JPH0757771B2 - Method for storing transition metal catalyst component for olefin polymerization - Google Patents
Method for storing transition metal catalyst component for olefin polymerizationInfo
- Publication number
- JPH0757771B2 JPH0757771B2 JP62288302A JP28830287A JPH0757771B2 JP H0757771 B2 JPH0757771 B2 JP H0757771B2 JP 62288302 A JP62288302 A JP 62288302A JP 28830287 A JP28830287 A JP 28830287A JP H0757771 B2 JPH0757771 B2 JP H0757771B2
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- metal catalyst
- catalyst component
- diffraction spectrum
- olefin polymerization
- 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 title claims description 28
- 229910052723 transition metal Inorganic materials 0.000 title claims description 21
- 150000003624 transition metals Chemical class 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 17
- 238000006116 polymerization reaction Methods 0.000 title claims description 11
- 150000001336 alkenes Chemical class 0.000 title claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 8
- 238000001228 spectrum Methods 0.000 claims description 24
- -1 titanium halide Chemical class 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KLWZLMKMCYTORE-UHFFFAOYSA-N cyclohexane;hydrobromide Chemical compound Br.C1CCCCC1 KLWZLMKMCYTORE-UHFFFAOYSA-N 0.000 description 1
- BXQJYIXHTMSDRB-UHFFFAOYSA-N cyclohexane;hydrochloride Chemical compound Cl.C1CCCCC1 BXQJYIXHTMSDRB-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はオレフィン重合用遷移金属触媒成分の保存方法
に関する。詳しくは、特定の処理を施し精製した炭化水
素溶剤中、スラリー状態で保存する方法に関する。TECHNICAL FIELD The present invention relates to a method for storing a transition metal catalyst component for olefin polymerization. Specifically, it relates to a method of storing a slurry in a hydrocarbon solvent that has been subjected to a specific treatment and purified.
オレフィン重合用の触媒として、近来極めて高活性の遷
移金属触媒が開発され利用されている。なかでもマグネ
シウム化合物にチタン化合物を担持したものは高活性で
あり既に多くの種類のものが知られている（例えば、ダ
イヤモンド経営開発情報 公開情報レポート'87/2月版1
4〜17）。As a catalyst for olefin polymerization, a transition metal catalyst having extremely high activity has been recently developed and used. Among them, magnesium compounds supporting titanium compounds are highly active and many kinds are already known (for example, Diamond Management Development Information Public Information Report '87 / February Edition 1
4 to 17).
触媒の活性が向上すると、触媒そのものが重合阻害成分
に対して相対的に弱くなるうえに、触媒の使用量が減少
するため比較的低濃度で保存する必要が生じてくる。そ
のため従来より使用する分散媒体の精製は注意深く行わ
れ、水、アルコール等の含OH基化合物等は厳密に管理さ
れている。When the activity of the catalyst is improved, the catalyst itself becomes relatively weak against the polymerization inhibiting component, and the amount of the catalyst used is reduced, so that it becomes necessary to store the catalyst at a relatively low concentration. Therefore, the dispersion medium used conventionally is carefully purified, and OH-containing compounds such as water and alcohol are strictly controlled.
然しながら、実際に高活性の遷移金属触媒を使用するに
際して、単に上記含OH基化合物を厳密に除去した溶剤を
分散媒体として用いても活性が劣る場合があり、その原
因を除くことが望まれていた。However, when actually using a highly active transition metal catalyst, the activity may be inferior even if a solvent obtained by strictly removing the OH-containing compound is used as a dispersion medium, and it is desired to eliminate the cause. It was
本発明者らは上記問題を解決する方法について鋭意検討
した結果、特定の処理を施すことで、オレフィン重合用
遷移金属触媒成分の保存における活性低下の問題が解決
することを見出し本発明を完成した。As a result of intensive studies on the method for solving the above-mentioned problems, the present inventors have found that, by applying a specific treatment, the problem of activity reduction during storage of the transition metal catalyst component for olefin polymerization can be solved, and the present invention has been completed. .
