤及び必要に応じて(C)有機アルミニウム化合
物を追加しながら、ポンプ循環する連続重合装置
により主重合させる。一種または二種以上のオレ
フインが100重量部以下だと生産性が低下し、実
用的ではない。また上限は触媒の活性により決ま
るが、通常100000重量部程度まで使用できる。ポ
ンプ循環による循環量は、重合反応器の大きさ又
は様式等により決まり、特定できないが重合槽で
の除熱を効果的にする為には、通常、重合反応器
の内容物100重量部に対し、１分間に１重量部以
上を循環させて重合するのが一般的である。１分
間に１重量部以下では重合槽での除熱を効果的に
することは困難である。１分間に１重量部以上で
あれば重合反応を実施するに支障のない限り、い
くらでもよいが通常90重量部以下である。主重合
においては溶剤及び必要に応じて(C)有機アルミニ
ウム化合物を追加してもよい。連続重合装置とし
ては、重合槽が２槽以上直列に連結し、各槽間は
ポンプ循環により重合物を移液する機構を有する
通常公知のものが使用できる。
主重合の重合反応はこの分野において一般的に
行われている条件で行なうことができる。その際
の重合温度は20〜100℃、好ましくは、40〜90℃
の範囲であり、重合圧力は通常１〜60Kg／cm2−
abs好ましくは１〜50Kg／cm2−absの範囲である。
重合反応は一般に脂肪族、脂環族または芳香族
の炭化水素類またはそれらの混合物を溶媒として
使用することができ、例えばプロパン、ブタン、
ペンタン、ヘキサン、ヘプタン、シクロヘキサ
ン、ベンゼンなどおよびこれらの混合物が用いら
れる。
また予備重合を行なつた後の主重合において
は、液化したα−オレフインモノマーを媒体とし
た塊状重合、あるいは実質的に媒体が存在しない
条件下でα−オレフインを気相中で重合する気相
重合においても実施することができる。
本発明の方法によつて得られるポリマーの分子
量は、反応様式、触媒、重合条件などによつて変
化するが必要に応じて水素などの添加により制御
することができる。
以下に本発明の実施例を比較例と共に示すが本
発明の技術的範囲は、それらによつて制限される
ものではない。
実施例１〜３，比較例１
(a) 予備重合
10m3の重合反応器に溶剤として脱水精製したヘ
プタン2500、三塩化チタン組成物触媒（四塩化
チタンをジエチルアルミニウムクロライドで還元
した後、ジイソアミルエーテル処理し、更に四塩
化チタンで処理したもの）2.5Kg、ジエチルアル
ミニウムクロライド0.18を装入し、撹拌下、プ
ロピレンを３段階に調節しながら装入して常温で
１時間重合した。これらが実施例１〜３であり、
このサンプルから三塩化チタン組成物触媒１ｇ当
りの予備重合量を確認した。（表記載）また比較
例１として予備重合を全く行わない例を、さらに
予備重合を三塩化チタン組成物触媒１ｇ当り２ｇ
とした場合を比較例２とした。比較例２では予備
重合槽底部への付着、及びダイヤフラムポンプの
チエツク部閉塞トラブルが発生し、そのままでの
重合続行くが不可能となつた為、主重合は中止し
た。
(b) 主重合
20m3の連続重合反応器に溶剤として脱水精製し
たヘプタン2500／hrに上記(a)で得た予備重合物
を含む触媒系0.29Kg〜0.57Kg／hr〔予備重合物を
除いた触媒量は0.29Kg／hrであり、予備重合物は
実施例１では0.0145Kg／hr、実施例２では0.029
Kg／hr、実施例３では0.276Kg／hrであり、比較
例１では０である。予備重合物を含む触媒系は予
備重合物を除いた触媒量と予備重合物との和であ
り、予備重合量（ｇ／ｇ−TiCL3）の値はそれぞ
れ表に示す。〕に、ジエチルアルミニウムクロラ
イド0.7l／hrをそれぞれ連続して装入した。また
同時にプロピレンを1693Kg／hr、水素を気相濃度
1.09％となるように連続して装入し、重合温度70
℃、全圧8.5Kg／cm2−Ｇ、平均滞留時間約４時間
で連続重合を行なつた。冷却はジヤケツトおよび
ポンプを循環した外部循環方式の両方で行い、重
合反応内容物の循環は３m3／分の速度で行つた。
これは重合反応内容物100重量部に対し、１分間
に30重量部に相当する。得られたポリプロピレン
の取得量、嵩比重、粒度分布を表に示す。
実施例 ４
(c) 予備重合
10m3の重合反応器に溶剤として脱水精製したヘ
プタン2500、チタン化合物を担持させた担体触
媒成分2.5Kg、ジエチルアルミニウムクロライド
0.18、安息香酸エチル0.06を装入し、撹拌下
プロピレンを所定量装入し、常温で１時間重合し
た。
チタン化合物を担持させた担体触媒成分１ｇ当
りのプロピレン予備重合量は0.8ｇであつた。
(d) 主重合
20m3の連続重合反応器に溶剤として脱水精製し
たヘプタン2500l／hrに(C)で得た予備重合物を含
む触媒系0.522Kg／hr（予備重合物を除いた触媒量
は0.29Kg／hrであり、予備重合物は0.232Kg／hr
である）にジエチルアルミニウムクロライド1.65
／hr、トリエチルアルミニウム0.78／hr、安
息香酸エチル0.58／hrをそれぞれ連続して装入
した。また同時にプロピレンを1700Kg／hr、水素
を気相濃度1.5％となるように連続して装入し、
重合温度70℃、全圧8.5Kg／cm2−Ｇ、平均滞留時
間約４時間で連続重合を行なつた。冷却はジヤケ
ツトおよびポンプを循環した外部循環方式の両方
で行い、重合反応内容物の循環は３m3／分の速度
で行つた。これは重合反応内容物100重量部に対
し、１分間に30重量部に相当する。
