JPH01111449A - Method for preservation of transition metal catalyst - Google Patents
Method for preservation of transition metal catalystInfo
- Publication number
- JPH01111449A JPH01111449A JP62268203A JP26820387A JPH01111449A JP H01111449 A JPH01111449 A JP H01111449A JP 62268203 A JP62268203 A JP 62268203A JP 26820387 A JP26820387 A JP 26820387A JP H01111449 A JPH01111449 A JP H01111449A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- compound
- metal catalyst
- hydrocarbon solvent
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 24
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 11
- 238000004321 preservation Methods 0.000 title 1
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011777 magnesium Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- -1 magnesium halide Chemical class 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-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
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-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
- 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 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
- 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
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は遷移金属触媒の保存方法に関する。詳しくは、
特定の化合物を一定量以下しか含有しない炭化水素溶剤
中でスラリー状態で保存する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for preserving transition metal catalysts. For more information,
It relates to a method of preserving a specific compound in a slurry state in a hydrocarbon solvent containing only a certain amount or less.
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。Recently, extremely highly active transition metal catalysts have been developed and used as catalysts for olefin polymerization.
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しられてい
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１４〜１７）。Among them, those in which a titanium compound is supported on a magnesium compound are highly active, and many types are already known (for example, Diamond Management Development Information Public Information Report' 1987/February Edition 14-17).
触媒の活性が向上すると、触媒そのものの重合阻害成分
に対して相対的に弱（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０１１基化合物等は厳密に管
理されている。As the activity of the catalyst improves, it becomes relatively weak against the polymerization-inhibiting components of the catalyst itself (in addition, the amount of catalyst used decreases, making it necessary to store it at a relatively low concentration. The dispersion medium to be used is carefully purified, and water, alcohol, and other 011-containing compounds are strictly controlled.
しかしながら、実際に高活性の遷移金属触媒を使用する
に際して、上記含０■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ることがあ
り、その原因を除くことが望まれた。However, when actually using a highly active transition metal catalyst, the activity may be poor even if a solvent in which the above-mentioned 0 group-containing compounds are strictly removed is used as a dispersion medium, and the cause of this may be removed. It was desired.
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
した結果特定の構造の有機ケトン化合物が遷移金属触媒
の性能を大幅に低下させることを見出し本発明を完成し
た。The inventors of the present invention have conducted extensive studies on methods for solving the above-mentioned problems, and have discovered that organic ketone compounds with a specific structure significantly reduce the performance of transition metal catalysts, and have completed the present invention.
即ち本発明は、マグネシウム化合物にチタン化合物を担
持して得た遷移金属触媒を炭化水素溶剤中でスラリー状
態で保存する方法において、該炭化水素溶剤として一般
式１１’−Ｃｏ−Ｃ＝Ｃ−Ｒ２Ｒハ式中Ｒ１、ＲＪ２は
炭化水素残基）で表される共役ビニルケトン類の含有量
が１０ｐｐ−以下である炭化水素溶剤を用いることを特
徴とする遷移金属触媒の保存方法である。That is, the present invention provides a method for storing a transition metal catalyst obtained by supporting a titanium compound on a magnesium compound in a slurry state in a hydrocarbon solvent, in which a transition metal catalyst obtained by supporting a titanium compound on a magnesium compound is stored in a slurry state in a hydrocarbon solvent. This is a method for preserving a transition metal catalyst, characterized by using a hydrocarbon solvent having a content of conjugated vinyl ketones represented by the following formula (R1 and RJ2 are hydrocarbon residues) of 10 pp- or less.
本発明において、共役ビニルケトンとしては一般式Ｒ’
−Ｃｏ−Ｃ＝Ｃ−Ｒ２Ｒ’Ｃ式中Ｒ’、Ｒ”、Ｒりは炭
化水素残基）で表される化合物が挙げられるが、なかで
もｐｌ、Ｒ１，Ｒｆｆが比較的小さい、例えば、メチル
基、エチル基、プロピル基等である化合物が活性の低下
に影響を与える為厳密に管理し１０ｐｐｍ以下に制御す
る必要がある。好ましくは、全く存在しないことである
が、通常の遷移金属触媒の保存条件では１０ｐｐ＋ｗ以
下、特に５ｐｐｍ以下とすることで活性の低下は妨げる
。In the present invention, the conjugated vinyl ketone has the general formula R'
Examples include compounds represented by -Co-C=C-R2R'C (where R', R'' and R are hydrocarbon residues), among which pl, R1, and Rff are relatively small, for example, Compounds such as methyl groups, ethyl groups, propyl groups, etc. affect the reduction of activity, so they must be strictly controlled and controlled to 10 ppm or less.Preferably, they do not exist at all, but ordinary transition metal catalysts Under the storage conditions of 10 pp+w or less, especially 5 ppm or less, a decrease in activity is prevented.
