JP2946035B1 - Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymer - Google Patents
Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymerInfo
- Publication number
- JP2946035B1 JP2946035B1 JP7330498A JP7330498A JP2946035B1 JP 2946035 B1 JP2946035 B1 JP 2946035B1 JP 7330498 A JP7330498 A JP 7330498A JP 7330498 A JP7330498 A JP 7330498A JP 2946035 B1 JP2946035 B1 JP 2946035B1
- Authority
- JP
- Japan
- Prior art keywords
- polar vinyl
- polymer
- vinyl monomer
- catalyst
- 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
Abstract
【要約】
【課題】 空気中で安定であり、アクリロニトリル、メ
タクリル酸エステル等極性基を側鎖に有する極性ビニル
モノマー重合用触媒及び極性ビニルポリマーの製造方法
を提供する。
【解決手段】 シクロペンタジエニル骨格を有する配位
子を含むコバルト錯体と有機アルミニウム化合物とから
なることを特徴とする極性ビニルモノマー重合用触媒。The present invention provides a catalyst for polymerizing a polar vinyl monomer which is stable in the air and has a polar group such as acrylonitrile or methacrylic ester in a side chain, and a method for producing a polar vinyl polymer. A catalyst for polymerizing a polar vinyl monomer, comprising a cobalt complex containing a ligand having a cyclopentadienyl skeleton and an organoaluminum compound.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、極性ビニルモノマ
ー重合用触媒及び極性ビニルポリマーの製造方法に関す
る。The present invention relates to a catalyst for polymerizing a polar vinyl monomer and a method for producing a polar vinyl polymer.
【０００２】[0002]
【従来の技術】ポリアクリロニトリル、ポリメタクリル
酸メチル等の極性基を側鎖に有する極性ビニルポリマー
は、非極性ビニルポリマーと比較してさまざまな機能を
有することが知られている。これらのポリマーにさらに
高い機能を付与するためには、生成ポリマーの一次構造
のより厳密な制御が不可欠であると考えられる。従来こ
れらのポリマーは主としてラジカル重合法により合成さ
れているが、この重合法を用る場合、成長種は、フリー
なラジカルであるため他の重合法と比較してその反応性
が高く、コントロールが難しいため、生成ポリマーの一
次構造すなわち立体構造や分子量等の制御、あるいいは
厳密なブロックポリマーの生成や末端基の制御は困難
で、現在までのところ新たな機能性の付与に至っていな
い。これに対し、有機金属錯体触媒による重合では、金
属が常に成長種の近傍に存在するため、その中心金属、
配位子等の組み合わせを選択することにより、成長種の
反応性やモノマーの挿入方向をコントロールすることが
比較的容易に行えるため、上記のような機能性の付与に
はより適した重合法であると考えられる。すでにエチレ
ン、プロピレン、スチレン等の非極性ビニルモノマーに
ついては、このような考え方に基づき有機金属錯体触媒
を用いた立体規則性重合やリビング重合が可能となり、
ブロックポリマーや末端基の制御等による高い機能性の
付与が行われている。極性基を有するビニルモノマーの
有機金属錯体触媒による重合については、極性基がしば
しば触媒毒となるため、対応する非極性ビニルモノマー
の重合に比べて著しく困難であり、その報告例は限られ
ている。現在まで知られている有機金属錯体触媒による
極性ビニルモノマーの単独重合を例示すると、鉄、コバ
ルト、ルテニウム錯体触媒による種々の極性ビニルモノ
マーの重合（ジャーナル・オブ・ポリマー・サイエンス
・ポリマー・レビュウズ．，１３，１６１（１９７
８））、希土類錯体触媒によるメタクリル酸エステルの
重合（ジャーナル・オブ・アメリカン・ケミカル・ソサ
イエティ．，１１４，４９０８（１９９２））、希土類
錯体触媒による極性ビニルモノマーの重合（マクロモレ
キュールズ．，２９，８０１４（１９９６））、ジルコ
ノセン錯体とホウ素化合物からなる触媒によるメタクリ
ル酸エステルの重合（マクロモレキュールズ．，２８，
３０６７（１９９５））等が挙げられる。しかしながら
これらの錯体による重合はほとんどがメタクリル酸エス
テル類のものであり、アクリロニトリルの重合例は少な
い。さらにこれらの錯体はいずれも空気中で不安定であ
り、その取り扱いや作業性の点で大きな問題があるた
め、現在までのところ工業化に至っていない。2. Description of the Related Art It is known that a polar vinyl polymer having a polar group such as polyacrylonitrile and polymethyl methacrylate in a side chain has various functions as compared with a nonpolar vinyl polymer. In order to impart higher functions to these polymers, it is considered that strict control of the primary structure of the resulting polymer is essential. Conventionally, these polymers are mainly synthesized by a radical polymerization method. However, when this polymerization method is used, the growing species is a free radical, so its reactivity is higher than other polymerization methods, and the control is high. Because of the difficulty, it is difficult to control the primary structure, ie, the three-dimensional structure and the molecular weight, of the produced polymer, or it is difficult to strictly control the production of the block polymer and the terminal groups, and so far no new functionality has been imparted. In contrast, in the polymerization using an organometallic complex catalyst, since the metal is always present near the growing species, the center metal,