The present invention relates to a method for continuously producing polyolefin with good bulk density and particle size distribution. More specifically, the present invention relates to a method for continuously and stably producing these polyolefins of excellent quality by a method that involves pumping and circulating a catalyst system containing a solid catalyst component. Using a catalyst consisting of titanium trichloride or a titanium trichloride composition and an organoaluminum compound, or a catalyst system consisting of an organoaluminum compound and a carrier catalyst component in which a titanium compound is supported or chemically bonded, one or two types can be used. It is known to polymerize the above olefins. On the other hand, a titanium trichloride composition obtained by cyclizing titanium tetrachloride with an organoaluminum compound, or a trichloride composition obtained by treating this titanium trichloride composition with a complexing agent and then further treating it with titanium tetrachloride. It is also known that when used, a polyolefin with a uniform particle size distribution can be obtained. By the way, in the polyolefin manufacturing process, a slurry containing a catalyst component is circulated by a pump and continuously supplied to the polymerization tank, and a part of the polymer slurry is pumped outside using a pump to enhance heat removal in the polymerization tank. A circular method may be adopted. However, when a pump is used in these processes, the solid particles are broken down, the particle size distribution of the polymer is widened, and the amount of fine powder increases, even if the above-mentioned catalyst that produces a polyolefin with a uniform particle size distribution is used. In addition, in the case of other catalyst systems, the amount of fine particles of the obtained polymer increases, and the particle size distribution comes to include many fine particles. Along with these phenomena, the bulk density also tends to decrease. The above-mentioned phenomenon is unfavorable in terms of production, not only because it causes problems such as the loss of fine particles in the drying process, but also because it eliminates the advantage of using a catalyst with a uniform particle size distribution. As a result of intensive studies, the present inventors have found that these phenomena can be prevented by prepolymerizing 0.01 to 1 g per solid catalyst component and then polymerizing one or more olefins. We have arrived at the present invention. That is, the present invention provides a solid catalyst component of any one of (A) titanium trichloride or a titanium trichloride composition, or (B) a supported catalyst component supported or chemically bonded with a titanium compound, and (C) an organoaluminum compound. When producing a polyolefin using a catalyst system consisting of the above catalyst system, one or more kinds of olefins are produced at a rate of 0.01 per gram of the solid catalyst component (A) or (B).