即ち、本発明はマグネシウム化合物に４価のハロゲン化
チタンを担持して得たオレフィン重合用遷移金属触媒成
分を炭化水素溶剤中、スラリー状態で保存する方法にお
いて、該炭化水素溶剤としてＸ線回折スペクトルにおい
て強い回折スペクトルを有しない無水ハロゲン化マグネ
シウムで処理した炭化水素溶剤を用いることを特徴とす
るオレフィン重合用遷移金属触媒成分の保存方法であ
る。That is, the present invention is a method of storing a transition metal catalyst component for olefin polymerization obtained by supporting a tetravalent titanium halide on a magnesium compound in a hydrocarbon solvent in a slurry state, wherein an X-ray diffraction spectrum is used as the hydrocarbon solvent. In the method of storing a transition metal catalyst component for olefin polymerization, a hydrocarbon solvent treated with anhydrous magnesium halide having no strong diffraction spectrum is used.
本発明において、Ｘ線回折スペクトルにおいて強い回折
スペクトルを有しない無水ハロゲン化マグネシウムの製
造法としては特に制限はなく、種々の方法で製造可能で
あるが、例えば無水塩化マグネシウムであれば、5.75、
及び2.99オングストロールに観測される回折線が該部付
近のハローとして観測される。In the present invention, the method for producing anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum is not particularly limited and can be produced by various methods. For example, if anhydrous magnesium chloride is used, 5.75,
And the diffraction line observed at 2.99 angstroms is observed as a halo near this part.
またＸ線回折スペクトルにおいて強い回折スペクトルを
有しない無水ハロゲン化マグネシウムの簡便な製造法と
しては、通常市場で入手できる無水ハロゲン化マグネシ
ウム（ハロゲン化マグネシウム１モルに対し１モルより
少ない水分を含有していても良い）をボールミル等を用
いて粉砕処理することによってＸ線回折スペクトルにお
いて強い回折スペクトルを有しない無水ハロゲン化マグ
ネシウムとすることができる。またアルコキシマグネシ
ウム等のマグネシウム化合物をハロゲン化硅素等のハロ
ゲン化剤で処理し、Ｘ線回折スペクトルにおいて強い回
折スペクトルを有しない無水ハロゲン化マグネシウムと
する方法、或いは、アルキルマグネシウム等の有機マグ
ネシウムをハロゲン化剤で処理してＸ線回折スペクトル
において強い回折スペクトルを有しない無水ハロゲン化
マグネシウムとする方法等が例示される。Further, as a simple method for producing anhydrous magnesium halide having no strong diffraction spectrum in X-ray diffraction spectrum, anhydrous magnesium halide commercially available on the market (containing less than 1 mol of water per mol of magnesium halide) May be obtained) by pulverization using a ball mill or the like to obtain anhydrous magnesium halide having no strong diffraction spectrum in X-ray diffraction spectrum. Further, a method of treating a magnesium compound such as alkoxymagnesium with a halogenating agent such as silicon halide to obtain anhydrous magnesium halide having no strong diffraction spectrum in X-ray diffraction spectrum, or halogenating an organomagnesium such as alkylmagnesium An example is a method of treating with an agent to obtain anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum.
本発明においてＸ線回折スペクトルにおいて強い回折ス
ペクトルを有しない無水ハロゲン化マグネシウムによる
炭化水素溶剤の処理方法としては特に制限はないが、例
えばＸ線回折スペクトルにおいて強い回折スペクトルを
有しない無水ハロゲン化マグネシウムと炭化水素溶剤を
混合処理し、ついで濾過あるいは静置分離することによ
り得る方法、あるいは適当な円筒状の容器にＸ線回折ス
ペクトルにおいて強い回折スペクトルを有しない無水ハ
ロゲン化マグネシウムを入れ、そこに適当な流速で炭化
水素溶剤を通じることで処理することも可能である。In the present invention, the method of treating the hydrocarbon solvent with anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum is not particularly limited, but for example, anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum A method in which a hydrocarbon solvent is mixed and then filtered or statically separated, or anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum is put into a suitable cylindrical container, and a suitable container is put therein. It is also possible to treat by passing a hydrocarbon solvent at a flow rate.
本発明において、マグネシウム化合物に４価のハロゲン
化チタンを担持して得た遷移金属触媒成分としては特に
制限は無く、ハロゲン化マグネシウム或いはエステル、
エーテル等の電子供与性化合物で処理したハロゲン化マ
グネシウムに４価のハロゲン化チタンを担持したもの、
あるいは担体としてアルコキシマグネシウム、カルボン
酸のマグネシウム塩或いはマグネシウム化合物以外の不
活性な無機あるいは有機の化合物を含有するか、あるい
は更にそれらを電子供与性の化合物で処理したものであ
ってもよい。これらの遷移金属触媒成分の具体例として
は、上述の文献に特許が多数例示されている。In the present invention, the transition metal catalyst component obtained by supporting a tetravalent titanium halide on a magnesium compound is not particularly limited, and magnesium halide or ester,
Magnesium halide treated with an electron-donating compound such as ether and carrying tetravalent titanium halide,
Alternatively, the carrier may contain an inert inorganic or organic compound other than alkoxy magnesium, a magnesium salt of carboxylic acid, or a magnesium compound, or may be one treated with an electron donating compound. As specific examples of these transition metal catalyst components, many patents are illustrated in the above-mentioned documents.
