JPH01249782A - Potassium salt of organic silicon compound for catalyst having high activity and production thereof - Google Patents
Potassium salt of organic silicon compound for catalyst having high activity and production thereofInfo
- Publication number
- JPH01249782A JPH01249782A JP7458088A JP7458088A JPH01249782A JP H01249782 A JPH01249782 A JP H01249782A JP 7458088 A JP7458088 A JP 7458088A JP 7458088 A JP7458088 A JP 7458088A JP H01249782 A JPH01249782 A JP H01249782A
- Authority
- JP
- Japan
- Prior art keywords
- potassium salt
- formula
- catalyst
- organosilicon compound
- organic silicon
- 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 title abstract description 7
- 150000003377 silicon compounds Chemical class 0.000 title abstract 2
- 230000000694 effects Effects 0.000 title description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000105 potassium hydride Inorganic materials 0.000 claims abstract description 10
- LTOBXQFQSXFEER-UHFFFAOYSA-N bis(9h-fluoren-1-yl)-dimethylsilane Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2[Si](C)(C)C1=CC=CC2=C1CC1=CC=CC=C12 LTOBXQFQSXFEER-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000725 suspension Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 229910052747 lanthanoid Inorganic materials 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 150000002602 lanthanoids Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101150117004 atg18 gene Proteins 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- -1 silicon compound salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ZGFFKHWCLRFAAX-UHFFFAOYSA-N dimethyl-bis(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane Chemical compound CC1=C(C)C(C)=C(C)C1[Si](C)(C)C1C(C)=C(C)C(C)=C1C ZGFFKHWCLRFAAX-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process 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
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000054 lanthanide hydride Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエチレンの重合や各種オレフィンの水素化に高
度な触媒活性を示す物質として重要な有機ランタノイド
水素化物の原料となる有機珪素化合物塩とその製造方法
に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to organic silicon compound salts, which are raw materials for organic lanthanide hydrides, which are important substances that exhibit high catalytic activity in the polymerization of ethylene and the hydrogenation of various olefins. It relates to its manufacturing method.
近年エチレンの重合や各種オレフィンの水素化に関し、
従来の常識を破った高度な触媒活性を示す有機ランタノ
イド触媒が見出されている。（公表特許公報昭和６２−
５０２７５０号および、ジャーナルオブアメリカンケミ
カルソサイエティ １９８５年第１０７巻８０９１〜８
１１８頁）
この新規触媒は下記（１）の構造を有する一般式（（Ｃ
Ｉ（３）２ｓｔ （η’−（Ｃ）Ｉａ）＊Ｃ５）ＪＨ）
ｚにて表わされる、ビス（テトラメチルシクロペンタジ
ェニル）ジメチルシリルランタノイドヒドリド錯体であ
る。In recent years, regarding the polymerization of ethylene and the hydrogenation of various olefins,
Organic lanthanide catalysts have been discovered that exhibit high catalytic activity that goes beyond conventional wisdom. (Published Patent Publication 1986-
502750 and Journal of American Chemical Society 1985 Vol. 107 8091-8
(page 118) This new catalyst has the general formula ((C
I(3)2st (η'-(C)Ia)*C5)JH)
It is a bis(tetramethylcyclopentadienyl)dimethylsilyllanthanoid hydride complex represented by z.
（Ｍ＝ランタノイド金１、Ｍｅ ＝＋−ＣＨ５）化合物
（１）においては配位子として下記（Ａ）の構造を有す
るものが用いられており、そのシクロペンタジェニル環
（Ｃｐ）の置換基により高度な触媒活性を示すものと考
えられる。そこで、該置換基を変えることにより更に高
度の触媒活性を付与し得ることが期待される。(M = lanthanoid gold 1, Me = +-CH5) In compound (1), a ligand having the following structure (A) is used, and the substituent of its cyclopentagenyl ring (Cp) It is considered that the catalytic activity is higher due to the higher catalytic activity. Therefore, it is expected that a higher level of catalytic activity can be imparted by changing the substituents.