Prepolymerize to ~1 g, then use 100 parts by weight or more of one or more olefins per 1 part by weight of the catalyst system containing the prepolymerized product, and add a solvent and (C) as necessary. When adding an organoaluminum compound and performing continuous polymerization, 1 part by weight or more per minute per 100 parts by weight of the contents of the polymerization reactor.
This is a method for continuously producing polyolefin, characterized in that less than 90 parts by weight is continuously polymerized by circulating it with a pump. The titanium trichloride or titanium trichloride composition used in the catalyst system according to the present invention is not particularly limited as long as it is a known titanium trichloride used in the polymerization of olefins. For example, titanium trichloride obtained by cyclizing titanium tetrachloride with hydrogen, eutectic of titanium trichloride and metal halide obtained by reducing titanium tetrachloride with a metal, and reduction of titanium tetrachloride with an organoaluminum compound. or a titanium trichloride composition obtained by treating titanium trichloride with a complexing agent and then contacting it with titanium tetrachloride, or further subjecting these to pulverization, washing, and various other pretreatments. Examples include things that have been done. The carrier catalyst component to which a titanium compound is supported or chemically bonded in the present invention is not particularly limited as long as it can be used for the polymerization of olefins. For example, silica, alumina, boron oxide, magnesium compounds (magnesium halide, magnesium hydroxyhalide, magnesium hydroxide, magnesium carbonate, magnesium oxide, etc.), etc. can be used as they are, or if necessary, pretreated, and titanium tetrachloride, titanium trichloride can be used. Alternatively, titanium trichloride compositions may be suspended or chemically bonded. The magnesium halide used as a carrier may be, for example, one synthesized by a reaction between an organomagnesium compound and a halogenated silane, or one prepared by dissolving magnesium halide in alcohol or the like and then precipitating it. For these solid catalyst components, a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound, or a titanium trichloride composition obtained by treating this titanium trichloride composition with a complexing agent and then further treating it with titanium tetrachloride. A titanium trichloride composition, or a magnesium halide synthesized by the reaction of an organomagnesium compound and a halogenated silane, or a magnesium halide prepared by dissolving magnesium halide in alcohol, etc., and then precipitating the magnesium halide with titanium tetrachloride. Generally, when olefins are polymerized, the particle size distribution of the produced polyolefin is narrow, and when using a solid catalyst component that can produce a spherical or nearly spherical polyolefin, the shape of the produced polyolefin is It has a particularly remarkable effect in that it can be manufactured without collapsing during the manufacturing process. In particular, a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound, or a titanium trichloride composition obtained by treating this titanium trichloride with a complexing agent and then further treating it with titanium tetrachloride can be used as a catalyst. When used and polymerized by the method of the present invention, the particle size distribution of the resulting polyolefin is 95% or more in the range of 10 meshes to 100 meshes. Examples of the organoaluminum compound in the present invention include triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, diethylaluminum monochloride,
Examples include diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminium monoethoxide, diisobutylaluminum monoisobutoxide, diethylaluminum monohydride, diisobutylaluminum monohydride, ethylaluminum sesquichloride, and one or two of these. The above can be used. The catalyst system according to the present invention comprises a solid catalyst component of any one of the above-mentioned (A) titanium trichloride or a titanium trichloride composition, or (B) a carrier catalyst component supported or chemically bonded with a titanium compound; Although it is essential to use two components of organoaluminum compounds,
In addition to these components, a third component may be added as necessary. This third component is generally called an electron donor, such as ethers, alcohols, esters, amines, and organic phosphorus compounds.