本発明において炭化水素溶剤としては、ペンタン、ヘキ
サン、ヘプタン、ノナン、デカン、ベンゼン、トルエ
ン、キシレン、エチルベンゼン等、あるいはその混合物
が挙げられる。本発明の方法で処理された溶剤を用いる
場合にはスラリーの濃度はかなり薄くても充分に保存可
能であるが、保存に際し、遷移金属触媒成分は通常0.1g
/l以上好ましくは1g/l以上程度の濃度で保存するのがよ
り安全である。In the present invention, examples of the hydrocarbon solvent include pentane, hexane, heptane, nonane, decane, benzene, toluene, xylene, ethylbenzene and the like, or a mixture thereof. When using the solvent treated by the method of the present invention, the concentration of the slurry can be sufficiently preserved even if it is quite thin, but upon preservation, the transition metal catalyst component is usually 0.1 g.
It is safer to store at a concentration of 1 / l or more, preferably 1 g / l or more.
以下に実施例を示し本発明を更に説明する。 The present invention will be further described with reference to the following examples.
実験例１ 市販のｎ−ヘプタン１に対し100gの塩化マグネシウム
（市販の無水塩化マグネシウムをボールミルで40時間粉
砕、Ｘ線回折スペクトルでは強い吸収が観測できずハロ
ーが観測できただけである。）を入れ１時間攪拌処理
し、ついで静置分離して上澄みとして精製ｎ−ヘプタン
を得た。このｎ−ヘプタンを用いて以下の触媒成分を合
成した。Experimental Example 1 100 g of magnesium chloride (commercial anhydrous magnesium chloride was crushed for 40 hours in a ball mill with commercially available n-heptane 1 and strong absorption was not observed in the X-ray diffraction spectrum, and only halo was observed). The mixture was stirred for 1 hour, and then allowed to stand and separate to obtain purified n-heptane as a supernatant. The following catalyst components were synthesized using this n-heptane.
無水塩化マグネシウム20gとテトラエトキシシラン3ml、
２塩化エチレン4mlを40時間粉砕した。得られた共粉砕
物20gを300mlのフラスコに入れ100mlのｎ−ヘプタン、1
00mlの四塩化チタンを加え90℃で１時間加熱処理し、次
いで静置し上澄みを除去し、さらに同様に100mlのｎ−
ヘプタン、100mlの四塩化チタンを加え90℃で１時間加
熱処理した。静置し上澄みを除去したのち、固形分をｎ
−ヘプタンで洗浄して遷移金属触媒成分とした（参考例
１）。一部を取り出し5g/にヘプタンで希釈した（実
施例１）。また一部は市販のｎ−ヘプタンをそのまま
（比較例１）また一部は市販のｎ−ヘプタンをモレキュ
ラーシーブス3Aで処理したもの（比較例２）に5g/と
なるように希釈した。希釈直後と100時間経過後それぞ
れの遷移金属触媒成分について性能を５のオートクレ
ーブを用い、75℃で２時間塊状重合して評価した。この
時遷移金属触媒成分30mg、トリエチルアルミニウム0.08
ml、ジエチルアルミニウムクロリド0.128ml、トルイル
酸メチル0.06ml、プロピレン1.5kg、水素1.38Nl使用し
た。結果は表に示す。20g anhydrous magnesium chloride and 3ml tetraethoxysilane,
4 ml of ethylene dichloride was ground for 40 hours. 20 g of the obtained co-ground product was placed in a 300 ml flask and 100 ml of n-heptane, 1
00 ml of titanium tetrachloride was added, and the mixture was heat treated at 90 ° C. for 1 hour, then allowed to stand and the supernatant was removed, and similarly 100 ml of n-
Heptane and 100 ml of titanium tetrachloride were added, and the mixture was heated at 90 ° C for 1 hour. After leaving still to remove the supernatant, the solid content is n
-Washed with heptane to give a transition metal catalyst component (Reference Example 1). A part was taken out and diluted with heptane to 5 g / (Example 1). A part of the commercially available n-heptane was used as it was (Comparative Example 1) or a part of the commercially available n-heptane was treated with Molecular Sieves 3A (Comparative Example 2), and diluted to 5 g /. Immediately after dilution and after 100 hours, the performance of each transition metal catalyst component was evaluated by bulk polymerization at 75 ° C. for 2 hours using an autoclave of 5. At this time, transition metal catalyst component 30 mg, triethylaluminum 0.08
ml, diethyl aluminum chloride 0.128 ml, methyl toluate 0.06 ml, propylene 1.5 kg, and hydrogen 1.38 Nl were used. The results are shown in the table.