本発明者は、上記触媒の改良を試み、上記シクロペンタ
ジェニル環に代えて下記ＣＢ）に示すフルオレン環を有
する配位子を持つものが高い触媒活性を有することを見
呂した。The present inventor attempted to improve the above catalyst and found that one having a ligand having a fluorene ring as shown in CB) below in place of the cyclopentadienyl ring had high catalytic activity.
また上記シクロペンタジェニル環を有する有機珪素化合
物および上記フルオレン環を有する有機珪素化合物のア
ニオン化について、これら有機珪素化合物をテトラヒド
ロフラン中で水素化カリウムを反応させることにより容
易にアニオン化できることを見出した。Furthermore, regarding the anionization of the above-mentioned organosilicon compounds having a cyclopentadienyl ring and the above-mentioned organosilicon compounds having a fluorene ring, it has been found that these organosilicon compounds can be easily anionized by reacting them with potassium hydride in tetrahydrofuran. .
本発明によれば。According to the invention.
構造式
で表わされ、高触媒活性有機金属錯体の原料として用い
られる有機珪素化合物のカリウム塩が提供される。A potassium salt of an organosilicon compound represented by the structural formula and used as a raw material for a highly catalytically active organometallic complex is provided.
また本発明によれば、シクロペンタジェニル環を有する
有機珪素化合物をテトラヒドロフラン中で水素化カリウ
ムと反応させることにより、該有機珪素化合物のカリウ
ム塩を製造する方法が提供される。Further, according to the present invention, there is provided a method for producing a potassium salt of an organosilicon compound having a cyclopentadienyl ring by reacting the organosilicon compound with potassium hydride in tetrahydrofuran.
また上記製造方法の好適な態様として上記有機珪素化合
物として、ビスフルオレニルジメチルシランを用い上記
構造式の有機珪素化合物カリウム塩を製造する方法が提
供される。Further, as a preferred embodiment of the above production method, there is provided a method for producing an organosilicon compound potassium salt having the above structural formula using bisfluorenyldimethylsilane as the organosilicon compound.
下記の構造式で表わされるビスフルオレニルジメチルシ
ランについて、
その触媒活性作用に注目し、これを高活性触媒の原料に
利用する試みは従来全く行われていない。Regarding bisfluorenyldimethylsilane represented by the structural formula below, no attempt has been made to focus on its catalytic activity and to utilize it as a raw material for highly active catalysts.
本発明において、上記ビスフルオレニルジメチルシラン
のＣｐ部位をアニオン化して高活性触媒の原料とするこ
とが試みられた。In the present invention, an attempt was made to anionize the Cp site of the bisfluorenyldimethylsilane and use it as a raw material for a highly active catalyst.
該アニオン化方法について、前述の文献には。The anionization method is described in the above-mentioned literature.
ビステトラメチルシクロペンタジェニルシラン（Ｍｅ２
Ｓｉ（Ｍｅ４Ｃ，Ｈ））をテトラヒドロフラン中でノル
マルブチルリチウム（ｎ−ＢｕＬｉ）と反応させそのリ
チウム塩を製造することが開示されている。然し乍らこ
のアニオン化方法はその反応時間が約４８時間と長い。Bistetramethylcyclopentadienylsilane (Me2
It is disclosed that Si(Me4C,H)) is reacted with n-butyllithium (n-BuLi) in tetrahydrofuran to produce its lithium salt. However, this anionization method requires a long reaction time of about 48 hours.
本発明のアニオン化方法は、シクロペンタジェニル環（
Ｃｐ）を有する有機珪素化合物をテトラヒドロフラン中
で水素化カリウムと反応させることにより、該有機珪素
化合物のＣｐ部位をアニオン化し、そのカリウム塩を得
る。具体的には、Ｍｅ２Ｓｉ（Ｍｅ４ｃｓＨ）ｚ をテ
トラヒドロフランに溶解し、該液を水素化カリウムの懸
濁液に加え、室温下で攪拌する。約２０時間後に懸濁液
を濾過し、濾液からテトラヒドロフランを蒸留分離し、
残留物を回収後。The anionization method of the present invention comprises a cyclopentagenyl ring (
By reacting an organosilicon compound having Cp) with potassium hydride in tetrahydrofuran, the Cp site of the organosilicon compound is anionized to obtain its potassium salt. Specifically, Me2Si(Me4csH)z is dissolved in tetrahydrofuran, the solution is added to a suspension of potassium hydride, and the mixture is stirred at room temperature. After about 20 hours, the suspension was filtered, and tetrahydrofuran was distilled off from the filtrate.