One or more of these may be used. The weight ratio of component (A) or (B) to component (C) in the catalyst system is not particularly limited, but is usually 1:0.2 to 15. In the present invention, the complexing agents used in the treatment of the titanium trichloride composition obtained by reducing titanium tetrachloride with an alkyl aluminum compound include ether, thioether thiol, phosphine, amine, amide,
Examples include ketones and esters. Olefins that can be polymerized or copolymerized by the method of the present invention include ethylene, propylene, butene-
1, hexene-1, 4-methylpentene-1, styrene, and mixtures thereof. In the present invention, one or more olefins are prepolymerized in an amount of 0.01 to 1 g per 1 g of solid catalyst component. If the amount of prepolymerization is less than the above range, it will be difficult to fully achieve the above objective, and if the amount of prepolymerization is greater than the above range, the particle size of the solid catalyst will become large, and as a result, it will settle at the bottom of the prepolymerization tank. This is undesirable because it tends to cause adhesion and adhesion to piping bends, and it also tends to cause blockage of the check valve of the diaphragm pump for supplying the catalyst. Furthermore, since the polyolefin obtained within the above range has good properties, it has no further effect and is meaningless. Prepolymerization is preferably carried out under the following conditions.
There is no particular restriction on the polymerization temperature as long as it is below 90℃, but
Usually, the temperature ranges from room temperature to 50°C. The polymerization pressure is also not particularly limited, but is usually 1 to 6 kg/cm 2 -abs. The present invention provides one or more olefins per gram of a solid catalyst component, either (A) titanium trichloride or a titanium trichloride composition, or (B) a carrier catalyst component supported or chemically bonded with a titanium compound. Prepolymerize 0.1 to 1 g, then use 100 parts by weight or more of one or more olefins per 1 part by weight of the catalyst system containing this prepolymerization, and add a solvent and, if necessary, (C) an organoaluminum compound. Main polymerization is carried out using a continuous polymerization device that circulates with a pump while adding . If the amount of one or more olefins is less than 100 parts by weight, productivity decreases and is not practical. The upper limit is determined by the activity of the catalyst, but usually up to about 100,000 parts by weight can be used. The amount of circulation by pump circulation is determined by the size and style of the polymerization reactor, and cannot be specified, but in order to effectively remove heat in the polymerization tank, it is usually necessary to Generally, polymerization is carried out by circulating 1 part by weight or more per minute. If the amount is less than 1 part by weight per minute, it is difficult to effectively remove heat in the polymerization tank. The amount may be any amount as long as it is 1 part by weight or more per minute and does not hinder the polymerization reaction, but it is usually 90 parts by weight or less. In the main polymerization, a solvent and (C) an organoaluminum compound may be added as necessary. As the continuous polymerization apparatus, a conventionally known apparatus having two or more polymerization tanks connected in series and having a mechanism for transferring the polymer by pump circulation between each tank can be used. The main polymerization reaction can be carried out under conditions commonly used in this field. The polymerization temperature at that time is 20 to 100℃, preferably 40 to 90℃
The polymerization pressure is usually in the range of 1 to 60 kg/cm 2 -
abs is preferably in the range of 1 to 50 kg/cm 2 -abs. Polymerization reactions can generally use aliphatic, cycloaliphatic or aromatic hydrocarbons or mixtures thereof as solvents, such as propane, butane,
Pentane, hexane, heptane, cyclohexane, benzene, etc. and mixtures thereof are used. In addition, in the main polymerization after prepolymerization, bulk polymerization using liquefied α-olefin monomer as a medium, or gas phase polymerization in which α-olefin is polymerized in the gas phase under conditions where substantially no medium is present, is possible. It can also be carried out in polymerization. The molecular weight of the polymer obtained by the method of the present invention varies depending on the reaction mode, catalyst, polymerization conditions, etc., but can be controlled by adding hydrogen or the like as necessary. Examples of the present invention are shown below together with comparative examples, but the technical scope of the present invention is not limited thereto. Examples 1 to 3, Comparative Example 1 (a) Prepolymerization In a 10 m 3 polymerization reactor, dehydrated and purified heptane 2500 was used as a solvent, and a titanium trichloride composition catalyst (titanium tetrachloride was reduced with diethylaluminum chloride, then diisoamyl 2.5 kg of ether-treated and further treated with titanium tetrachloride) and 0.18 kg of diethylaluminum chloride were charged, and while stirring, propylene was charged in three stages and polymerized for 1 hour at room temperature. These are Examples 1 to 3,
From this sample, the amount of prepolymerization per 1 g of the titanium trichloride composition catalyst was confirmed. (Described in the table) Comparative Example 1 is an example in which no prepolymerization is carried out, and further prepolymerization is carried out at 2 g per 1 g of titanium trichloride composition catalyst.