実験例２ 実験例１と同様の操作でハロゲン化マグネシウムで処理
したトルエンを用いて以下の実験を行った。Experimental Example 2 The following experiment was performed by the same operation as in Experimental Example 1 using toluene treated with magnesium halide.
300mlの丸底フラスコにマグネシウム7.4g、ジエチルエ
ーテル20mlを入れ、エーテルの還流下に臭化シクロヘキ
サン25gとジエチルエーテル50mlの混合物を１時間かけ
て滴下した。ついで塩化シクロヘキサン18gを１時間か
けて添加し、さらに２時間還流下攪拌処理し、C6H11MgB
r0.5Cl0.5のエチルエーテル溶液を調製した。Magnesium (7.4 g) and diethyl ether (20 ml) were placed in a 300 ml round bottom flask, and a mixture of cyclohexane bromide (25 g) and diethyl ether (50 ml) was added dropwise under reflux of ether over 1 hour. Then, 18 g of cyclohexane chloride was added over 1 hour, and the mixture was stirred under reflux for 2 hours, and C 6 H 11 MgB
An ethyl ether solution of r 0.5 Cl 0.5 was prepared.
次いで、エチルエーテルの還流下にアリルクロライド24
gを50mlのエチルエーテルに溶解したものを３時間かけ
て滴下し、さらに還流下で４時間攪拌した。Then allyl chloride 24 under reflux of ethyl ether
What melt | dissolved g in 50 ml of ethyl ether was dripped over 3 hours, and also it stirred under reflux for 4 hours.
次いで室温でろ過し、固形分をエチルエーテルで洗浄
し、窒素気流で乾燥して、固形分41gを得た。得られた
固形分はMg:Cl:Brがほぼ1:0.5:1.5であり、MgBr0.5Cl
1.5であった。Then, the mixture was filtered at room temperature, the solid content was washed with ethyl ether, and dried with a nitrogen stream to obtain a solid content of 41 g. The obtained solid content was Mg: Cl: Br was approximately 1: 0.5: 1.5, and MgBr 0.5 Cl
It was 1.5 .
上記固形分10gを200mlの丸底フラスコに入れ、四塩化チ
タン50ml、トルエン50mlを入れ、90℃で１時間攪拌処理
し、次いで静置して上澄を除去した。さらに四塩化チタ
ン50ml、トルエン50mlを入れ、90℃で１時間攪拌処理
し、次いで静置して上澄を除去し、得られた固形分を実
施例１と同様の 操作で市販のトルエンを処理した精製トルエンで７回洗
浄して遷移金属触媒成分とした。分析の結果はチタンを
1.3wt％含有していた。10 g of the solid content was placed in a 200 ml round bottom flask, 50 ml of titanium tetrachloride and 50 ml of toluene were placed therein, and the mixture was stirred at 90 ° C. for 1 hour and then left to stand to remove the supernatant. Further, 50 ml of titanium tetrachloride and 50 ml of toluene were added, and the mixture was stirred at 90 ° C. for 1 hour and then left to stand to remove the supernatant, and the solid content obtained was the same as in Example 1. The transition metal catalyst component was obtained by washing 7 times with purified toluene obtained by treating commercially available toluene by operation. The result of the analysis is titanium
It contained 1.3 wt%.