After collecting the residue.
ジエチルエーテルを用いて洗浄することにより上記化合
物のカリウム塩を得る。The potassium salt of the above compound is obtained by washing with diethyl ether.
本発明のアニオン化方法はシクロペンタジェニル環を有
する有機珪素化合物に広く適用できる。The anionization method of the present invention can be widely applied to organosilicon compounds having a cyclopentadienyl ring.
上記アニオン化方法によりビスフルオレニルジメチルシ
ランをアニオン化して上記構造式（Ｃ）のカリウム塩を
得る。Bisfluorenyldimethylsilane is anionized by the above anionization method to obtain the potassium salt of the above structural formula (C).
本発明の有機珪素化合物カリウム塩を原料として用いる
ことにより高度の触媒活性を有する有機ランタノイド錯
体を製造することができる。By using the organosilicon compound potassium salt of the present invention as a raw material, an organo-lanthanide complex having a high degree of catalytic activity can be produced.
また本発明のアニオン化方法によれば、従来方法より大
幅に反応時間を短縮できる。−例として従来ｎ−ＢｕＬ
ｉを用いたアニオン化方法は約４０時間の反応時間を要
しているが１本発明の水素化カリウムを用いる方法では
約２０時間の反応時間で足りる。Furthermore, according to the anionization method of the present invention, the reaction time can be significantly shortened compared to conventional methods. -For example, conventional n-BuL
The anionization method using i requires a reaction time of about 40 hours, but the method using potassium hydride of the present invention requires a reaction time of about 20 hours.
実施例１
〈ビスフルオレニルジメチルシランの合成〉フルオレン
２０．４５ｇ（０，１２３モル）を溶解したテトラヒド
ロフラン（以下ＴＨＦ）溶液２５０ｃｍ３に濃度１．５
４Ｍのｎ−ＢｕＬｉヘキサン溶液８０ｃｍ３（ｎ−Ｂｕ
Ｌｉ； ０．１２３モル）を室温でゆっくり滴下した０
滴下後１時間攪拌し。Example 1 <Synthesis of bisfluorenyldimethylsilane> A concentration of 1.5 was added to 250 cm3 of a tetrahydrofuran (THF) solution in which 20.45 g (0,123 mol) of fluorene was dissolved.
80 cm3 of 4M n-BuLi hexane solution (n-Bu
Li; 0.123 mol) was slowly added dropwise at room temperature.
After dropping, stir for 1 hour.
濃赤色になったフルオレンアニオン溶液にジクロロジメ
チルシラン７．４ｃｍ’ （０，０６１６モル）を５０
ｃｍ’のＴＨＦに希釈した溶液をゆっくり滴下した。２
日間加熱還流後、溶媒を除去し生成物をヘキサンで抽出
した。このヘキサン溶液を約６０ｃｍ’ に濃縮し。Add 7.4 cm' (0,0616 mol) of dichlorodimethylsilane to the deep red fluorene anion solution.
cm' of THF diluted solution was slowly added dropwise. 2
After heating under reflux for 1 day, the solvent was removed and the product was extracted with hexane. This hexane solution was concentrated to about 60 cm'.
再結晶し精製した。It was recrystallized and purified.