The case was designated as Comparative Example 2. In Comparative Example 2, troubles such as adhesion to the bottom of the prepolymerization tank and clogging of the check part of the diaphragm pump occurred, making it impossible to continue the polymerization as it was, so the main polymerization was stopped. (b) Main polymerization Catalyst system containing the prepolymerized product obtained in (a) above in 2500/hr of dehydrated heptane as a solvent in a 20m3 continuous polymerization reactor [excluding the prepolymerized product] The amount of catalyst used was 0.29Kg/hr, and the amount of prepolymerized product was 0.0145Kg/hr in Example 1 and 0.029Kg/hr in Example 2.
Kg/hr, in Example 3 it is 0.276 Kg/hr, and in Comparative Example 1 it is 0. The catalyst system containing a prepolymerized product is the sum of the catalyst amount excluding the prepolymerized product and the prepolymerized product, and the values of the prepolymerized amount (g/g-TiCL 3 ) are shown in the table. ], 0.7 l/hr of diethylaluminium chloride was continuously charged to each of them. At the same time, propylene was supplied at 1693Kg/hr and hydrogen at a gas phase concentration.
Continuously charge the polymer at a polymerization temperature of 1.09% at a polymerization temperature of 70%.
Continuous polymerization was carried out at a temperature of 8.5 Kg/cm 2 -G and an average residence time of about 4 hours. Cooling was carried out by both a jacket and an external circulation system using a pump, and the polymerization reaction contents were circulated at a rate of 3 m 3 /min.
This corresponds to 30 parts by weight per minute per 100 parts by weight of the polymerization reaction contents. The obtained amount, bulk specific gravity, and particle size distribution of the obtained polypropylene are shown in the table. Example 4 (c) Prepolymerization In a 10 m 3 polymerization reactor, dehydrated and purified heptane 2500 was used as a solvent, 2.5 kg of a carrier catalyst component supporting a titanium compound, and diethylaluminium chloride.
0.18 and 0.06 of ethyl benzoate were charged, and a predetermined amount of propylene was charged while stirring, and polymerization was carried out at room temperature for 1 hour. The amount of propylene prepolymerized per 1 g of the carrier catalyst component on which the titanium compound was supported was 0.8 g. (d) Main polymerization A catalyst system containing the prepolymerized product obtained in (C) in 2500l/hr of dehydrated heptane as a solvent in a 20m3 continuous polymerization reactor (the amount of catalyst excluding the prepolymerized material is 0.29Kg/hr, prepolymerized product 0.232Kg/hr
) to diethylaluminum chloride 1.65
/hr, triethylaluminum 0.78/hr, and ethyl benzoate 0.58/hr were each continuously charged. At the same time, propylene was continuously charged at 1700 kg/hr and hydrogen at a gas phase concentration of 1.5%.
Continuous polymerization was carried out at a polymerization temperature of 70° C., a total pressure of 8.5 Kg/cm 2 -G, and an average residence time of about 4 hours. Cooling was carried out by both a jacket and an external circulation system using a pump, and the polymerization reaction contents were circulated at a rate of 3 m 3 /min. This corresponds to 30 parts by weight per minute per 100 parts by weight of the polymerization reaction contents.
【表】
得られたポリプロピレンの取得量、炭比重粒度
分布を表に示す。
比較例 ３
実施例４で(C)の予備重合をしない以外は実施例
４と同様にした。結果を表に示す。
表より本発明に従つて予備重合を行なうことに
より、嵩比重、および粒度分布の良好なポリマー
が得られることがわかる。[Table] The obtained amount of polypropylene and charcoal specific gravity particle size distribution are shown in the table. Comparative Example 3 The same procedure as Example 4 was carried out except that (C) was not prepolymerized. The results are shown in the table. It can be seen from the table that by carrying out the prepolymerization according to the present invention, polymers with good bulk specific gravity and particle size distribution can be obtained.