By selecting a combination of ligands and the like, the reactivity of the growing species and the direction of insertion of the monomer can be controlled relatively easily. It is believed that there is. For non-polar vinyl monomers such as ethylene, propylene, and styrene, stereoregular polymerization and living polymerization using organometallic complex catalysts have become possible based on this concept.
High functionality is imparted by controlling the block polymer and terminal groups. The polymerization of a vinyl monomer having a polar group by an organometallic complex catalyst is significantly more difficult than the polymerization of the corresponding non-polar vinyl monomer, since the polar group often acts as a catalyst poison. . Examples of the homopolymerization of polar vinyl monomers with organometallic complex catalysts known to date include polymerization of various polar vinyl monomers with iron, cobalt and ruthenium complex catalysts (Journal of Polymer Science Polymer Reviews., 13, 161 (197
8)), polymerization of methacrylates with rare earth complex catalysts (Journal of American Chemical Society, 114, 4908 (1992)), polymerization of polar vinyl monomers with rare earth complex catalysts (Macromolecules, 29) , 8014 (1996)), polymerization of methacrylic acid esters with a catalyst comprising a zirconocene complex and a boron compound (Macromolecules., 28,
3067 (1995)). However, most of the polymerization by these complexes is based on methacrylic esters, and there are few polymerization examples of acrylonitrile. Furthermore, these complexes are unstable in the air, and have serious problems in handling and workability, and thus have not been industrialized so far.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、空気中で安
定であり、アクリロニトリル、メタクリル酸エステル等
極性基を側鎖に有する極性ビニルモノマー重合用触媒及
び極性ビニルポリマーの製造方法を提供することをその
課題とする。SUMMARY OF THE INVENTION The present invention provides a catalyst for the polymerization of a polar vinyl monomer which is stable in the air and has a polar group such as acrylonitrile or methacrylic ester in a side chain, and a process for producing a polar vinyl polymer. Is the subject.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を行った結果、分子内にシクロペ
ンタジエニル骨格を有する配位子を含むコバルト錯体と
有機アルミニウム化合物を組み合わせることにより得ら
れる触媒を用いて極性基を有するビニルモノマーを重合
すると、高重合度のポリマーが得られることを見出して
本発明を完成するに至った。すなわち、本発明によれ
ば、一般式（１） Ｃ5Ｈ5ＣｏＸＩ2 （１） 〔式中、Ｘはピリジン、ＰＲ1 3（Ｒ1：脂肪族基又は芳
香族基）又はＰＯＲ2 3（Ｒ2：脂肪族基又は芳香族基）
を示す。〕で表されるシクロペンタジエニル骨格を有す
る配位子を含むコバルト錯体と有機アルミニウム化合物
とからなることを特長とする酸性ビニルモノマー重合用
触媒が提供される。また、本発明によれば、前記極性ビ
ニルモノマー重合用触媒の存在下、極性ビニルモノマー
を重合させることを特徴とする極性ビニルポリマーの製
造方法が提供される。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a cobalt complex containing a ligand having a cyclopentadienyl skeleton in a molecule and an organoaluminum compound are obtained. The inventors have found that a polymer having a high degree of polymerization can be obtained by polymerizing a vinyl monomer having a polar group using a catalyst obtained by the combination, thereby completing the present invention. That is, according to the present invention, the general formula (1) C 5 H 5 CoXI 2 (1) wherein, X is pyridine, PR 1 3 (R 1: an aliphatic group or an aromatic group), or POR 2 3 ( R 2 : aliphatic group or aromatic group)
Is shown. And a cobalt complex containing a ligand having a cyclopentadienyl skeleton represented by the formula: and an organoaluminum compound. Further, according to the present invention, there is provided a method for producing a polar vinyl polymer, which comprises polymerizing a polar vinyl monomer in the presence of the above-mentioned catalyst for polymerizing a polar vinyl monomer.