本発明において、マグネシウム化合物にチタン化合物を
担持して得た遷移金属触媒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ハ
ロゲン含有化合物を担持したもの、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、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を用いたものであっても
よい。これらの遷移金属触媒の具体例としては、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 obtained by supporting a titanium compound on a magnesium compound is not particularly limited, and a halogen-containing compound may be supported on magnesium halide or magnesium halide treated with an electron-donating compound such as ester or ether. or contain an alkoxymagnesium, a magnesium salt of carboxylic acid, or an inert inorganic or organic compound other than a magnesium compound as a carrier, or use a carrier that has been further treated with an electron-donating compound. You can. As specific examples of these transition metal catalysts, many patents are exemplified in the above-mentioned literature.
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、エチルベンゼンなどあるいはその混合物が
挙げられる。保存にさいし遷移金属触媒は通常１ｇ八以
上好ましくは５ｇ八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, hydrocarbon solvents include pentane, hexane, heptane, nonane, decane, benzene, toluene, xylene, ethylbenzene, etc., or mixtures thereof. During storage, it is safer to store the transition metal catalyst at a concentration of usually 1 g or more, preferably 5 g 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 explained with reference to Examples below.
実験例１
市販のへブタンを硫酸で処理しついで水洗した後、カル
シウムハイドライド上で還流処理しさらに蒸留後、シリ
カゲルで繰り返し処理しついでモレキュラーシープス３
＾で乾燥した。このヘプタン中には共役ビニルケトンは
全く含まれていなかった。Experimental Example 1 Commercially available hebutane was treated with sulfuric acid, washed with water, refluxed over calcium hydride, further distilled, repeatedly treated with silica gel, and then treated with Molecular Sheeps 3.
Dry with ^. This heptane contained no conjugated vinyl ketone.
無水の塩化マグネシウム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。20 g of anhydrous magnesium chloride, 3 ml of tetraethoxysilane, and 4 ml of ethylene dichloride were ground for 40 hours.
得られた共粉砕物２０ｇを３００ｍ ｌのフラスコに入
れ１００ｍ１のへブタン、１００１の四塩化チタンを加
え９０”Ｃで１時間加熱処理し、ついで静置し上澄みを
除去しさらに同様に１００＋ｍｌのへブタン、１００ｍ
１の四塩化チタンを加え９０°Ｃで１時間加熱処理した
。静置し上澄みを除去したのち、固形分をヘプタンで洗
浄して遷移金属触媒とした（参考例１）、一部を取り出
しＬｏｇ／Ｌにヘプタンで希釈した（実施例１）、また
一部はメシチルオキシドを８１）ｐ−（実施例２）、２
０ｐｐｍ（比較例り 含むヘプタンに１０ｇ／Ｌとなる
ように希釈した、また比較のためアセトンを２０ｐｐ＋
ｗ含むヘプタンに１０ｇ／Ｌとなるように希釈した（参
考例２）、希釈後直後と１００時間経過後それぞれの遷
移金属触媒について性能を５Ｌのオートクレーブを用い
、７５１Ｃで２時間塊状重合して評価した。この時遷移
金属触媒３０ａ＋ｇ、 ）リエチルアルミニウム０．
０８ｍ＋１．ジエチルアルミニウムクロリド０．１２８
ｍ１ 、）ルイル酸メチル０．０６ｍ１．プロピレン１
．５ｋｇ 、水素１．３８Ｎｌ使用した。結果は表に示
す。20 g of the obtained co-pulverized product was placed in a 300 ml flask, 100 ml of hebutane and 1001 titanium tetrachloride were added, and the mixture was heated at 90"C for 1 hour, then allowed to stand, the supernatant was removed, and the flask was poured into a 100+ ml flask in the same manner. Butane, 100m
Titanium tetrachloride (1) was added and heat treated at 90°C for 1 hour. After standing still and removing the supernatant, the solid content was washed with heptane to prepare a transition metal catalyst (Reference Example 1), a portion was taken out and diluted with heptane to Log/L (Example 1), and a portion was Mesityl oxide 81) p- (Example 2), 2
0ppm (as a comparative example, diluted to 10g/L in heptane, and for comparison, 20pp+ acetone)
The performance of each transition metal catalyst was diluted to 10 g/L in heptane containing W (Reference Example 2), immediately after dilution and after 100 hours, using a 5 L autoclave, and performing bulk polymerization at 751C for 2 hours to evaluate the performance. did. At this time, transition metal catalyst 30a+g, ) ethyl aluminum 0.
08m+1. Diethylaluminium chloride 0.128
m1,) methyl rulyate 0.06 m1. propylene 1
．． 5 kg and 1.38 Nl of hydrogen were used. The results are shown in the table.
実験例２
実験例１と同様の共役ビニルケトンを含有しないヘプタ
ンを用いて以下の実験を行った。Experimental Example 2 The following experiment was conducted using the same heptane as in Experimental Example 1 that does not contain a conjugated vinyl ketone.