Claims (1)
物または(B)チタン化合物を担持もしくは化学結合
させた担体触媒成分のいずれか一種の固体触媒成
分と(C)有機アルミニウム化合物とからなる触媒系
を用いて、ポリオレフインを製造するに際し、 前記触媒系により一種または二種以上のオレ
フインを(A)または(B)の固体触媒成分１ｇ当り0.01
〜１ｇになるように予備重合し、次いで該予備
重合物を含む触媒系１重量部に、一種または二種
以上のオレフインを100重量部以上使用し、これ
らに溶剤及び必要に応じて(C)有機アルミニウム化
合物を追加して連続重合する際に、重合反応器の
内容物100重量部に対し、１分間に１重量部以上
90重量部未満をポンプ循環させ連続重合すること
を特徴とするポリオレフインの連続製造方法。 ２ (A)の三塩化チタン組成物が、四塩化チタンを
アルキルアルミニウム化合物で還元して得た三塩
化チタン組成物、またはこの三塩化チタン組成物
を錯化剤で処理した後、更に四塩化チタンと接触
処理した三塩化チタン組成物であることを特徴と
する特許請求の範囲第１項記載のポリオレフイン
の連続製造方法。[Scope of Claims] 1. A solid catalyst component of any one of (A) titanium trichloride or a titanium trichloride composition, or (B) a supported catalyst component supported or chemically bonded with a titanium compound, and (C) an organoaluminum. When producing a polyolefin using a catalyst system consisting of a compound, one or more olefins are produced by the catalyst system at a rate of 0.01 per 1 g of the solid catalyst component (A) or (B).
Prepolymerize to ~1 g, then use 100 parts by weight or more of one or more olefins per 1 part by weight of the catalyst system containing the prepolymerized product, and add a solvent and (C) as necessary. When adding an organoaluminum compound and performing continuous polymerization, 1 part by weight or more per minute per 100 parts by weight of the contents of the polymerization reactor.
A method for continuously producing polyolefin, characterized in that less than 90 parts by weight is continuously polymerized by circulating it with a pump. 2. The titanium trichloride composition of (A) is a titanium trichloride composition obtained by reducing titanium tetrachloride with an alkyl aluminum compound, or after treating this titanium trichloride composition with a complexing agent, it is further treated with tetrachloride. 2. The method for continuously producing a polyolefin according to claim 1, which is a titanium trichloride composition that has been subjected to a contact treatment with titanium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3724081A JPS57151602A (en) | 1981-03-17 | 1981-03-17 | Continuous preparation of polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3724081A JPS57151602A (en) | 1981-03-17 | 1981-03-17 | Continuous preparation of polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57151602A JPS57151602A (en) | 1982-09-18 |
| JPS6411649B2 true JPS6411649B2 (en) | 1989-02-27 |
Family
ID=12492083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3724081A Granted JPS57151602A (en) | 1981-03-17 | 1981-03-17 | Continuous preparation of polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57151602A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826093B2 (en) * | 1986-08-18 | 1996-03-13 | 三菱化学株式会社 | Polymerization method of α-olefin |
| JPH0798842B2 (en) | 1990-03-14 | 1995-10-25 | 住友化学工業株式会社 | Method for producing solid catalyst component for α-olefin polymerization |
| DE69623308T2 (en) | 1995-10-18 | 2002-12-19 | Chisso Corp | OLEFIN (CO) POLYMER COMPOSITION, METHOD FOR THE PRODUCTION THEREOF, CATALYST FOR OLEFIN (CO) POLYMERIZATION AND METHOD FOR THE PRODUCTION THEREOF |
| US6231804B1 (en) | 1997-04-02 | 2001-05-15 | Chisso Corporation | Modified olefin (co)polymer composition, process for preparing the same, and modified olefin (co)polymer composition molding |
| US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
| TW504515B (en) | 1997-08-07 | 2002-10-01 | Chisso Corp | Olefin (co)polymer composition |
-
1981
- 1981-03-17 JP JP3724081A patent/JPS57151602A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57151602A (en) | 1982-09-18 |
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