【０００５】[0005]
【発明の実施の形態】本発明の極性ビニルモノマー重合
用触媒は、単独では極性ビニルポリマーに対し重合能を
有しないコバルト錯体（以下、Ｃｏ錯体という）と有機
アルミニウム化合物（以下、Ａｌ化合物ともいう）とか
らなるものである。本発明のＣｏ錯体は、下記一般式
（１）で表されるものである。 Ｃ5Ｈ5ＣｏＸＩ2 （１） 式中、Ｘはピリジン、ＰＲ1 3（Ｒ1：脂肪族基又は芳香
族基）又はＰ（ＯＲ2）3（Ｒ2：脂肪族基又は芳香族
基）を示す。BEST MODE FOR CARRYING OUT THE INVENTION The polar vinyl monomer polymerization catalyst of the present invention comprises a cobalt complex (hereinafter, referred to as a Co complex) and an organoaluminum compound (hereinafter, also referred to as an Al compound) which have no polymerization ability with respect to a polar vinyl polymer by itself. ). The Co complex of the present invention is represented by the following general formula (1). C 5 H 5 CoXI 2 (1), X is pyridine, PR 1 3 (R 1: an aliphatic group or an aromatic group) or P (OR 2) 3 (R 2: an aliphatic group or an aromatic group) Is shown.
【０００６】前記脂肪族基には、鎖状又は環状のアルキ
ル基が包含され、その炭素数は１〜１８、好ましくは１
〜３である。また、前記芳香族基には、アリール基又は
アリールアルキル基が包含され、その例としては、フェ
ニル、トリル、ナフチル、ベンジル等が挙げられる。The aliphatic group includes a chain or cyclic alkyl group having 1 to 18, preferably 1 carbon atoms.
~ 3. Further, the aromatic group includes an aryl group or an arylalkyl group, and examples thereof include phenyl, tolyl, naphthyl, and benzyl.
【０００７】本発明の触媒の他の成分であるＡｌ化合物
としては、トリアルキルアルミニウム（Ｒ3Ａｌ、Ｒ：
炭素数１〜１８、好ましくは１〜３のアルキル基）やポ
リ（メチルアミノキサン）等が挙げられる。The Al compound as another component of the catalyst of the present invention includes a trialkylaluminum (R 3 Al, R:
Examples thereof include an alkyl group having 1 to 18 carbon atoms, preferably 1 to 3 carbon atoms) and poly (methylaminoxan).
【０００８】本発明で用いる極性ビニルモノマーは、シ
アノ基、カルボキシル基、アルコキシカルボニル基、ア
セトキシ基等の極性基を側鎖に有するビニルモノマーで
ある。このようなものとしては、アクリロニトリル、メ
タクリロニトリル、メタクリル酸エステル、アクリル酸
エステル、酢酸ビニル等があげられる。本発明触媒は、
特にアクリロニトリル、メタクリル酸メチルを単独重合
してそれらのポリマーを製造するのに適している。The polar vinyl monomer used in the present invention is a vinyl monomer having a polar group such as a cyano group, a carboxyl group, an alkoxycarbonyl group and an acetoxy group in a side chain. Such materials include acrylonitrile, methacrylonitrile, methacrylate, acrylate, vinyl acetate, and the like. The catalyst of the present invention
In particular, it is suitable for homopolymerizing acrylonitrile and methyl methacrylate to produce those polymers.