上記操作で得た遷移金属触媒成分を用い実験例１の参考
例１、実施例１、比較例１、比較例２と同様に保存テス
トを実施した（参考例２、実施例２、比較例３、比較例
４）。但し実施例２では塩化マグネシウムで処理したト
ルエンを用い、比較例３では市販のトルエンをそのま
ま、比較例４ではモレキュラーシーブス3Aで乾燥処理し
たトルエンを用いた。また重合の際遷移金属触媒成分20
mg、トリエチルアルミニウム0.20ml、トリメトキシフェ
ニルシラン0.05mlを用いた。Using the transition metal catalyst component obtained by the above operation, a storage test was carried out in the same manner as in Reference Example 1, Example 1, Comparative Example 1 and Comparative Example 2 of Experimental Example 1 (Reference Example 2, Example 2, Comparative Example 3). , Comparative Example 4). However, in Example 2, toluene treated with magnesium chloride was used, in Comparative Example 3 commercially available toluene was used as it was, and in Comparative Example 4, toluene dried with Molecular Sieves 3A was used. During the polymerization, the transition metal catalyst component 20
mg, triethylaluminum 0.20 ml, and trimethoxyphenylsilane 0.05 ml were used.
比較例５ トルエンを処理するのに市販の無水塩化マグネシウム
（和光純薬（株）製（Ｘ線回折スペクトルで塩化マグネ
シウムの結晶に基づく強いピークが観測される。））を
用いた他は実施例２と同様にしたところ、希釈直後の収
率が20500g/g−遷移金属触媒成分であったのに対し、10
0時間後は12800g/g−遷移金属触媒成分であった。Comparative Example 5 An example except that commercially available anhydrous magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd. (a strong peak based on magnesium chloride crystals is observed in X-ray diffraction spectrum)) was used to treat toluene. When the same procedure as in Example 2 was performed, the yield immediately after dilution was 20500 g / g-transition metal catalyst component, whereas
It was 12800 g / g-transition metal catalyst component after 0 hour.
本発明の方法を実施することでエチレン、プロピレン、
ブテン−１、ヘキセン−１、スチレンなどの重合、ある
いは共重合触媒として好適な高活性な遷移金属触媒成分
を性能を低下させることなく保存でき工業的に極めて価
値がある。By carrying out the method of the present invention, ethylene, propylene,
A highly active transition metal catalyst component suitable as a polymerization or copolymerization catalyst for butene-1, hexene-1, styrene or the like can be stored without deteriorating the performance and is industrially extremely valuable.
第１図は本発明の理解を助けるためのフローチャート図
である。FIG. 1 is a flow chart for facilitating the understanding of the present invention.
Claims (2)
タンを担持して得たオレフィン重合用遷移金属触媒成分
を炭化水素溶剤中、スラリー状態で保存する方法におい
て、該炭化水素溶剤としてＸ線回折スペクトルにおいて
強い回折スペクトルを有しない無水ハロゲン化マグネシ
ウムで処理した炭化水素溶剤を用いることを特徴とする
オレフィン重合用遷移金属触媒成分の保存方法。1. A method of storing a transition metal catalyst component for olefin polymerization obtained by supporting a tetravalent titanium halide on a magnesium compound in a hydrocarbon solvent in a slurry state, wherein the hydrocarbon solvent is an X-ray diffraction spectrum. A method for storing a transition metal catalyst component for olefin polymerization, which comprises using a hydrocarbon solvent treated with anhydrous magnesium halide having no strong diffraction spectrum in 1.
クトルを有しない無水ハロゲン化マグネシウムが無水ハ
ロゲン化マグネシウムを粉砕処理して得たものである特
許請求の範囲第１項記載の保存方法。2. The storage method according to claim 1, wherein the anhydrous magnesium halide having no strong diffraction spectrum in the X-ray diffraction spectrum is obtained by pulverizing anhydrous magnesium halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288302A JPH0757771B2 (en) | 1987-11-17 | 1987-11-17 | Method for storing transition metal catalyst component for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288302A JPH0757771B2 (en) | 1987-11-17 | 1987-11-17 | Method for storing transition metal catalyst component for olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01131207A JPH01131207A (en) | 1989-05-24 |
| JPH0757771B2 true JPH0757771B2 (en) | 1995-06-21 |
Family
ID=17728409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288302A Expired - Lifetime JPH0757771B2 (en) | 1987-11-17 | 1987-11-17 | Method for storing transition metal catalyst component for olefin polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757771B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680092B2 (en) * | 1985-02-09 | 1994-10-12 | 三菱油化株式会社 | Method for preparing catalyst component for olefin polymerization |
-
1987
- 1987-11-17 JP JP62288302A patent/JPH0757771B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01131207A (en) | 1989-05-24 |
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