３００１の丸底フラスコにマグネシウム７．４ｇ、ジエ
チルエーテル２０ｍ１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５０ｍ ｌ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
ンを１８ｇを１時間かけて添加しさら２時間還流下撹拌
処理し、Ｃ６ＨＩ １ＭｇＢｒｏ、 ｓｃＩ＋、 ｓの
エチルエーテル溶液を調製した。7.4 g of magnesium and 20 ml of diethyl ether were placed in a No. 3001 round bottom flask, and a mixture of 25 g of cyclohexane bromide and 50 ml of diethyl ether was added dropwise over 1 hour while the ether was refluxing. Next, 18 g of cyclohexane chloride was added over 1 hour and stirred under reflux for another 2 hours to prepare an ethyl ether solution of C6HI 1MgBro, scI+, s.
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５０ｍ１のエチルエーテルを３時間かけて滴下し、
さらに還流下に４時間撹拌した。Allyl chloride 24 was then added under reflux of ethyl ether.
g was added dropwise to 50ml of ethyl ether over 3 hours,
The mixture was further 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：Ｃｊ！：Ｏｒがほぼ１：０．５：１、５
であり、ＭｇＢｒ＋． ｓＣ ｊ！ ＋． ｓであった
。Then, it was filtered at room temperature, and the solid content was washed with ethyl ether and dried with a nitrogen stream to obtain 41 g of solid content. The obtained solid content is Mg:Cj! :Or is almost 1:0.5:1,5
and MgBr+. sC j! +. It was s.
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、ヘプタン５０ｍｌを入れ、９０
°Ｃで１時間撹拌処理し、次いで静置して上澄を除去し
た。さらに四塩化チタン５０ｍ ｌ 、ヘプタン５０ｍ
ｌを入れ、９０°Ｃで１時間撹拌処理し、次いで静置し
て上澄を除去し、得られた固形分をトルエンで７回洗浄
して遷移金属触媒とした．分析の結果はチタンを１．３
ｗｔχ含有していた。Put 10g of the above solid content into a 200ml round bottom flask,
Add 50 ml of titanium tetrachloride and 50 ml of heptane,
The mixture was stirred at °C for 1 hour, then allowed to stand and the supernatant was removed. Additionally, 50 ml of titanium tetrachloride and 50 ml of heptane
The mixture was stirred at 90°C for 1 hour, then left to stand, the supernatant was removed, and the resulting solid was washed seven times with toluene to prepare a transition metal catalyst. The analysis results show that titanium is 1.3
It contained wtχ.
上記操作で得た遷移金属触媒を用いた他は実験例１の実
施例１（実施例３）、比較例１（比較例２） と同様に
した．但し、重合の際遷移金属触媒２０ｆｉｇ、トリエ
チルアルミニウム０．２０ａ＋１、トリメトキシフェニ
ルシラン０ 、 ０５ｍ ｌを用いた。The same procedures as in Example 1 (Example 3) and Comparative Example 1 (Comparative Example 2) of Experimental Example 1 were conducted except that the transition metal catalyst obtained in the above procedure was used. However, during the polymerization, 20 figs of a transition metal catalyst, 0.20a+1 of triethylaluminum, and 0.05 ml of trimethoxyphenylsilane were used.
本発明の方法を実施することで高活性な遷移金属触媒を
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, highly active transition metal catalysts can be preserved without deteriorating their performance, which is extremely valuable industrially.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
金属触媒を炭化水素溶剤中で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一般式Ｒ＾１−ＣＯ
−Ｃ＝Ｃ−Ｒ＾２Ｒ＾３（式中Ｒ＾１、Ｒ＾２、Ｒ＾３
は炭化水素残基）で表される共役ビニルケトン類の含有
量が１０ｐｐｍ以下である炭化水素溶剤を用いることを
特徴とする遷移金属触媒の保存方法。In a method of preserving a transition metal catalyst obtained by supporting a titanium compound on a magnesium compound in a slurry state in a hydrocarbon solvent, the hydrocarbon solvent is a compound having the general formula R^1-CO.
-C=C-R^2R^3 (in the formula R^1, R^2, R^3
A method for preserving a transition metal catalyst, comprising using a hydrocarbon solvent having a content of conjugated vinyl ketones (represented by hydrocarbon residue) of 10 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62268203A JP2507489B2 (en) | 1987-10-26 | 1987-10-26 | Storage method for transition metal catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62268203A JP2507489B2 (en) | 1987-10-26 | 1987-10-26 | Storage method for transition metal catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01111449A true JPH01111449A (en) | 1989-04-28 |
| JP2507489B2 JP2507489B2 (en) | 1996-06-12 |
Family
ID=17455353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62268203A Expired - Fee Related JP2507489B2 (en) | 1987-10-26 | 1987-10-26 | Storage method for transition metal catalysts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2507489B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002292285A (en) * | 2001-03-30 | 2002-10-08 | Nippon Shokubai Co Ltd | Preservation method of resin catalyst for addition reaction of alkylene oxide and its use |
-
1987
- 1987-10-26 JP JP62268203A patent/JP2507489B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002292285A (en) * | 2001-03-30 | 2002-10-08 | Nippon Shokubai Co Ltd | Preservation method of resin catalyst for addition reaction of alkylene oxide and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2507489B2 (en) | 1996-06-12 |
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