【０００９】本発明により極性ビニルポリマーを得るに
は、前記重合触媒の存在下、極性ビニルモノマーを重合
させる。この場合の重合反応は、無溶媒、あるいは重合
反応に対して不活性で、重合時に液体である溶媒中で行
うのが望ましい。この場合の重合溶媒としては、ペンタ
ン、ヘキサン、ヘプタン等の飽和脂肪族炭化水素、シク
ロヘキサン、シクロヘプタン等の飽和環式炭化水素、ベ
ンゼン、トルエン等の芳香族炭化水素等が挙げられる。In order to obtain a polar vinyl polymer according to the present invention, a polar vinyl monomer is polymerized in the presence of the polymerization catalyst. In this case, the polymerization reaction is desirably performed without a solvent or in a solvent that is inert to the polymerization reaction and is liquid at the time of polymerization. Examples of the polymerization solvent in this case include saturated aliphatic hydrocarbons such as pentane, hexane and heptane, saturated cyclic hydrocarbons such as cyclohexane and cycloheptane, and aromatic hydrocarbons such as benzene and toluene.
【００１０】前記極性ビニルモノマーを単独重合させる
際の触媒使用量は一概に規定できないが、例えば、極性
ビニルモノマー１モル当たり、Ｃｏ錯体が１×１０-4モ
ル〜１×１０-2モルの割合である。なお、Ｃｏ錯体１モ
ル当たり、Ａｌ化合物は１０〜１０００モルの割合であ
る。The amount of the catalyst used when the polar vinyl monomer is homopolymerized cannot be specified unconditionally. For example, the ratio of the Co complex is from 1 × 10 -4 mol to 1 × 10 -2 mol per mol of the polar vinyl monomer. It is. The Al compound is in a ratio of 10 to 1000 mol per 1 mol of the Co complex.
【００１１】前記重合反応は、通常０〜８０℃で０．５
〜１００時間行われる。得られるポリマーの収率は、重
合温度、重合時間、触媒量、溶媒の種類及びその量等に
より変化するが、概ね６０％以下である。また、得られ
るポリマーの数平均分子量はやはり重合条件等に依存す
るが、約１０００〜約１００００である。The polymerization reaction is usually carried out at 0 to 80 ° C. for 0.5
Performed for ~ 100 hours. The yield of the obtained polymer varies depending on the polymerization temperature, the polymerization time, the amount of the catalyst, the type of the solvent and the amount thereof, but is generally about 60% or less. The number average molecular weight of the obtained polymer also depends on the polymerization conditions and the like, but is about 1,000 to about 10,000.
【００１２】[0012]
【実施例】以下、本発明を、実施例により具体的に説明
する。なお、重合体の分子量測定は、ＧＰＣを用い、展
開溶媒はＮ，Ｎ−ジメチルホルムアミド、カラム温度は
４０℃とした。測定された数平均分子量は、ポリスチレ
ン換算である。The present invention will be described below in more detail with reference to examples. The molecular weight of the polymer was measured using GPC, the developing solvent was N, N-dimethylformamide, and the column temperature was 40 ° C. The measured number average molecular weight is in terms of polystyrene.
【００１３】参考例１ 窒素ガスで十分に置換した２００ｍＬのフラスコに、９
ｇのＣ5Ｈ5Ｃｏ(ＣＯ)2、１３．１ｇのＰＰｈ3、テトラ
ヒドロフラン（ＴＨＦ）４０ｍＬを入れ、これに室温で
よう素１２．７ｇのＴＨＦ溶液を適下した。生成した結
晶を濾別し、少量のベンゼンで洗い、減圧乾燥したとこ
ろ、２１ｇのＣ5Ｈ5Ｃｏ(ＰＰｈ3)Ｉ2が得られた。Reference Example 1 9 mL was placed in a 200 mL flask sufficiently purged with nitrogen gas.
C 5 H 5 Co (CO) 2 in g, PPh 3 of 13.1 g, were placed tetrahydrofuran (THF) 40 mL, was Tekika a THF solution of iodine 12.7g for Less room temperature thereto. The product is filtered off crystals were washed with a small amount of benzene, and vacuum dried, 21g C 5 H 5 Co ( PPh 3) of I 2 was obtained.