得られた結晶を元素分析、赤外、Ｎ Ｍ Ｒ１質量分析
によって検定したところＣ，８６，５５； Ｈ，６，１
３；Ｓｉ、 ７．３２（重量％）であり、またマススペ
クトルは図示の通りであった。この結果によりＣｚｉＨ
２＋ＳＬが合成されたことを確認した。The obtained crystal was tested by elemental analysis, infrared, and NMR1 mass spectrometry, and found to be C, 86,55; H, 6,1
3; Si, 7.32 (wt%), and the mass spectrum was as shown. Based on this result, CziH
It was confirmed that 2+SL was synthesized.
くビスフルオレニルジメチルシランアニオンカリウム塩
の合成〉
上述の方法で得られた結晶１．９４０ｇ（５ミリモル）
を含むＴＨＦ溶液１０ｃｍ”を、水素化カリウム０．４
０１ｇ（１０ミリモル）を愚濁させた１０ｃｍ’のＴＨ
Ｆに加え、室温で２０時間攪拌した。Synthesis of bisfluorenyldimethylsilane anion potassium salt> 1.940 g (5 mmol) of crystals obtained by the above method
10 cm of THF solution containing 0.4 cm of potassium hydride
10cm' of TH that made 01g (10 mmol) cloudy
F and stirred at room temperature for 20 hours.
溶液は褐色を帯びた乳白色懸濁液になった。The solution became a brownish milky suspension.
この懸濁液を濾過し、濾液からＴ旺を減圧蒸留により除
去した残留物をジエチルエーテルを用いて洗浄し、再結
晶して１．３９２ｇの結晶を得た（収率６０％）。This suspension was filtered, and the residue was washed with diethyl ether and recrystallized to obtain 1.392 g of crystals (yield: 60%).
赤外、ＮＭＲ１質量分析によってこの物質はｃ２６ Ｈ
２□５ｉＫ２であることを確認した。Infrared, NMR1 mass spectrometry reveals that this material is c26 H
I confirmed that it was 2□5iK2.
実施例２
（、’ｌｅ、 Ｓｌ （Ｎ８４ Ｃ，Ｘ ）Ｊの合成〉
ビス（２，３，４，５−テトラメチルシクロペンタジェ
ニル）ジメチルシラン（ＮｅｚＳｉ（Ｍａ４ＣｇＨ）Ｊ
と水素化カリウムの反応による上記化合物のカリウム
塩Ｍｅ２Ｓｉ（Ｍｅ４Ｃ，Ｋ）、の合成を試みた。Example 2 (Synthesis of ,'le,Sl(N84C,X)J)
Bis(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane (NezSi(Ma4CgH)J
An attempt was made to synthesize the potassium salt of the above compound, Me2Si(Me4C,K), by the reaction of Me2Si(Me4C,K) and potassium hydride.
水素化カリウム０．６７２１ｇ（１６，フロミリモル）
を懸濁させたＴ）ＩＦ１０ｃｍ’に、Ｍｅ、ＳＬ（Ｍｅ
、Ｃ，Ｈ）＝ ２．５１３９ｇ（８，３８０ミリモル）
のＴＨＦ溶液１０ｃｍ３を加え、室温で２０時間攪拌し
た６反応は定量的に進行しＭｅ！ＳＬ（Ｍｅ４ＣｓＫ）
＝８．３８ミリモルが単離された。Potassium hydride 0.6721g (16, fromimole)
Me, SL (Me
, C, H) = 2.5139g (8,380 mmol)
6 reaction proceeded quantitatively by adding 10 cm3 of THF solution of Me! and stirring at room temperature for 20 hours. SL(Me4CsK)
=8.38 mmol isolated.
