JPH01110510A - Pretreatment of transition metal catalyst - Google Patents
Pretreatment of transition metal catalystInfo
- Publication number
- JPH01110510A JPH01110510A JP62268205A JP26820587A JPH01110510A JP H01110510 A JPH01110510 A JP H01110510A JP 62268205 A JP62268205 A JP 62268205A JP 26820587 A JP26820587 A JP 26820587A JP H01110510 A JPH01110510 A JP H01110510A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- metal catalyst
- hydrocarbon solvent
- inert hydrocarbon
- pretreatment
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 28
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002170 ethers Chemical class 0.000 claims abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 5
- 238000012685 gas phase polymerization Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000012808 vapor phase Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 ethylene, propylene, butene Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000006228 supernatant Substances 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
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- 238000007865 diluting Methods 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- URGLIMIKUNFFMT-UHFFFAOYSA-N 1-chloro-1-ethoxyethane Chemical compound CCOC(C)Cl URGLIMIKUNFFMT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 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
- 230000006866 deterioration Effects 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
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
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前処理方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for pretreating transition metal catalysts.
詳しくは、特定の化合物を一定量以下しか含有しない炭
化水素溶剤中で遷移金属触媒を前処理する方法に関する
。Specifically, the present invention relates to a method of pretreating a transition metal catalyst in a hydrocarbon solvent containing a specific amount of a specific compound or less.
エチレン、プロピレン、ブテン、ヘキセン等のオレフィ
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。中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１４〜
１７）。Recently, extremely highly active transition metal catalysts have been developed and used as catalysts for polymerizing olefins such as ethylene, propylene, butene, and hexene. 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 Disclosure Information Report' 1987/February Edition 14~
17).
触媒の活性が向上すると触媒そのものも重合阻害成分に
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取り扱う必要性が生じてくる。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。−方近来の重合技術の進歩により、より
合理化されたプロセス、即ち、塊状重合法、気相重合法
が採用されつつあり、それらのプロセスでは重合系に送
入する遷移金属触媒は触媒の装入の際の閉塞防止とか、
触媒性能の低下の防止のため、通常不活性炭化水素化合
物中で少量のオレフィンで前処理して用いられている。As the activity of the catalyst increases, the catalyst itself becomes relatively weak against polymerization-inhibiting components, and the amount of catalyst used decreases, making it necessary to handle the catalyst at a relatively low concentration. Therefore, conventionally used dispersion media have been carefully purified, and 011-containing compounds such as water and alcohol have been strictly controlled. - Recent advances in polymerization technology have led to the adoption of more streamlined processes, namely bulk polymerization and gas phase polymerization, in which the transition metal catalyst introduced into the polymerization system is To prevent blockage when
In order to prevent deterioration of catalyst performance, it is usually used after being pretreated with a small amount of olefin in an inert hydrocarbon compound.
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０１１基化合物を厳密に除去した不活
性炭化水素化合物溶剤を用いて遷移金属触媒をオレフィ
ンで前処理して使用し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 highly active transition metal catalysts, even if the transition metal catalysts are pretreated with olefin using an inert hydrocarbon compound solvent from which the above-mentioned 011 group-containing compounds have been strictly removed, the activity remains. In some cases, the performance may be inferior, and it was desirable to eliminate the cause.
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 conducted intensive studies on methods for solving the above problems, and as a result, they discovered that an organic ketone compound with a specific structure significantly reduces the performance of a transition metal catalyst, and 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不活性炭化水素溶剤中で少量
のオレフィンで処理し次いで実質的に不活性炭化水素溶
剤の存在しない塊状重合法か或いは気相重合法でオレフ
ィンを重合する方法において、該不活性炭化水素溶剤と
して一般式Ｒ１−０−ＣＺ ＩＩ ｓ −ＣＩ （式中
Ｒ１は炭化水素残基）で表される塩素化エーテル類の含
有量が１０ｐｐｍ以下である不活性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前処理方法である。That is, the present invention involves treating a transition metal catalyst obtained by supporting a titanium compound on a magnesium compound with a small amount of olefin in an inert hydrocarbon solvent, and then using a bulk polymerization method substantially free of the inert hydrocarbon solvent, or In the method of polymerizing olefins by gas phase polymerization, the inert hydrocarbon solvent contains chlorinated ethers represented by the general formula R1-0-CZIIs-CI (wherein R1 is a hydrocarbon residue). A method for pre-treating a transition metal catalyst, characterized by using an inert hydrocarbon solvent in an amount of 10 ppm or less.
本発明において、塩素かエーテル類としては一般式Ｒ’
０−Ｃ！ｌｌ５−ＣＩ （式中Ｒ１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１７１が比較的
小さい、例えば、メチル基、エチル基、プロピル基ブチ
ル基、ヘキシ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
遷移金属触媒の前処理条件では１０ｐｐｍ以下、特に５
ｐｐ−以下とすることで活性の低下は妨げる。In the present invention, as chlorine or ether, the general formula R'
0-C! Examples include compounds represented by ll5-CI (in the formula, R1 is a hydrocarbon residue), and among them, compounds in which 171 is relatively small, such as a methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. Since it affects the reduction of activity, it is necessary to strictly control and control it to 10 ppm or less. Preferably, it is not present at all, but under normal transition metal catalyst pretreatment conditions, it is present in an amount of 10 ppm or less, especially 5
A decrease in activity is prevented by setting it below pp-.
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 a magnesium halide or a magnesium halide treated with an electron-donating compound such as an ester or ether. alkoxymagnesium, magnesium salts of carboxylic acids,
Alternatively, it may contain an inert inorganic or organic compound other than a magnesium compound, or may be further treated with an electron-donating compound. 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。前処理にさいし遷移金属触媒は通常１ｇ八
以上で行う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. It is safer to use the transition metal catalyst in the pretreatment in an amount of 1 g or more.
以下に実施例を示し本発明をさらに説明する。 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エラーシーブ
ス３Ａで乾燥した。このヘプタン中には塩素化エーテル
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, and further distilled.
It was treated repeatedly with silica gel and dried with Molecule sieves 3A. This heptane contained no chlorinated ether.
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
。得られた共粉砕物２０ｇを３００＋＊Ｉのフラスコに
入れ１００ｍ１のへブタン、１０ｈｌ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１００ｍ１のへブタン、１００ｗ
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ら、固形分をヘプタンで
洗浄して遷移金属触媒とした。一部を取り出し遷移金属
触媒１ｇ八にヘプタンで希釈し、遷移金属触媒１ｇあた
りジエチルアルミニウム４．２＋ｍｌ 、 ）ルイル
酸メチル２ｍｌ 、を加えプロピレンを４ｇ室温で装入
して前処理した（実施例１）、また一部は２−エトキシ
−１−クロルエタンを８ｐｐｍ （実施例２）、２０ｐ
ｐｍ （比較例１）含むヘプタンにＩｇ／Ｌとなるよう
に希釈した、また比較のためエーテルを２０ｐｐ−含む
ヘプタンにＩｇ／Ｌとなるように希釈して同様の前処理
をおこなった（参考例２）。前処理直後と２４時間経過
後それぞれの前処理した遷移金属触媒について性能を５
Ｌのオートクレーブを用い、７５°Ｃ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に対し、
トリエチルアルミニウムＯ，Ｏｈｌ、プロピレン１．５
ｋｇ 、水素１．７５Ｎｌ使用した。結果は表に示す。20 g of anhydrous magnesium chloride, 3 ml of tetraethoxysilane, and 4 ml of ethylene dichloride were ground for 40 hours. 20 g of the obtained co-pulverized material was placed in a 300+*I flask, 100 ml of hebutane and 10 hl of titanium tetrachloride were added, and the mixture was heated at 90°C for 1 hour, left to stand, the supernatant was removed, and 100 ml of Hebutane, 100w
1 titanium tetrachloride 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 obtain a transition metal catalyst. A portion was taken out and 1 g of transition metal catalyst was added. 8 was diluted with heptane, 4.2+ ml of diethylaluminium and 2 ml of ) methyl rulyate were added per 1 g of transition metal catalyst, and 4 g of propylene was charged at room temperature for pretreatment (Example 1). 8 ppm of ethoxy-1-chloroethane (Example 2), 20 p
pm (Comparative Example 1) The same pretreatment was carried out by diluting it to Ig/L in heptane containing ether and for comparison, diluting it to Ig/L in heptane containing 20 pp- of ether (Reference Example 2). The performance of each pretreated transition metal catalyst immediately after pretreatment and after 24 hours was evaluated as 5.
Bulk polymerization was performed at 75° C. for 2 hours using a No. L autoclave for evaluation. At this time, for the transition metal catalyst 30a+g,
Triethyl aluminum O, Ohl, propylene 1.5
kg, and 1.75 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.
３００ｍ１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５０−１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、Ｃ６１１１１ＭｇＢｒｏ、 ５ｃ１１１． 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 300 ml round bottom flask, and a mixture of 25 g of cyclohexane bromide and 50-1 diethyl ether was added dropwise over 1 hour while the ether was refluxing. Then, 18 g of cyclohexane chloride was added over 1 hour and stirred under reflux for another 2 hours to obtain C61111MgBro, 5c111. S
An ethyl ether solution of 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
ｇ８５０ｍ１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、さらに還流下に４時間撹拌した。Allyl chloride 24 was then added under reflux of ethyl ether.
A solution of g850ml of ethyl ether was added dropwise over 3 hours, and 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
固形分は阿ｇ：ｃｊ！：Ｂｒがほぼ１：０．５：１．５
であり、ＭｇＲｒｏ、 ｓＣｌ ＋、 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 Ag:cj! :Br is approximately 1:0.5:1.5
and MgRro, sCl +, s.
上記固形分Ｌｏｇを２００ｍ ｌの丸底フラスコに入れ
、四塩化チタン５０ｍ１、ヘプタン５０ｍ１を入れ、９
０℃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５０１、ヘプタン５０＋ｗ Ｉ
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０分析の結果はチタンを１ 、３
ｗ ｔｚ金含有ていた。Put the above solid content Log into a 200 ml round bottom flask, add 50 ml of titanium tetrachloride and 50 ml of heptane, and
The mixture was stirred at 0° C. for 1 hour, then allowed to stand, and the supernatant was removed. Furthermore, titanium tetrachloride 501, heptane 50+w I
was stirred at 90°C for 1 hour, then left to stand, the supernatant was removed, and the resulting solid content was washed with toluene 7 times to use as a transition metal catalyst. ,3
w tz It contained gold.
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（但し２−エトキシ−１
−クロルエタンに変え２−イソプロポキシ−１−クロル
エタンを用いた）（比較例２） と同様にした。但し、
前処理の際、遷移金属触媒１ｇに対しトリエチルアルミ
ニウム０．２ｍｌ 、 トリットキシフェニルシラン
０．０５ｍ１を使用し、塊状重合の際には遷移金属触媒
２０曽ｇに対し、トリエチルアルミニウム０．２０ｍ１
、トリメトキシフェニルシラン０．０５ｍ１を追加して
用いた。Example 1 (Example 3) of Experimental Example 1, Comparative Example 1 (However, 2-ethoxy-1
-2-isopropoxy-1-chloroethane was used instead of chloroethane) (Comparative Example 2). however,
During pretreatment, 0.2 ml of triethylaluminum and 0.05 ml of tritoxyphenylsilane were used per 1 g of transition metal catalyst, and during bulk polymerization, 0.20 ml of triethyl aluminum was used per 20 g of transition metal catalyst.
, 0.05 ml of trimethoxyphenylsilane was additionally 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前処理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 pretreated 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)
金属触媒を不活性炭化水素溶剤中で少量のオレフィンで
処理し次いで実質的に不活性炭化水素溶剤の存在しない
塊状重合法か或いは気相重合法でオレフィンを重合する
方法において、該不活性炭化水素溶剤として一般式▲数
式、化学式、表等があります▼（式中Ｒ＾１は炭化水素
残基）で表される塩素化エーテル類の含有量が１０ｐｐ
ｍ以下である不活性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前処理方法A transition metal catalyst obtained by supporting a titanium compound on a magnesium compound is treated with a small amount of olefin in an inert hydrocarbon solvent, and then subjected to bulk polymerization in the absence of substantially an inert hydrocarbon solvent or gas phase polymerization. In the method of polymerizing olefins, the content of chlorinated ethers represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R^1 is a hydrocarbon residue) is used as the inert hydrocarbon solvent. 10pp
A pretreatment method for a transition metal catalyst characterized by using an inert hydrocarbon solvent having a molecular weight of less than m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62268205A JPH01110510A (en) | 1987-10-26 | 1987-10-26 | Pretreatment of transition metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62268205A JPH01110510A (en) | 1987-10-26 | 1987-10-26 | Pretreatment of transition metal catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01110510A true JPH01110510A (en) | 1989-04-27 |
Family
ID=17455379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62268205A Pending JPH01110510A (en) | 1987-10-26 | 1987-10-26 | Pretreatment of transition metal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01110510A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57131204A (en) * | 1981-02-05 | 1982-08-14 | Mitsubishi Chem Ind Ltd | Production of polyolefin |
| JPS5928754A (en) * | 1982-08-10 | 1984-02-15 | Nippon Telegr & Teleph Corp <Ntt> | Facsimile device |
| JPS59140206A (en) * | 1983-02-01 | 1984-08-11 | Mitsubishi Chem Ind Ltd | Production of propylene polymer |
| JPS62268204A (en) * | 1985-05-10 | 1987-11-20 | ゼネラル・エレクトリック・カンパニイ | Charge coupler |
| JPS6327511A (en) * | 1986-07-21 | 1988-02-05 | Mitsubishi Chem Ind Ltd | Production of propylene polymer |
| JPS63202604A (en) * | 1987-02-19 | 1988-08-22 | Mitsui Petrochem Ind Ltd | Polymerization of alpha-olefin |
-
1987
- 1987-10-26 JP JP62268205A patent/JPH01110510A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57131204A (en) * | 1981-02-05 | 1982-08-14 | Mitsubishi Chem Ind Ltd | Production of polyolefin |
| JPS5928754A (en) * | 1982-08-10 | 1984-02-15 | Nippon Telegr & Teleph Corp <Ntt> | Facsimile device |
| JPS59140206A (en) * | 1983-02-01 | 1984-08-11 | Mitsubishi Chem Ind Ltd | Production of propylene polymer |
| JPS62268204A (en) * | 1985-05-10 | 1987-11-20 | ゼネラル・エレクトリック・カンパニイ | Charge coupler |
| JPS6327511A (en) * | 1986-07-21 | 1988-02-05 | Mitsubishi Chem Ind Ltd | Production of propylene polymer |
| JPS63202604A (en) * | 1987-02-19 | 1988-08-22 | Mitsui Petrochem Ind Ltd | Polymerization of alpha-olefin |
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