【００１４】参考例２ 窒素ガスで十分に置換した２００ｍＬのフラスコに、９
ｇのＣ5Ｈ5Ｃｏ(ＣＯ)2、６．２ｇのＰ(ＯＭｅ)3、ＴＨ
Ｆ４０ｍＬを入れ、これに室温でよう素１２．７ｇのＴ
ＨＦ溶液を適下した。生成した結晶を濾別し、少量のベ
ンゼンで洗い、減圧乾燥したところ、１０．３ｇのＣ5
Ｈ5Ｃｏ(Ｐ(ＯＭｅ)3）Ｉ2が得られた。Reference Example 2 9 mL was placed in a 200 mL flask sufficiently purged with nitrogen gas.
g C for 5 H 5 Co (CO) 2 , 6.2g of P (OMe) 3, TH
F (40 mL), and at room temperature 12.7 g of T
The HF solution was dropped. The product is filtered off crystals were washed with a small amount of benzene, and vacuum dried, C 5 of 10.3g
H 5 Co (P (OMe) 3 ) I 2 was obtained.
【００１５】参考例３ 窒素ガスで十分に置換した２００ｍＬのフラスコに、９
ｇのＣ5Ｈ5Ｃｏ(ＣＯ)2、４．０ｇのＣ5Ｈ5Ｎ、ＴＨＦ
４０ｍＬを入れ、これに室温でよう素１２．７ｇのＴＨ
Ｆ溶液を適下した。生成した結晶を濾別し、少量のベン
ゼンで洗い、減圧乾燥したところ、９．１ｇのＣ5Ｈ5Ｃ
ｏ(Ｃ5Ｈ5Ｎ)Ｉ2が得られた。REFERENCE EXAMPLE 3 9 mL was placed in a 200 mL flask sufficiently purged with nitrogen gas.
g of C 5 H 5 Co (CO) 2, 4.0g of C 5 H 5 N, THF
40 mL, and 12.7 g of TH at room temperature
The F solution was dropped. The formed crystals were separated by filtration, washed with a small amount of benzene, and dried under reduced pressure to obtain 9.1 g of C 5 H 5 C.
o (C 5 H 5 N) I 2 was obtained.
【００１６】実施例１ 窒素ガスで十分に置換した２０ｍＬのフラスコに、トル
エン３ｍＬ、アクリロニトリル３ｍＬ、７．５ミリモル
Ｃ5Ｈ5Ｃｏ(ＰＰｈ3)Ｉ2、及び１．５モルのトリエチル
アルミニウムを入れ、室温で２４時間撹拌した。反応液
を塩酸酸性メタノールに注ぎポリマーを析出させ、これ
を乾燥したところ、仕込みモノマーに対し４６％のポリ
マーが得られた。生成したポリマーをＧＰＣ分析したと
ころ、数平均分子量（Ｍｎ）は４８００であった。Example 1 A 20 mL flask sufficiently purged with nitrogen gas was charged with 3 mL of toluene, 3 mL of acrylonitrile, 7.5 mmol of C 5 H 5 Co (PPh 3 ) I 2 , and 1.5 mol of triethylaluminum. And stirred at room temperature for 24 hours. The reaction solution was poured into hydrochloric acid-methanol to precipitate a polymer, which was dried. As a result, 46% of the polymer relative to the charged monomers was obtained. GPC analysis of the resulting polymer showed a number average molecular weight (Mn) of 4,800.
【００１７】実施例２ 実施例１と同様に、メタクリル酸メチルを室温で２４時
間重合したところ収率２０％でポリマーが得られた。生
成したポリマーをＧＰＣ分析したところ、Ｍｎは３６０
０であった。Example 2 In the same manner as in Example 1, methyl methacrylate was polymerized at room temperature for 24 hours to obtain a polymer with a yield of 20%. GPC analysis of the produced polymer revealed that Mn was 360
It was 0.
【００１８】実施例３ 空気中室温で２４時間放置したＣ5Ｈ5Ｃｏ(ＰＰｈ3)Ｉ2
を用いて実施例１と同様の重合を行ったところ４３％の
収率でＭｎ５０００のポリマーが得られた。Example 3 C 5 H 5 Co (PPh 3 ) I 2 left in air at room temperature for 24 hours
Was carried out in the same manner as in Example 1 to obtain a polymer having Mn of 5000 with a yield of 43%.