図は実施例１で合成したビスフルオレニルジメチルシラ
ンのマススペクトルである。
特許出願人 三菱金属株式□会社
代理人 弁理士松井政広（外１名）
四〇 ３００ ３５０ ４００Ｍ／Ｅ手
続補正書
昭和６３年７月１１日
特許庁長官 吉 １）文毅 殿
１、事件の表示
昭和６３年 特 許 願第０７４５８０号２、発明の名
称
３、補正をする者
事件との関係 特許出願人
名称 （６２６）呉菱金属株式会社
４、代理人（〒１６４）
住 所 東京都中野区本町１丁目３１番４号シティーハ
イムコスモ１００３号室
電話（０３）３７３−５５７１（代）The figure is a mass spectrum of bisfluorenyldimethylsilane synthesized in Example 1. Patent applicant: Mitsubishi Metals Co., Ltd. Company agent: Patent attorney Masahiro Matsui (1 other person) 40 300 350 400 M/E procedural amendment July 11, 1988 Commissioner of the Japan Patent Office Yoshi 1) Bunki Tono 1, Indication of the case 1986 Patent Application No. 074580 2, Title of the invention 3, Relationship with the case of the person making the amendment Patent applicant name (626) Kureki Kinzoku Co., Ltd. 4, Agent (164) Address Nakano-ku, Tokyo Honmachi 1-31-4 City Heim Cosmo Room 1003 Telephone: (03) 373-5571 (Main)
Claims (1)
られる有機珪素化合物のカリウム塩。 ２、シクロペンタジエニル環を有する有機珪素化合物を
テトラヒドロフラン中で水素化カリウムと反応させるこ
とにより、該有機珪素化合物のカリウム塩を製造する方
法。 ３、上記有機珪素化合物として、ビスフルオレニルジメ
チルシランを用い、第１請求項の有機珪素化合物カリウ
ム塩を製造する方法。[Claims] 1. A potassium salt of an organosilicon compound represented by the structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ and used as a raw material for a highly catalytically active organometallic complex. 2. A method for producing a potassium salt of an organosilicon compound having a cyclopentadienyl ring by reacting the organosilicon compound with potassium hydride in tetrahydrofuran. 3. A method for producing the organosilicon compound potassium salt according to claim 1, using bisfluorenyldimethylsilane as the organosilicon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7458088A JPH01249782A (en) | 1988-03-30 | 1988-03-30 | Potassium salt of organic silicon compound for catalyst having high activity and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7458088A JPH01249782A (en) | 1988-03-30 | 1988-03-30 | Potassium salt of organic silicon compound for catalyst having high activity and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01249782A true JPH01249782A (en) | 1989-10-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7458088A Pending JPH01249782A (en) | 1988-03-30 | 1988-03-30 | Potassium salt of organic silicon compound for catalyst having high activity and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01249782A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5786495A (en) * | 1995-03-03 | 1998-07-28 | Montell Technology Company Bv | Bridged bis-fluorenyl metallocenes, process for the preparation thereof and use thereof in catalysts for the polymerization of olefins |
| EP0604908B1 (en) * | 1992-12-30 | 2001-09-19 | Basell Technology Company B.V. | Process for the polymerisation of alpha-olefins using metallocene compounds having ligands of fluorenylic type |
| CN108598196A (en) * | 2018-04-19 | 2018-09-28 | 山东冬瑞高新技术开发有限公司 | A kind of high-weatherability solar cell backboard and preparation method thereof |
-
1988
- 1988-03-30 JP JP7458088A patent/JPH01249782A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0604908B1 (en) * | 1992-12-30 | 2001-09-19 | Basell Technology Company B.V. | Process for the polymerisation of alpha-olefins using metallocene compounds having ligands of fluorenylic type |
| US5786495A (en) * | 1995-03-03 | 1998-07-28 | Montell Technology Company Bv | Bridged bis-fluorenyl metallocenes, process for the preparation thereof and use thereof in catalysts for the polymerization of olefins |
| US6054404A (en) * | 1995-03-03 | 2000-04-25 | Montell Technology Company Bv | Bridged bis-fluorenyl metallocenes, process for the preparation thereof and use thereof in catalysts for the polymerization of olefins |
| US6365764B1 (en) * | 1995-03-03 | 2002-04-02 | Basell Technology Company Bv | Bridged bis-fluorenyl metallocenes process for the preparation thereof and use thereof in catalysts for the polymerization of olefins |
| CN108598196A (en) * | 2018-04-19 | 2018-09-28 | 山东冬瑞高新技术开发有限公司 | A kind of high-weatherability solar cell backboard and preparation method thereof |
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