【００１９】実施例４ 実施例１と同様に、Ｃ5Ｈ5Ｃｏ(Ｐ(ＯＭｅ)3）Ｉ2を用
いてアクリロニトリルを室温で２４時間重合したところ
収率４９％でポリマーが得られた。生成したポリマーを
ＧＰＣ分析したところ、Ｍｎは４３００であった。Example 4 In the same manner as in Example 1, acrylonitrile was polymerized at room temperature for 24 hours using C 5 H 5 Co (P (OMe) 3 ) I 2 to obtain a polymer in a yield of 49%. Gn analysis of the produced polymer revealed that Mn was 4,300.
【００２０】実施例５ 実施例１と同様に、Ｃ5Ｈ5Ｃｏ(Ｃ5Ｈ5Ｎ)I2を用いてア
クリロニトリルを室温で２４時間重合したところ収率２
５％でポリマーが得られた。生成したポリマーをＧＰＣ
分析したところ、Ｍｎは３５００であった。Example 5 In the same manner as in Example 1, acrylonitrile was polymerized using C 5 H 5 Co (C 5 H 5 N) I 2 at room temperature for 24 hours.
Polymer was obtained at 5%. GPC generated polymer
Upon analysis, Mn was 3,500.
【００２１】実施例の結果から明らかなように、Ｃｏ錯
体とＡｌ化合物からなる触媒は、これをアクリロニトリ
ルやメタクリル酸エステル等の極性ビニルモノマーの重
合に用いると、Ｃｏ錯体のみからなる触媒からは生成し
ないポリマーを生成する。また、Ｃｏ錯体は空気中に長
時間放置することによってもその効果を減じない。As is evident from the results of the examples, when a catalyst comprising a Co complex and an Al compound is used for the polymerization of a polar vinyl monomer such as acrylonitrile or methacrylic acid ester, the catalyst is formed from a catalyst comprising only the Co complex. Not produce polymer. The effect of the Co complex does not decrease even when it is left in the air for a long time.
【００２２】[0022]
【発明の効果】本発明の空気中において安定な触媒を用
いて極性ビニルモノマーを重合することにより、良好な
収率でポリマーを得ることができる。According to the present invention, a polymer can be obtained in good yield by polymerizing a polar vinyl monomer using a stable catalyst in air.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅井 道彦 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 鈴木 靖三 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 宮沢 哲 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 村田 昌英 東京都文京区水道二丁目３番15−504号 (72)発明者 川辺 正直 茨城県つくば市竹園二丁目６番２−203 号 (72)発明者 尾崎 裕之 茨城県つくば市小野川四丁目６−202号 (72)発明者 福井 祥文 茨城県つくば市二の宮四丁目６番３− 507号 (72)発明者 岸 直哉 石川県金沢市額乙丸長222−201号 審査官 藤本 保 (58)調査した分野(Int.Cl.6，ＤＢ名) C08F 4/70 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Michihiko Asai 1-1-1, Higashi, Tsukuba City, Ibaraki Pref. Institute of Industrial Science and Technology (72) Inventor Yasumi Suzuki 1-1-1 Higashi, Tsukuba City, Ibaraki Pref. (72) Inventor: Satoshi Miyazawa 1-1-1, Higashi, Tsukuba, Ibaraki Pref., Japan Institute of Materials Science and Technology (72) Inventor: Masahide Murata 2-3-15-1504, Suido, Bunkyo-ku, Tokyo (72) Inventor Masanao Kawabe 2-6-1203 Takezono, Tsukuba-shi, Ibaraki Prefecture (72) Hiroyuki Ozaki 4-6-202 Onogawa, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Yoshifumi Fukui Ninomiya, Tsukuba-city, Ibaraki Prefecture 4-Chome 6-3-507 (72) Inventor Naoya Kishi 222-201 Naotomaru Naga, Kanazawa City, Ishikawa Prefecture Examiner Tamotsu Fujimoto (58) Field surveyed (Int.Cl. 6 , DB name) C08F 4/70 CA (STN)
Claims (2)
香族基）又はＰＯＲ2 3（Ｒ2：脂肪族基又は芳香族基）
を示す。〕で表されるシクロペンタジエニル骨格を有す
る配位子を含むコバルト錯体と有機アルミニウム化合物
とからなることを特徴とする極性ビニルモノマー重合用
触媒。1. A general formula (1) C 5 H 5 CoXI 2 (1) wherein, X is pyridine, PR 1 3 (R 1: an aliphatic group or an aromatic group), or POR 2 3 (R 2: Aliphatic or aromatic group)
Is shown. ] A polar vinyl monomer polymerization catalyst comprising a cobalt complex containing a ligand having a cyclopentadienyl skeleton represented by the formula: and an organoaluminum compound.
合用触媒の存在下、極性ビニルモノマーを重合させるこ
とを特徴とする極性ビニルポリマーの製造方法。2. A method for producing a polar vinyl polymer, comprising polymerizing a polar vinyl monomer in the presence of the catalyst for polymerizing a polar vinyl monomer according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7330498A JP2946035B1 (en) | 1998-03-06 | 1998-03-06 | Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7330498A JP2946035B1 (en) | 1998-03-06 | 1998-03-06 | Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2946035B1 true JP2946035B1 (en) | 1999-09-06 |
| JPH11255818A JPH11255818A (en) | 1999-09-21 |
Family
ID=13514300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7330498A Expired - Lifetime JP2946035B1 (en) | 1998-03-06 | 1998-03-06 | Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2946035B1 (en) |
-
1998
- 1998-03-06 JP JP7330498A patent/JP2946035B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11255818A (en) | 1999-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6114482A (en) | Process for the controlled radical polymerization or copolymerization of (meth) acrylic and vinyl monomers and (co) polymers obtained | |
| JPS6368608A (en) | Living polymer and its production | |
| KR20150143579A (en) | A novel transition metal based pro-catalyst and a process for its preparation | |
| JP2854013B2 (en) | Method for producing 1-olefin polymer, catalyst used therefor, metallocene as transition metal component thereof, and method for producing this metallocene | |
| US5328970A (en) | Living polymerization method | |
| JPH07649B2 (en) | Method for producing catalyst component for olefin polymerization | |
| CN108530572B (en) | Preparation method of ethylene-styrene derivative copolymer | |
| Stuhldreier et al. | A cationic bridged zirconocene complex as the catalyst for the stereospecific polymerization of methyl methacrylate | |
| CN111556878B (en) | Supported metallocene catalyst and method for preparing polypropylene using the same | |
| Tian et al. | Ethylene Polymerization with Sila‐Bridged Dinuclear Zirconocene Catalysts | |
| JP2946035B1 (en) | Polar vinyl monomer polymerization catalyst and method for producing polar vinyl polymer | |
| JPH1017633A (en) | Production of acrylic block copolymer | |
| JP2003246791A (en) | Trivalent organic lanthanoid complex, catalyst for manufacturing (meth)acrylic polymer, and (meth)acrylic polymer | |
| JPH01108203A (en) | Manufacture of polyalkenyl ether | |
| KR102520078B1 (en) | Catalyst for Addition Polymerization of Polar Vinyl Monomers and Method for Preparing Polar Vinyl Polymer Using the Same | |
| US5489651A (en) | Polymerization using bimetallic bis-lanthanoid initiators | |
| JPH11322835A (en) | Catalyst for polymerizing polar vinyl monomer and production of polymer from the monomer | |
| JP2850152B2 (en) | Method for producing ethylene copolymer | |
| JP2794891B2 (en) | Method for producing ethylene-vinyl acetate copolymer | |
| JP2999307B2 (en) | Propylene / styrene block copolymer and method for producing the same | |
| EP1092729B1 (en) | Polymerization catalyst, novel transition metal compound, and polymerization method and copolymer using them | |
| JP3393722B2 (en) | Method for polymerizing alkyl methacrylate | |
| JP2001114818A (en) | Catalyst for polymerizing acrylonitrile and method for producing polyacrylonitrile using the same | |
| JP4742410B2 (en) | Method for producing vinyl chloride polymer | |
| JP2000178293A (en) | Semi-sandwich complex of non-cross-linked mononucle, bisalkyl metal having polymerization activity based on rare earth metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313118 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 Free format text: JAPANESE INTERMEDIATE CODE: R313118 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080702 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |