JP5575702B2 - Catalyst composition for polymerization of vinyl monomers and use of the monomer for polymerization of vinyl monomers using the composition - Google Patents

Catalyst composition for polymerization of vinyl monomers and use of the monomer for polymerization of vinyl monomers using the composition Download PDF

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JP5575702B2
JP5575702B2 JP2011113568A JP2011113568A JP5575702B2 JP 5575702 B2 JP5575702 B2 JP 5575702B2 JP 2011113568 A JP2011113568 A JP 2011113568A JP 2011113568 A JP2011113568 A JP 2011113568A JP 5575702 B2 JP5575702 B2 JP 5575702B2
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京子 野崎
誠 山下
大嗣 井田
俊也 魚住
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Kuraray Co Ltd
University of Tokyo NUC
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本発明は、周期律表第１０族の元素とホスフィン配位子を含有するビニル系モノマー重合用触媒組成物、およびそれを用いたビニル系モノマーの重合方法に関する。   The present invention relates to a vinyl monomer polymerization catalyst composition containing an element belonging to Group 10 of the periodic table and a phosphine ligand, and a method for polymerizing a vinyl monomer using the same.

ポリマーの高機能化の手段として、種々の官能基を重合体中に導入する方法がある。例えば、側鎖に官能基を有するビニル系モノマーの付加重合法により、様々な性能を有するポリマーが得られる。ビニル系モノマーの種類は豊富であることからも、この方法は簡便かつ有用な手段といえる。   As a means for enhancing the functionality of the polymer, there is a method of introducing various functional groups into the polymer. For example, polymers having various performances can be obtained by an addition polymerization method of a vinyl monomer having a functional group in a side chain. Since there are a wide variety of vinyl monomers, this method is a simple and useful means.

ビニル系モノマーの付加重合法としては、ラジカル重合、カチオン重合、アニオン重合、配位重合等が知られている。ラジカル重合法は重合可能なモノマーの適用範囲が広く、α−オレフィン、スチレン誘導体等の炭化水素系モノマーのみならず、エステル基、水酸基、アミノ基、カルボキシル基等の官能基を有するモノマーでも重合可能である。その反面、ラジカル重合法は重合を開始させるためには高温に加熱することを必要とする。また、低温下でも重合開始能のある開始剤を用いた場合には生産性に乏しく、生産性を確保するために乳化剤を用いた乳化重合法を行う場合には操作が煩雑となる、といった問題がある。   As addition polymerization methods for vinyl monomers, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like are known. The radical polymerization method has a wide range of applications for polymerizable monomers and can be used to polymerize not only hydrocarbon monomers such as α-olefins and styrene derivatives, but also monomers having functional groups such as ester groups, hydroxyl groups, amino groups, and carboxyl groups. It is. On the other hand, the radical polymerization method requires heating to a high temperature in order to initiate the polymerization. In addition, when an initiator capable of initiating polymerization even at low temperatures is used, the productivity is poor, and the operation is complicated when an emulsion polymerization method using an emulsifier is used to ensure productivity. There is.

一方、カチオン重合法およびアニオン重合法は、重合可能なモノマーの適用範囲が狭いという欠点がある。チーグラー・ナッタ触媒、メタロセン触媒等を用いた重合に代表される配位重合では、近年、官能基を有するモノマーを重合可能とする後周期金属錯体を用いた重合法も開発され、アクリル酸エステル、ノルボルネオールといった水酸基含有オレフィン等の官能基含有モノマーとエチレンとの共重合法も開発されている（特許文献１〜８）。   On the other hand, the cationic polymerization method and the anionic polymerization method have a drawback that the application range of the polymerizable monomer is narrow. In coordination polymerization represented by polymerization using a Ziegler-Natta catalyst, a metallocene catalyst, etc., recently, a polymerization method using a late metal complex capable of polymerizing a monomer having a functional group has been developed. A copolymerization method of ethylene with a functional group-containing monomer such as a hydroxyl group-containing olefin such as norbornol has also been developed (Patent Documents 1 to 8).

しかしながら、このような重合方法でも官能基含有モノマーを主成分とする重合は困難であり、官能基を有さないα−オレフィン等のモノマーに少量の官能基含有モノマーを導入した共重合を製造できるにすぎない。   However, even with such a polymerization method, it is difficult to polymerize with a functional group-containing monomer as a main component, and a copolymer in which a small amount of a functional group-containing monomer is introduced into a monomer such as an α-olefin having no functional group can be produced. Only.

国際公開第９６／２３０１０号パンフレットInternational Publication No. 96/23010 Pamphlet 国際公開第９８／４２６６４号パンフレットInternational Publication No. 98/42664 Pamphlet 国際公開第９８／４２６６５号パンフレットInternational Publication No. 98/42665 Pamphlet 国際公開第９８／５６８３９号パンフレットInternational Publication No. 98/56839 Pamphlet 米国特許第６３０３７２０号明細書US Pat. No. 6,303,720 国際公開第０１／９２３５４号パンフレットInternational Publication No. 01/92354 Pamphlet 国際公開第０１／９６４０６号パンフレットInternational Publication No. 01/96406 Pamphlet 国際公開第０２／０５９１６５号パンフレットInternational Publication No. 02/059165 Pamphlet

したがって本発明の課題は、ビニル系モノマー、特に官能基を含有するビニル系モノマーを比較的温和な条件下で生産性高く重合するための触媒組成物およびそれを用いた重合方法を提供することにある。   Accordingly, an object of the present invention is to provide a catalyst composition for polymerizing a vinyl monomer, particularly a vinyl monomer containing a functional group, under relatively mild conditions with high productivity and a polymerization method using the same. is there.

上記の課題を解決すべく鋭意研究を重ねた結果、本発明者等は、周期律表第１０族の金属元素と１金属当たり一つのホスフィン配位子を有する金属化合物を触媒組成物として用いることにより、ビニル系モノマー、特に官能基を含有するビニル系モノマーを比較的温和な条件下で生産性高く重合できることを見出し、本発明を完成するに至った。   As a result of earnest research to solve the above problems, the present inventors use a metal compound having a metal element of Group 10 of the periodic table and one phosphine ligand per metal as a catalyst composition. Thus, it has been found that vinyl monomers, particularly vinyl monomers containing a functional group, can be polymerized with high productivity under relatively mild conditions, and the present invention has been completed.

すなわち本発明は、ビニル系モノマー重合用触媒組成物であって、下記式（Ｉ）、（ＩＩ）および（ＩＩＩ）：

Figure 0005575702
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基または置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ｘ１、Ｘ２、Ｘ３およびＸ４はそれぞれ、水素、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基、ハロゲン、アセトキシ基、アミノ基、アミド基、カルボキシル基、ニトロ基、カルボニル、置換基を有してもよいトリフルオロメタンスルホニル基、またはパークロロを表し、Ｍ１およびＭ２はそれぞれ周期律表第１０族の元素を表す。）で示される金属化合物からなる群から選ばれた少なくとも１種の金属化合物を含む成分Ａを含有する、前記重合用触媒組成物に関する。 That is, the present invention relates to a vinyl monomer polymerization catalyst composition comprising the following formulas (I), (II) and (III):
Figure 0005575702
 (In the formula, each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 has an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent. Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, and X 1 , X 2 , X 3 and X 4 are each hydrogen and an optionally substituted aliphatic hydrocarbon having 1 to 20 carbon atoms Group, optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen, acetoxy group, amino group, amide group, carboxyl group, nitro group, carbonyl, trifluoro group optionally having substituent Component A containing at least one metal compound selected from the group consisting of metal compounds represented by the following: a lomethanesulfonyl group, or perchloro, wherein M 1 and M 2 each represent an element of Group 10 of the periodic table. Containing the polymerization catalyst composition About.

また本発明は、（ａ）周期律表第１、２、１１、１２、１３、１５および１６族から選ばれた少なくとも１種の元素、（ｂ）置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基および／または置換基を有してもよい炭素数６〜４０の芳香族炭化水素基ならびに（ｃ）過塩素酸基、からなる３つの群のうちの少なくとも２つの群からそれぞれ１種以上選ばれた、元素および／または基を有する化合物を含む成分Ｂをさらに含有する、請求項１に記載の重合用触媒組成物に関する。   The present invention also provides (a) at least one element selected from Groups 1, 2, 11, 12, 13, 15, and 16 of the periodic table, and (b) carbon number 1 which may have a substituent. At least two of the three groups consisting of an aliphatic hydrocarbon group of -20 and / or an aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent and (c) a perchloric acid group It is related with the catalyst composition for polymerization of Claim 1 which further contains the component B containing the compound which has an element and / or group each chosen 1 or more types from the group.

さらに本発明は、Ｍ１および／またはＭ２の金属がパラジウムである、前記重合用触媒組成物に関する。 Furthermore, the present invention relates to the polymerization catalyst composition, wherein the metal of M 1 and / or M 2 is palladium.

また本発明は、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、置換基を有してもよいｔｅｒｔ−ブチル基、置換基を有してもよいシクロヘキシル基、置換基を有してもよいビフェニル基、置換基を有してもよいナフチル基、置換基を有してもよいアントリル基、置換基を有してもよいフェナントリル基、または置換基を有してもよいトリル基である、前記重合用触媒組成物に関する。 In the present invention, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may have a tert-butyl group which may have a substituent, a cyclohexyl group which may have a substituent, or a substituent. A biphenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthryl group which may have a substituent, a phenanthryl group which may have a substituent, or a substituent It is related with the said catalyst composition for polymerization which is a good tolyl group.

さらに本発明は、Ｘ１、Ｘ２、Ｘ３およびＸ４がそれぞれ、水素、置換基を有してもよいメチル基、臭素、塩素、ヨウ素、置換基を有してもよいフェニル基、置換基を有してもよいトリフルオロメタンスルホニル基、またはパークロロである、前記重合用触媒組成物に関する。 Furthermore, in the present invention, X 1 , X 2 , X 3 and X 4 are each hydrogen, a methyl group which may have a substituent, bromine, chlorine, iodine, a phenyl group which may have a substituent, a substituted group It is related with the said catalyst composition for polymerization which is the trifluoromethanesulfonyl group which may have a group, or perchloro.

また本発明は、成分Ｂが有機リチウム化合物、有機マグネシウム化合物、トリフルオロメタンスルホン酸塩、過塩素酸塩、有機亜鉛化合物、有機ホウ素化合物、有機ホウ酸塩、または有機アルミニウム化合物である、前記重合用触媒組成物に関する。   In the present invention, the component B is an organic lithium compound, an organic magnesium compound, a trifluoromethanesulfonate, a perchlorate, an organic zinc compound, an organic boron compound, an organic borate, or an organic aluminum compound. The present invention relates to a catalyst composition.

さらに本発明は、前記重合用触媒組成物のビニル系モノマーの重合への使用に関する。   The present invention further relates to the use of the polymerization catalyst composition for the polymerization of vinyl monomers.

また本発明は、ビニル系モノマーが、アクリル酸エステル、メタクリル酸エステル、ビニルエーテル、ビニルエステル、エチレン、α-オレフィン、スチレン誘導体およびジエン誘導体からなる群から選ばれた少なくとも１種である、前記ビニル系モノマーの重合への使用に関する。   In the present invention, the vinyl monomer may be at least one selected from the group consisting of acrylic acid esters, methacrylic acid esters, vinyl ethers, vinyl esters, ethylene, α-olefins, styrene derivatives, and diene derivatives. It relates to the use of monomers for polymerization.

以上のとおり、本発明のビニル系モノマー重合用触媒組成物は、周期律表第１０族の元素と、１金属原子当り一つのホスフィン配位子を有する金属化合物からなる成分Ａを含有するので、官能基を含有するモノマーを含む重合体を、比較的温和な条件下で生産性高く製造することが可能である。   As described above, the catalyst composition for vinyl-based monomer polymerization of the present invention contains a component A composed of a metal compound having an element of Group 10 of the periodic table and one phosphine ligand per metal atom. A polymer containing a monomer containing a functional group can be produced with high productivity under relatively mild conditions.

本発明のビニル系モノマー重合用触媒組成物に含まれる成分Ａは、下記式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される金属化合物からなる群から選ばれた少なくとも１種の金属化合物を含有する。該金属化合物は１金属原子当り一つのホスフィン配位子を有する。金属化合物の金属Ｍ１およびＭ２はそれぞれ、周期律表第１０族のニッケル、パラジウムまたは白金であり、特にパラジウムが好ましい。 Component A contained in the vinyl monomer polymerization catalyst composition of the present invention comprises at least one metal compound selected from the group consisting of metal compounds represented by the following formulas (I), (II) and (III): contains. The metal compound has one phosphine ligand per metal atom. The metals M 1 and M 2 of the metal compound are each nickel, palladium or platinum belonging to Group 10 of the periodic table, and palladium is particularly preferable.

Figure 0005575702
式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基または置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表す。上記炭素数１〜２０の脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基等の直鎖、分枝鎖または環状の脂肪族炭化水素基が挙げられ、炭素数６〜２０の芳香族炭化水素基としては、フェニル基、ナフチル基、ビフェニル基、アントリル基、フェナントリル基、インデニル基、フルオレニル基、アズレニル基等が挙げられる。また、これらの基の置換基としては、上記の炭素数１〜２０の脂肪族炭化水素基、上記の炭素数６〜２０の芳香族炭化水素基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、tert−ブトキシ基等のアルコキシ基、フェノキシ基等のアリロキシ基、ハロゲン（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、アセトキシ基、ニトロ基、スルホン酸基、カルボキシル基、アミノ基等の官能基等が挙げられる。これらの置換基はさらに置換基を有していてもよい。
Figure 0005575702
 In the formula, each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may have an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent. It represents a good aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Straight, branched or cyclic fat such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group, and azulenyl group. Moreover, as a substituent of these groups, said C1-C20 aliphatic hydrocarbon group, said C6-C20 aromatic hydrocarbon group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group , Alkoxy groups such as tert-butoxy group, allyloxy groups such as phenoxy group, functional groups such as halogen (F, Cl, Br, I), acetoxy group, nitro group, sulfonic acid group, carboxyl group, amino group, etc. It is done. These substituents may further have a substituent.

Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６の好ましい例としては、置換基を有してもよいｔｅｒｔ−ブチル基、置換基を有してもよいシクロヘキシル基、置換基を有してもよいビフェニル基、置換基を有してもよいナフチル基、置換基を有してもよいアントリル基、置換基を有してもよいフェナントリル基、置換基を有してもよいｏ−トリル基、ｍ−トリル基またはｐ−トリル基等が挙げられる。 Preferred examples of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include a tert-butyl group which may have a substituent, a cyclohexyl group which may have a substituent, and a substituent. Biphenyl group which may have, naphthyl group which may have substituent, anthryl group which may have substituent, phenanthryl group which may have substituent, o which may have substituent -Tolyl group, m-tolyl group, p-tolyl group and the like can be mentioned.

Ｘ１、Ｘ２、Ｘ３およびＸ４はそれぞれ、水素、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基、ハロゲン、アセトキシ基、アミノ基、アミド基、カルボキシル基、ニトロ基、カルボニル、置換基を有してもよいトリフルオロメタンスルホニル基、またはパークロロを表す。ここで、炭素数１〜２０の脂肪族炭化水素基および炭素数６〜２０の芳香族炭化水素基としては、上記Ｒ１〜Ｒ６で挙げた脂肪族炭化水素基および芳香族炭化水素基が挙げられる。またこれらの基の置換基としては、上記の炭素数１〜２０の脂肪族炭化水素基、上記の炭素数６〜２０の芳香族炭化水素基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔｅｒｔ−ブトキシ基等のアルコキシ基、フェノキシ基等のアリロキシ基、ハロゲン（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、アセトキシ基、ニトロ基、スルホン酸基、カルボキシル基、アミノ基等の官能基等が挙げられる。また、これらの置換基はさらに置換基を有していてもよい。Ｘ１、Ｘ２、Ｘ３およびＸ４の好ましい例としては、水素、置換基を有してもよいメチル基、置換基を有してもよいフェニル基、１−アセトキシプロピル基、塩素、臭素、ヨウ素、カルボニル、置換基を有してもよいトリフルオロメタンスルホニル基、パークロロ等が挙げられる。 X 1 , X 2 , X 3 and X 4 are each hydrogen, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and optionally having 6 to 20 carbon atoms. An aromatic hydrocarbon group, a halogen, an acetoxy group, an amino group, an amide group, a carboxyl group, a nitro group, a carbonyl, a trifluoromethanesulfonyl group which may have a substituent, or perchloro is represented. Here, examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 20 carbon atoms include the aliphatic hydrocarbon groups and aromatic hydrocarbon groups mentioned in the above R 1 to R 6. Can be mentioned. Moreover, as a substituent of these groups, the above-mentioned aliphatic hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, Examples include alkoxy groups such as tert-butoxy group, allyloxy groups such as phenoxy group, functional groups such as halogen (F, Cl, Br, I), acetoxy group, nitro group, sulfonic acid group, carboxyl group and amino group. . Moreover, these substituents may further have a substituent. Preferred examples of X 1 , X 2 , X 3 and X 4 include hydrogen, an optionally substituted methyl group, an optionally substituted phenyl group, a 1-acetoxypropyl group, chlorine and bromine. , Iodine, carbonyl, an optionally substituted trifluoromethanesulfonyl group, perchloro and the like.

また、式（Ｉ）、（ＩＩ）および（ＩＩＩ）において示される実線は、それぞれ共有結合、イオン結合および配位結合のいずれかを表す。    In addition, the solid lines shown in the formulas (I), (II), and (III) each represent a covalent bond, an ionic bond, or a coordinate bond.

式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される金属化合物としては、例えば下記の構造で示される化合物が挙げられる。

Figure 0005575702
Examples of the metal compounds represented by the formulas (I), (II) and (III) include compounds represented by the following structures.
Figure 0005575702

式（Ｉ）、（ＩＩ）、および（ＩＩＩ）で示される金属化合物の具体例としては、（トリｔｅｒｔ−ブチルホスフィン）ジクロロパラジウム、（トリｔｅｒｔ−ブチルホスフィン）クロロメチルパラジウム、（トリｔｅｒｔ−ブチルホスフィン）ジメチルパラジウム、（トリｔｅｒｔ−ブチルホスフィン）ジブロモパラジウムダイマー、（トリシクロヘキシルホスフィン）ジクロロパラジウム、（トリシクロヘキシルホスフィン）クロロメチルパラジウム、（トリシクロヘキシルホスフィン）ジメチルパラジウム、[（ジｔｅｒｔ−ブチル）ビフェニル]ホスフィンジクロロパラジウム、[（ジｔｅｒｔ−ブチル）ビフェニル]ホスフィンクロロメチルパラジウム、[（ジｔｅｒｔ−ブチル）ビフェニル]ホスフィンジメチルパラジウム、（トリｏ−トリルホスフィン）ジクロロパラジウム、（トリｏ−トリルホスフィン）クロロメチルパラジウム、（トリｏ−トリルホスフィン）ジメチルパラジウム等が挙げられる。   Specific examples of the metal compounds represented by the formulas (I), (II), and (III) include (tritert-butylphosphine) dichloropalladium, (tritert-butylphosphine) chloromethylpalladium, (tritert-butyl). Phosphine) dimethylpalladium, (tritert-butylphosphine) dibromopalladium dimer, (tricyclohexylphosphine) dichloropalladium, (tricyclohexylphosphine) chloromethylpalladium, (tricyclohexylphosphine) dimethylpalladium, [(ditert-butyl) biphenyl] Phosphinedichloropalladium, [(ditert-butyl) biphenyl] phosphinechloromethylpalladium, [(ditert-butyl) biphenyl] phosphinedimethylpalladium, (tri o- Lil phosphine) dichloropalladium, (tri o- tolylphosphine) chloromethyl palladium, (tri-o- tolylphosphine) dimethyl palladium.

成分Ｂは、（ａ）周期律表第１、２、１１、１２、１３、１５および１６族から選ばれた少なくとも１種の元素、（ｂ）置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基および／または置換基を有してもよい炭素数６〜４０の芳香族炭化水素基ならびに（ｃ）過塩素酸基、からなる３つの群のうちの少なくとも２つの群からそれぞれ１種以上選ばれた、元素および／または基を有する化合物を含む。置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基および置換基を有してもよい炭素数６〜４０の芳香族炭化水素基は、上記のＲ１〜Ｒ６におけるこれらの基と同義である。 Component B is (a) at least one element selected from Groups 1, 2, 11, 12, 13, 15, and 16 of the periodic table, and (b) an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 aliphatic hydrocarbon groups and / or an aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and (c) a perchloric acid group, at least two of the three groups 1 or more compounds each having an element and / or a group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent are the above-described R 1 to R 6 . It is synonymous with the group of

成分Ｂに含まれる化合物としては、アルキルリチウム、アルキルナトリウム、アルキルマグネシウム、トリフルオロメタンスルホン酸塩、過塩素酸塩、アルキル亜鉛、アルキルホウ素、ホウ酸塩、アルキルアルミニウム等が挙げられる。具体例としては、メチルリチウム、ブチルリチウム、フェニルリチウム、ブチルナトリウム、ブチルエチルマグネシウム、臭化メチルマグネシウム、臭化エチルマグネシウム、臭化ブチルマグネシウム、臭化フェニルマグネシウム、塩化メチルマグネシウム、塩化エチルマグネシウム、塩化ブチルマグネシウム、塩化フェニルマグネシウム、トリフルオロメタンスルホン酸銀、過塩素酸銀、過塩素酸トリフェニルメチル、ジエチル亜鉛、トリスペンタフルオロフェニルホウ素、トリス（トリフルオロメチル）ホウ素、テトラキスペンタフルオロフェニルホウ酸トリフェニルメチル、テトラキス[３,５−ジ（トリフルオロメチル）フェニル]ホウ酸トリフェニルメチル、テトラキス[３,５−ジ（トリフルオロメチル）フェニル]ホウ酸ナトリウム、テトラキス[３,５−ジ（トリフルオロメチル）フェニル]ホウ酸ビス（ジエチルエーテル）、トリメチルアルミニウム、トリエチルアルミニウム、トリイソプロピルアルミニウム、トリイソブチルアルミニウム、ジメチルアルミニウムクロライド、ジエチルアルミニウムクロライド、エチルアルミニウムジクロライド、エチルアルミニウムセスキクロライド、イソブチルアルミニウムメトキシド、イソブチルアルミニウムエトキシド、イソブチルアルミニウムイソプロポキシド、ジエチルアルミニウムエトキシド、ジブチルアルミニウムブトキシド、エチルアルミニウムセスキエトキシド、ブチルアルミニウムセスキブトキシド、水素化ジイソプロピルアルミニウム、メチルアルミニウムビス（２，６−ジtert−ブチルフェノキシド）、メチルアルミニウムビス（２，６−ジtert−ブチル−４−メチルフェノキシド）、イソブチルアルミニウムビス（２，６−ジtert−ブチルフェノキシド）、イソブチルアルミニウムビス（２，６−ジtert-ブチル−４−メチルフェノキシド）、メチルアルミニウムビス{２−（Ｎ−フェニルイミノ）フェノキシド}、イソブチルアルミニウムビス{２−（Ｎ−フェニルイミノ）フェノキシド}、ジメチルアルミニウム{２−（Ｎ−フェニルイミノ）フェノキシド}、ジメチルアルミニウム（Ｎ，Ｎ’−ジイソプロピルアセトアミジナート）、ジメチルアルミニウム（Ｎ，Ｎ’−ジシクロヘキシルアセトアミジナート）、ジメチルガリウム（Ｎ，Ｎ’−ジイソプロピルアセトアミジナート）、ジメチルガリウム（Ｎ，Ｎ’−ジシクロヘキシルアセトアミジナート）、酸素原子や窒素原子を介して２個以上のアルミニウムが結合したアルミノキサン化合物等が挙げられる。中でもトリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、ジエチルアルミニウムクロライド、エチルアルミニウムジクロライド、アルミノキサン化合物等が好ましい。成分Ｂは、これらの化合物の１種又は２種以上を混合して用いることができる。   Examples of the compound contained in Component B include alkyl lithium, alkyl sodium, alkyl magnesium, trifluoromethane sulfonate, perchlorate, alkyl zinc, alkyl boron, borate, and alkyl aluminum. Specific examples include methyl lithium, butyl lithium, phenyl lithium, butyl sodium, butyl ethyl magnesium, methyl magnesium bromide, ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium bromide, methyl magnesium chloride, ethyl magnesium chloride, chloride. Butyl magnesium, phenyl magnesium chloride, silver trifluoromethanesulfonate, silver perchlorate, triphenylmethyl perchlorate, diethyl zinc, trispentafluorophenyl boron, tris (trifluoromethyl) boron, tetraphenyl pentakis pentafluorophenyl borate Methyl, tetrakis [3,5-di (trifluoromethyl) phenyl] triphenylmethylborate, tetrakis [3,5-di (trifluoromethyl) phenyl] borate, Trakis [3,5-di (trifluoromethyl) phenyl] borate bis (diethyl ether), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum Sesquichloride, isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, diisopropylaluminum hydride, methylaluminum bis (2, 6-ditert-butylphenoxide), methyla Minium bis (2,6-ditert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-ditert-butylphenoxide), isobutylaluminum bis (2,6-ditert-butyl-4-methylphenoxide) , Methylaluminum bis {2- (N-phenylimino) phenoxide}, isobutylaluminum bis {2- (N-phenylimino) phenoxide}, dimethylaluminum {2- (N-phenylimino) phenoxide}, dimethylaluminum (N, N'-diisopropylacetamidinate), dimethylaluminum (N, N'-dicyclohexylacetamidinate), dimethylgallium (N, N'-diisopropylacetamidinate), dimethylgallium (N, N'-dicyclohexylacetate) Amidinate), acid Aluminoxane compounds in which two or more aluminum through the atom or nitrogen atom is bonded and the like. Of these, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, an aluminoxane compound and the like are preferable. Component B can be used by mixing one or more of these compounds.

本発明で用いるビニル系モノマーとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ドデシル、アクリル酸フェニル等のアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ドデシル、メタクリル酸フェニル等のメタクリル酸エステル、メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、フェニルビニルエーテル等のビニルエーテル、ギ酸ビニル、酢酸ビニル、ｎ−プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、２−エチルへキサン酸ビニル、安息香酸ビニル、酢酸イソプロペニル等のビニルエステル、エチレン、プロピレン、１−ブテン、２−ブテン、イソブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１,５−ヘキサジエン、１,７−オクタジエン、シクロペンタジエン、ノルボルナジエン等のα−オレフィン、スチレン、α−メチルスチレン、ｐ−メチルスチレン等のスチレン誘導体、１,３−ブタジエン、イソプレン、クロロプレン、ネオプレン等のジエン誘導体が挙げられる。これらは単独でも２種以上を組み合わせて用いてもよい。   Examples of the vinyl monomer used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, dodecyl acrylate, phenyl acrylate, and other acrylic esters, methyl methacrylate, and ethyl methacrylate. , Methacrylates such as n-propyl methacrylate, n-butyl methacrylate, dodecyl methacrylate, phenyl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl Vinyl ethers such as vinyl ether and phenyl vinyl ether, vinyl formate, vinyl acetate, vinyl n-propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, 2-ethylhexa Vinyl esters such as vinyl acid vinyl, vinyl benzoate and isopropenyl acetate, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1,5-hexadiene Examples include α-olefins such as 1,7-octadiene, cyclopentadiene, norbornadiene, styrene derivatives such as styrene, α-methylstyrene, and p-methylstyrene, and diene derivatives such as 1,3-butadiene, isoprene, chloroprene, and neoprene. It is done. These may be used alone or in combination of two or more.

重合条件は特に限定されないが、ビニル系モノマーと不活性溶媒との混合溶液を用いるのが好ましい。この不活性溶媒は、重合を阻害しないものであればいかなる溶媒でも使用できるが、特に炭素数４〜２０の脂肪族炭化水素、例えばイソブタン、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等、芳香族炭化水素、例えばトルエン、キシレン等、炭素数１〜２０のハロゲン化脂肪族炭化水素、例えばクロロホルム、塩化メチレン、四塩化水素、ジブロモエタン、テトラクロロエタン等、ハロゲン化芳香族炭化水素、例えばクロロベンゼン、ジクロロベンゼン等、炭素数３〜２０の脂肪族エステル、例えば酢酸メチル、酢酸エチル、酢酸２−エチルへキシル、酢酸フェニル、ヘキサン酸エチル等、または芳香族エステル、例えば安息香酸メチル、安息香酸エチル等が適当である。   The polymerization conditions are not particularly limited, but it is preferable to use a mixed solution of a vinyl monomer and an inert solvent. As the inert solvent, any solvent can be used as long as it does not inhibit the polymerization, and in particular, an aliphatic hydrocarbon having 4 to 20 carbon atoms such as isobutane, pentane, hexane, heptane, cyclohexane and the like, For example, toluene, xylene, etc., halogenated aliphatic hydrocarbons having 1 to 20 carbon atoms, such as chloroform, methylene chloride, hydrogen tetrachloride, dibromoethane, tetrachloroethane, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc. Suitable are aliphatic esters having 3 to 20 carbon atoms such as methyl acetate, ethyl acetate, 2-ethylhexyl acetate, phenyl acetate and ethyl hexanoate, or aromatic esters such as methyl benzoate and ethyl benzoate. .

上記ビニル系モノマーとしてビニルエステルを用い、単独重合またはエチレン系モノマー、プロピレン系モノマー等と共重合する場合、得られるポリビニルエステルまたはその共重合体は、常法に従って鹸化し、ポリビニルアルコールまたはその共重合体に変換してもよい。    When vinyl ester is used as the vinyl monomer and is homopolymerized or copolymerized with ethylene monomer, propylene monomer, etc., the resulting polyvinyl ester or copolymer thereof is saponified according to a conventional method to obtain polyvinyl alcohol or copolymer thereof. It may be converted to coalescence.

本発明の実施にあたり、成分Ａはビニル系モノマーと不活性溶媒を含有する混合溶液１Lあたり、周期律表第１０族の金属原子０．００１〜２．５モルに相当する量で使用するのが好ましく、条件によりさらに高い濃度で使用することもできる。   In the practice of the present invention, component A is used in an amount corresponding to 0.001 to 2.5 moles of metal atoms in Group 10 of the periodic table per liter of a mixed solution containing a vinyl monomer and an inert solvent. Preferably, higher concentrations can be used depending on the conditions.

成分Ｂは、成分Ａの種類等により適宜濃度を変更し得るが、ビニル系モノマーと不活性溶媒を含有する混合溶液１Lあたり、通常周期表第１、２、１１、１２または１３族の金属原子０．０２〜５０モルの濃度で使用する。触媒組成物の成分Ｂ／成分Ａのモル比は特に限定されないが、通常０〜１０００であり、好ましくは０〜５００であり、より好ましくは０．１〜１００である。   The concentration of component B can be appropriately changed depending on the type of component A, etc., but it is usually a metal atom of Group 1, 2, 11, 12 or 13 of the periodic table per liter of mixed solution containing a vinyl monomer and an inert solvent. Used at a concentration of 0.02 to 50 mol. The molar ratio of component B / component A of the catalyst composition is not particularly limited, but is usually 0 to 1000, preferably 0 to 500, and more preferably 0.1 to 100.

本発明における重合操作は、通常の単一の重合条件で行う一段重合のみならず、複数の重合条件下で行う多段重合においても行うことができる。   The polymerization operation in the present invention can be performed not only in a single-stage polymerization performed under normal single polymerization conditions but also in a multi-stage polymerization performed under a plurality of polymerization conditions.

本発明における重合温度は特に限定されないが、通常−１００℃〜１００℃であり、好ましくは−３０℃〜８０℃である。   Although the polymerization temperature in this invention is not specifically limited, Usually, it is -100 degreeC-100 degreeC, Preferably it is -30 degreeC-80 degreeC.

以下の実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、合成例、実施例および比較例に用いた測定方法は次の通りである。   The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples. In addition, the measuring method used for the synthesis example, the Example, and the comparative example is as follows.

（成分Ａの同定）
核磁気共鳴装置（日本電子（株）製、JNM-ECP-500）を用い、1H NMR、13C NMR、および31P NMRを測定した。また、元素分析装置（YANACO社製、CHN CORDER MT-6）を用い、炭素および水素の含量を測定した。
（重合体の分子量）
カラム（東ソー（株）製、ＴＳＫｇｅｌＧＭＨＨＲ−ＭおよびＴＳＫｇｅｌＧ２０００ＨＨＲ）および示差屈折率計（東ソー（株）製、ＲＩ−８０２０）を備えたゲル浸透クロマトグラフ（東ソー（株）製）により、４０℃、テトラヒドロフラン溶媒中で、重合体の重量平均分子量（Ｍｗ）および分散度〔重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）〕をポリスチレン換算で求めた。
またポリエチレンについてはカラム（（株）センシュー科学製、GPC3506およびShodex社製、UT-802.5）および示差屈折率計（（株）センシュー科学製、SSC−7100）を備えたゲル浸透クロマトグラフ（（株）センシュー科学製）により、１２０℃、ｏ−ジクロロベンゼン溶媒中で重量平均分子量（Ｍｗ）および分散度〔重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）〕をポリスチレン換算で求めた。 (Identification of component A)
1 H NMR, 13 C NMR, and 31 P NMR were measured using a nuclear magnetic resonance apparatus (JNM-ECP-500, manufactured by JEOL Ltd.). Moreover, the content of carbon and hydrogen was measured using an elemental analyzer (manufactured by YANACO, CHN CORDER MT-6).
(Molecular weight of polymer)
A gel permeation chromatograph (manufactured by Tosoh Corp., RI-8020) equipped with a column (manufactured by Tosoh Corp., TSKgelGMHHR-M and TSKgelG2000HHR) and a differential refractometer (manufactured by Tosoh Corp.), 40 ° C, tetrahydrofuran In a solvent, the weight average molecular weight (Mw) and dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer were determined in terms of polystyrene.
For polyethylene, gel permeation chromatograph (Co., Ltd., manufactured by Senshu Kagaku Co., Ltd., GPC3506 and Shodex, UT-802.5) and a differential refractometer (manufactured by Senshu Kagaku Co., Ltd., SSC-7100). The weight average molecular weight (Mw) and the dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] were determined in polystyrene conversion at 120 ° C. in an o-dichlorobenzene solvent.

合成例１
［成分Ａの調製］
（トリtert−ブチルホスフィン）クロロメチルパラジウム（(tBu)3PPd(Me)Cl）の合成
アルゴン置換したシュレンクフラスコに(tBu)3 P(411 mg, 2.03 mmol) と(cod)Pd(Me)Cl (539 mg, 2.03 mmol)を投入した。この混合物に室温で塩化メチレン(1 mL)を加え、５分間撹拌した。反応溶液をヘキサン(25 mL)中に滴下し、生成した沈殿物を濾別、乾燥して標記の錯体を得た（収量：560 mg, 収率：77％）。 Synthesis example 1
[Preparation of component A]
Synthesis of (tri-tert-butylphosphine) chloromethylpalladium ((tBu) 3 PPd (Me) Cl) In a Schlenk flask substituted with argon, (tBu) 3 P (411 mg, 2.03 mmol) and (cod) Pd (Me) Cl (539 mg, 2.03 mmol) was added. To this mixture was added methylene chloride (1 mL) at room temperature and stirred for 5 minutes. The reaction solution was dropped into hexane (25 mL), and the formed precipitate was filtered and dried to obtain the title complex (yield: 560 mg, yield: 77%).

1H NMR (CDCl3, 500 MHz) 1.49 (d, J = 13 Hz, 27H), 1.75 (d, J = 0.8 Hz, 3H); 13C NMR (CDCl3, 125 MHz) -1.90, 31.8, 39.8; 31P NMR (CDCl3, 202 MHz) 70.1; Anal. calcd. for C13H30ClPPd: C, 43.47; H, 8.42. Found: C, 43.47; H, 8.29. 1 H NMR (CDCl 3 , 500 MHz) 1.49 (d, J = 13 Hz, 27H), 1.75 (d, J = 0.8 Hz, 3H); 13 C NMR (CDCl 3 , 125 MHz) -1.90, 31.8, 39.8 31 P NMR (CDCl 3 , 202 MHz) 70.1; Anal.calcd.for C 13 H 30 ClPPd: C, 43.47; H, 8.42.Found: C, 43.47; H, 8.29.

合成例２
［成分Aの調製］
[２−ビフェニル（ジtert−ブチル）]ホスフィンクロロメチルパラジウム（(biphenyl) (tBu)2PPd(Me)Cl）の合成
アルゴン置換したシュレンクフラスコに(biphenyl)(tBu)2P (2.16 g, 7.22 mmol) と(cod)Pd(Me)Cl (1.85 g, 6.98 mmol)を投入した。この混合物に室温で塩化メチレン(10 mL)を加え、５分間撹拌した。反応溶液をヘキサン(100 mL)中に滴下し、生成した沈殿物を濾別、乾燥して標記の錯体を得た(収量：2.91 g, 収率：92％)。 Synthesis example 2
[Preparation of component A]
Synthesis of [2-biphenyl (ditert-butyl)] phosphine chloromethylpalladium ((biphenyl) (tBu) 2 PPd (Me) Cl) In a Schlenk flask substituted with argon, (biphenyl) (tBu) 2 P (2.16 g, 7.22 mmol) and (cod) Pd (Me) Cl (1.85 g, 6.98 mmol). To this mixture was added methylene chloride (10 mL) at room temperature and stirred for 5 minutes. The reaction solution was dropped into hexane (100 mL), and the formed precipitate was filtered and dried to obtain the title complex (yield: 2.91 g, yield: 92%).

1H NMR (CDCl3, 500 MHz) 1.47 (d, J = 14Hz, 18H), 1.55 (d, J = 2Hz, 3H), 6.80-6.83 (m, 1H), 7.15 (d, J = 7.5Hz, 2H), 7.36-7.40 (m, 2H), 7.50(t, J = 7.8Hz, 2H), 7.75 (t, J = 7.5 Hz, 1H), 7.92-7.95 (m, 1H); 13C NMR (CDCl3, 125 MHz) −0.71, 31.3, 38.5, 126.1, 126.2, 130.4, 131.0, 130.4, 131.9, 133.2, 133.6, 134.5, 149.2; 31P NMR (CDCl3, 202 MHz) 62.4; Anal. calcd. for C21H30ClPPd: C, 55.40; H, 6.64. Found: C, 55.15; H, 6.77. 1 H NMR (CDCl 3 , 500 MHz) 1.47 (d, J = 14Hz, 18H), 1.55 (d, J = 2Hz, 3H), 6.80-6.83 (m, 1H), 7.15 (d, J = 7.5Hz, 2H), 7.36-7.40 (m, 2H), 7.50 (t, J = 7.8Hz, 2H), 7.75 (t, J = 7.5 Hz, 1H), 7.92-7.95 (m, 1H); 13 C NMR (CDCl (3 , 125 MHz) −0.71, 31.3, 38.5, 126.1, 126.2, 130.4, 131.0, 130.4, 131.9, 133.2, 133.6, 134.5, 149.2; 31 P NMR (CDCl 3 , 202 MHz) 62.4; Anal.calcd. For C 21 H 30 ClPPd: C, 55.40; H, 6.64. Found: C, 55.15; H, 6.77.

合成例３
［成分Aの調製］
（トリo−トリルホスフィン）クロロメチルパラジウム（(o-Tolyl)3PPd(Me)Cl）の合成
アルゴン置換した20 mLシュレンクフラスコに(o-Tolyl)3P (660 mg, 2.17 mmol) と(cod)PdMeCl (574 mg, 2.17 mmol)を投入した。この混合物に室温で塩化メチレン(1 mL)を加え、５分間撹拌した。反応溶液をヘキサン(25 mL)中に滴下し、生成した沈殿物を濾別、乾燥して標記の錯体を得た(収量：907 mg, 収率：91％)。 Synthesis example 3
[Preparation of component A]
Synthesis of (tri-o-tolylphosphine) chloromethylpalladium ((o-Tolyl) 3 PPd (Me) Cl)
(O-Tolyl) 3 P (660 mg, 2.17 mmol) and (cod) PdMeCl (574 mg, 2.17 mmol) were charged into a 20 mL Schlenk flask purged with argon. To this mixture was added methylene chloride (1 mL) at room temperature and stirred for 5 minutes. The reaction solution was dropped into hexane (25 mL), and the resulting precipitate was filtered and dried to obtain the title complex (yield: 907 mg, yield: 91%).

1H NMR (CDCl3, 500 MHz) 0.35-0.65 (br, 3H), 1.45-3.55 (br, 9H), 6.95-7.65 (br, 12H); 13C NMR (CDCl3, 125 MHz) 0.33, 31.8, 23.7, 125.7, 127.9, 130.9, 143.3; 31P NMR (CDCl3, 202 MHz) 36.2; Anal. calcd. for C22H25ClPPd: C, 57.28; H, 5.24. Found: C, 57.00; H, 5.33. 1 H NMR (CDCl 3 , 500 MHz) 0.35-0.65 (br, 3H), 1.45-3.55 (br, 9H), 6.95-7.65 (br, 12H); 13 C NMR (CDCl 3 , 125 MHz) 0.33, 31.8 , 23.7, 125.7, 127.9, 130.9, 143.3; 31 P NMR (CDCl 3 , 202 MHz) 36.2; Anal.calcd. For C 22 H 25 ClPPd: C, 57.28; H, 5.24. Found: C, 57.00; H, 5.33.

実施例１
(tBu)3PPd(Me)Clを用いたアクリル酸メチルの重合
アルゴン置換した20 mLシュレンクフラスコに (tBu)3PPd(Me)Cl (3.60 mg, 11.0 μmol) とNaB(3,5-(CF3)2C6H3)4 (10.0 mg, 11μmol) を投入した。この混合物に塩化メチレン (0.75 mL) を加え、室温で30分間撹拌した。減圧下で塩化メチレンを蒸発させ、そこへアクリル酸メチル (1.00 mL, 11.0 mmol) を加え14時間撹拌した。反応溶液を減圧下で濃縮し、ポリアクリル酸メチルを得た (収量：290 mg, 収率：30.3％)。Mn = 3,600,000 ; Mw / Mn = 1.12。 Example 1
Polymerization of methyl acrylate using (tBu) 3 PPd (Me) Cl In a 20 mL Schlenk flask purged with argon, (tBu) 3 PPd (Me) Cl (3.60 mg, 11.0 μmol) and NaB (3,5- (CF 3 ) 2 C 6 H 3 ) 4 (10.0 mg, 11 μmol) was added. To this mixture was added methylene chloride (0.75 mL), and the mixture was stirred at room temperature for 30 minutes. Methylene chloride was evaporated under reduced pressure, methyl acrylate (1.00 mL, 11.0 mmol) was added thereto, and the mixture was stirred for 14 hours. The reaction solution was concentrated under reduced pressure to obtain polymethyl acrylate (yield: 290 mg, yield: 30.3%). M n = 3,600,000; M w / M n = 1.12.

実施例２
(tBu)3PPd(Me)Clを用いたアクリル酸メチルの重合
アルゴン置換した20 mLシュレンクフラスコに(tBu)3PPd(Me)Cl (3.80 mg, 11.0 μmol) とNaB(3,5-(CF3)2C6H3)4 (11.5 mg, 12.0μmol) を投入した。この混合物にアセトニトリル (1.00 mL) 、続いてアクリル酸メチル (1.00 mL, 11.0 mmol) を加え、室温で８時間撹拌した。反応溶液を減圧下で濃縮し、ポリアクリル酸メチルを得た (収量：151 mg, 収率：15.8 ％)。Mn = 4,000,000 ; Mw / Mn = 1.22。 Example 2
Polymerization of methyl acrylate with (tBu) 3 PPd (Me) Cl In a 20 mL Schlenk flask purged with argon, (tBu) 3 PPd (Me) Cl (3.80 mg, 11.0 μmol) and NaB (3,5- (CF 3 ) 2 C 6 H 3 ) 4 (11.5 mg, 12.0 μmol) was added. Acetonitrile (1.00 mL) was added to this mixture, followed by methyl acrylate (1.00 mL, 11.0 mmol), and the mixture was stirred at room temperature for 8 hours. The reaction solution was concentrated under reduced pressure to obtain polymethyl acrylate (yield: 151 mg, yield: 15.8%). Mn = 4,000,000; Mw / Mn = 1.22.

実施例３
(tBu)3PPd(Me)Clを用いたアクリル酸メチルの重合
アルゴン置換した20 mLシュレンクフラスコに (tBu)3PPd(Me)Cl (3.80 mg, 11.0 μmol) とNaB(3,5-(CF3)2C6H3)4 (11.5 mg, 12 μmol) を投入した。この混合物にアセトニトリル (1.00 mL) 、続いて塩化メチレン (1.00 mL) 、そしてアクリル酸メチル (1.00 mL, 11.0 mmol) を加え、室温で８時間撹拌した。反応溶液をエバポレーションし、減圧下で乾燥し、ポリアクリル酸メチルを得た (収量：480 mg, 収率：50.2 %)。Mn = 3,300,000 ; Mw / Mn = 1.17。 Example 3
Polymerization of methyl acrylate using (tBu) 3 PPd (Me) Cl In a 20 mL Schlenk flask purged with argon, (tBu) 3 PPd (Me) Cl (3.80 mg, 11.0 μmol) and NaB (3,5- (CF 3 ) 2 C 6 H 3 ) 4 (11.5 mg, 12 μmol) was added. Acetonitrile (1.00 mL) was added to this mixture, followed by methylene chloride (1.00 mL) and methyl acrylate (1.00 mL, 11.0 mmol), and the mixture was stirred at room temperature for 8 hours. The reaction solution was evaporated and dried under reduced pressure to obtain polymethyl acrylate (yield: 480 mg, yield: 50.2%). Mn = 3,300,000; Mw / Mn = 1.17.

実施例４
(biphenyl)(tBu)2PPd(Me)Clを用いたメタクリル酸メチルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.0 mmol) を加え、さらに室温でメタクリル酸メチル (10.0 mL, 93.5 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリメタクリル酸メチルを得た (収量：2.45 g, 収率：26.2 %)。Mn = 33,000 ; Mw / Mn = 1.90。 Example 4
Polymerization of methyl methacrylate using (biphenyl) (tBu) 2 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and (biphenyl) (tBu) 2 PPd (Me) Cl. (22.8 mg, 0.05 mmol) and methylaluminoxane (2.0 mmol in terms of aluminum atom) was added, methyl methacrylate (10.0 mL, 93.5 mmol) was further added at room temperature, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polymethyl methacrylate (yield: 2.45 g, yield: 26.2%). Mn = 33,000; Mw / Mn = 1.90.

実施例５
(o-Tolyl)3PPd(Me)Clを用いたメタクリル酸メチルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (o-Tolyl)3PPd(Me)Cl (23.1 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.0 mmol) を加え、さらに室温でメタクリル酸メチル (10.0 mL, 93.5 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリメタクリル酸メチルを得た (収量：4.10 g, 収率：43.8 %)。Mn = 21,700 ; Mw / Mn = 1.94。 Example 5
Polymerization of methyl methacrylate using (o-Tolyl) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and (o-Tolyl) 3 PPd (Me) Cl (23.1 mg, 0.05 mmol) and methylaluminoxane (2.0 mmol in terms of aluminum atom) was added, methyl methacrylate (10.0 mL, 93.5 mmol) was further added at room temperature, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polymethyl methacrylate (yield: 4.10 g, yield: 43.8%). M n = 21,700; M w / M n = 1.94.

実施例６
(tBu)3PPd(Me)Clを用いたイソブチルビニルエーテルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに室温でイソブチルビニルエーテル(14.1 mL, 108 mmol) を加えて24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリイソブチルビニルエーテルを得た (収量：9.29 g, 収率：85.9 %)。Mn = 32,500 ; Mw / Mn = 4.81。 Example 6
Polymerization of isobutyl vinyl ether using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, and isobutyl vinyl ether (14.1 mL, 108 mmol) was further added at room temperature, followed by stirring for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyisobutyl vinyl ether (yield: 9.29 g, yield: 85.9%). Mn = 32,500; Mw / Mn = 4.81.

実施例７
(tBu)3PPd(Me)Clを用いたイソブチルビニルエーテルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 0℃で(tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにイソブチルビニルエーテル(14.1 mL, 108 mmol) を加えて24時間0℃で撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100ml中に投入し、クロロホルムで生成物を抽出し、ポリイソブチルビニルエーテルを得た (収量：941 mg, 収率：8.7 %)。Mn = 8,900; Mw / Mn = 2.60。 Example 7
Polymerization of isobutyl vinyl ether using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, isobutyl vinyl ether (14.1 mL, 108 mmol) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction solution was put into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyisobutyl vinyl ether (yield: 941 mg, yield: 8.7%). M n = 8,900; M w / M n = 2.60.

実施例８
（Biphenyl）(tBu)2PPd(Me)Clを用いたイソブチルビニルエーテルの重合
アルゴン置換した100 mLシュレンクフラスコにクロロホルム（10 ml）を装入し、 （Biphenyl）(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とトルフルオロメタンスルホン酸銀 (12.8 mg 0.05 mmol) を加え、さらにイソブチルビニルエーテル(14.1 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリイソブチルビニルエーテルを得た (収量：10.8 g, 収率：99.9 %)。Mn = 2,200 ; Mw / Mn = 3.42。 Example 8
Polymerization of isobutyl vinyl ether using (Biphenyl) (tBu) 2 PPd (Me) Cl Chloroform (10 ml) was placed in a 100 mL Schlenk flask purged with argon, and (Biphenyl) (tBu) 2 PPd (Me) Cl ( 22.8 mg, 0.05 mmol) and silver trifluoromethanesulfonate (12.8 mg 0.05 mmol) was added, isobutyl vinyl ether (14.1 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyisobutyl vinyl ether (yield: 10.8 g, yield: 99.9%). Mn = 2,200; Mw / Mn = 3.42.

実施例９
（Biphenyl）(tBu)2PPd(Me)Clを用いたイソブチルビニルエーテルの重合
アルゴン置換した100 mLシュレンクフラスコにクロロホルム（10 ml）を装入し、（Biphenyl）(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とテトラキス[3,5-ジ（トリフルオロメチル）フェニル]ホウ酸ナトリウム(44.3 mg、 0.05 mmol) を加え、さらにイソブチルビニルエーテル(14.1 mL, 99.9 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100ml中に投入し、クロロホルムで生成物を抽出し、ポリイソブチルビニルエーテルを得た (収量：10.8 g, 収率：99.9 %)。Mn = 5,400; Mw / Mn = 2.31。 Example 9
Polymerization of isobutyl vinyl ether using (Biphenyl) (tBu) 2 PPd (Me) Cl Chloroform (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (Biphenyl) (tBu) 2 PPd (Me) Cl ( 22.8 mg, 0.05 mmol) and sodium tetrakis [3,5-di (trifluoromethyl) phenyl] borate (44.3 mg, 0.05 mmol) were added, and then isobutyl vinyl ether (14.1 mL, 99.9 mmol) was added at room temperature. Stir for hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyisobutyl vinyl ether (yield: 10.8 g, yield: 99.9%). M n = 5,400; M w / M n = 2.31.

実施例１０
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：3.92 g, 収率：42.0 %)。Mn = 12,300 ; Mw / Mn = 1.85。 Example 10
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 3.92 g, yield: 42.0%). M n = 12,300; M w / M n = 1.85.

実施例１１
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて50℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：5.40 g, 収率：57.8 %)。Mn = 9,100 ; Mw / Mn = 2.28。 Example 11
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at 50 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 5.40 g, yield: 57.8%). M n = 9,100; M w / M n = 2.28.

実施例１２
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、0℃で (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて0℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：1.18 g, 収率：12.6 %)。Mn = 14,700 ; Mw / Mn = 1.87。 Example 12
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Charged an argon-substituted 100 mL Schlenk flask with toluene (10 ml), and at 0 ° C, (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 1.18 g, yield: 12.6%). M n = 14,700; M w / M n = 1.87.

実施例１３
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、(tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて75℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：5.91 g, 収率：63.3 %)。Mn = 7,700 ; Mw / Mn = 2.36。 Example 13
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at 75 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 5.91 g, yield: 63.3%). M n = 7,700; M w / M n = 2.36.

実施例１４
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにヘプタン（10 ml）を装入し、(tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：4.03 g, 収率：43.2 %)。Mn = 28,300 ; Mw / Mn = 2.33。 Example 14
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Argon-substituted 100 mL Schlenk flask was charged with heptane (10 ml) and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M aqueous hydrochloric acid solution, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 4.03 g, yield: 43.2%). M n = 28,300; M w / M n = 2.33.

実施例１５
(biphenyl)(tBu)2PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、(biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：1.32 g, 収率：14.1 %)。Mn = 11,200 ; Mw / Mn = 2.00。 Example 15
Polymerization of vinyl acetate using (biphenyl) (tBu) 2 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and (biphenyl) (tBu) 2 PPd (Me) Cl ( 22.8 mg, 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 1.32 g, yield: 14.1%). M n = 11,200; M w / M n = 2.00.

実施例１６
(biphenyl)(tBu)2PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、(biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 5.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：1.81 g, 収率：19.4 %)。Mn =8,400 ; Mw / Mn = 1.94。 Example 16
Polymerization of vinyl acetate using (biphenyl) (tBu) 2 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and (biphenyl) (tBu) 2 PPd (Me) Cl ( 22.8 mg, 0.05 mmol) and methylaluminoxane (5.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 1.81 g, yield: 19.4%). Mn = 8,400; Mw / Mn = 1.94.

実施例１７
(o-Tolyl)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、(o-Tolyl)3PPd(Me)Cl (23.1 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：1.32 g, 収率：14.1 %)。Mn = 10,500 ; Mw / Mn = 2.04。 Example 17
Polymerization of vinyl acetate using (o-Tolyl) 3 PPd (Me) Cl Argon-substituted 100 mL Schlenk flask was charged with toluene (10 ml) and (o-Tolyl) 3 PPd (Me) Cl (23.1 mg , 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 1.32 g, yield: 14.1%). M n = 10,500; M w / M n = 2.04.

実施例１８
(tBu)3PPd(Me)Clを用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、(tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とトリイソブチルアルミニウム (19.8 mg, 0.10 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：196 mg, 収率：2.1 %)。Mn = 6,400 ; Mw / Mn = 1.75 Example 18
Polymerization of vinyl acetate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And triisobutylaluminum (19.8 mg, 0.10 mmol) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M aqueous hydrochloric acid solution, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 196 mg, yield: 2.1%). M n = 6,400; M w / M n = 1.75

実施例１９
ジブロモビス（トリ-t-ブチルホスフィノ）ジパラジウム（[(tBu)3PPdBr]2）を用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、[(tBu)3PPdBr]2 (19.4 mg, 0.025 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol)を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：0.88 g, 収率：9.4 %)。Mn = 10,000 ; Mw / Mn = 1.76。 Example 19
Polymerization of vinyl acetate using dibromobis (tri-t-butylphosphino) dipalladium ([(tBu) 3 PPdBr] 2) To a 100 mL Schlenk flask purged with argon was charged toluene (10 ml) and [(tBu ) 3 PPdBr] 2 (19.4 mg, 0.025 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M aqueous hydrochloric acid solution, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 0.88 g, yield: 9.4%). M n = 10,000; M w / M n = 1.76.

実施例２０
ジブロモビス（トリ-t-ブチルホスフィノ）ジパラジウム（[(tBu)3PPdBr]2）を用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、[(tBu)3PPdBr]2 (19.4 mg, 0.025 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol)を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ酢酸ビニルを得た (収量：1.16 g, 収率：12.4 %)。Mn = 10,000 ; Mw / Mn = 1.76。 Example 20
Polymerization of vinyl acetate using dibromobis (tri-t-butylphosphino) dipalladium ([(tBu) 3 PPdBr] 2 ) A 100 mL Schlenk flask purged with argon was charged with toluene (10 ml) and [(tBu ) 3 PPdBr] 2 (19.4 mg, 0.025 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl acetate (10.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain polyvinyl acetate (yield: 1.16 g, yield: 12.4%). M n = 10,000; M w / M n = 1.76.

実施例２１
(tBu)3PPd(Me)Clを用いたピバリン酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにピバリン酸ビニル (15.9 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100ml中に投入し、クロロホルムで生成物を抽出し、ポリピバリン酸ビニルを得た (収量：9.42 g, 収率：68.3 %)。Mn =14,400 ; Mw / Mn =2.52 。 Example 21
Polymerization of vinyl pivalate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol ) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl pivalate (15.9 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain vinyl polypivalate (yield: 9.42 g, yield: 68.3%). M n = 14,400; M w / M n = 2.52.

実施例２２
(tBu)3PPd(Me)Clを用いたピバリン酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにピバリン酸ビニル(15.9 mL, 108 mmol) を加えて50℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリピバリン酸ビニルを得た (収量：11.2 g, 収率：80.9 %)。Mn = 13,600 ; Mw / Mn = 2.58。 Example 22
Polymerization of vinyl pivalate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol ) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl pivalate (15.9 mL, 108 mmol) was further added, and the mixture was stirred at 50 ° C. for 24 hours. After 24 hours, the reaction solution was put into 100 ml of a 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain vinyl polypivalate (yield: 11.2 g, yield: 80.9%). Mn = 13,600; Mw / Mn = 2.58.

実施例２３
(tBu)3PPd(Me)Clを用いたピバリン酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、0℃で (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにピバリン酸ビニル(15.9 mL, 108 mmol) を加えて0℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリピバリン酸ビニルを得た (収量：4.98 g, 収率：36.1 %)。Mn = 26,500; Mw / Mn = 2.71。 Example 23
Polymerization of vinyl pivalate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg , 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl pivalate (15.9 mL, 108 mmol) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain vinyl polypivalate (yield: 4.98 g, yield: 36.1%). M n = 26,500; M w / M n = 2.71.

実施例２４
(tBu)3PPd(Me)Clを用いた安息香酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに安息香酸ビニル(15.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ安息香酸ビニルを得た (収量：1.93 g, 収率：12.1 %)。Mn = 5,400 ; Mw / Mn = 1.89。 Example 24
Polymerization of vinyl benzoate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol ) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl benzoate (15.0 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain poly (vinyl benzoate) (yield: 1.93 g, yield: 12.1%). M n = 5,400; M w / M n = 1.89.

実施例２５
(tBu)3PPd(Me)Clを用いた安息香酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに安息香酸ビニル(15.0 mL, 108 mmol) を加えて50℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ安息香酸ビニルを得た (収量：4.23 g, 収率：26.4 %)。Mn = 7,200 ; Mw / Mn = 1.83。 Example 25
Polymerization of vinyl benzoate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol ) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, and vinyl benzoate (15.0 mL, 108 mmol) was further added, followed by stirring at 50 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain poly (vinyl benzoate) (yield: 4.23 g, yield: 26.4%). M n = 7,200; M w / M n = 1.83.

実施例２６
(tBu)3PPd(Me)Clを用いた安息香酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、0℃で (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに安息香酸ビニル(15.0 mL, 108 mmol) を加えて0℃で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリ安息香酸ビニルを得た (収量：1.49 g, 収率：9.3 %)。Mn = 5,800 ; Mw / Mn = 1.78。 Example 26
Polymerization of vinyl benzoate using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (tBu) 3 PPd (Me) Cl (18.0 mg , 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, vinyl benzoate (15.0 mL, 108 mmol) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain poly (vinyl benzoate) (yield: 1.49 g, yield: 9.3%). Mn = 5,800; Mw / Mn = 1.78.

実施例２７
(tBu)3PPd(Me)Clを用いたエチレンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、そこにエチレンガス（１atm）を 吹き込みながら室温で24時間撹拌した。24時間後、反応溶液を1M塩酸メタノール溶液100 ml中に投入し、ポリエチレンを得た (収量：991 mg)。Mn = 30,700 ; Mw / Mn = 1.71。 Example 27
Polymerization of ethylene using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) and Methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, and the mixture was stirred at room temperature for 24 hours while blowing ethylene gas (1 atm) therein. After 24 hours, the reaction solution was poured into 100 ml of 1M hydrochloric acid methanol solution to obtain polyethylene (yield: 991 mg). M n = 30,700; M w / M n = 1.71.

実施例２８
(o-Tolyl)3PPd(Me)Clを用いたエチレンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、 (o-Tolyl)3PPd(Me)Cl (23.1 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、そこにエチレンガス（１atm）を 吹き込みながら室温で24時間撹拌した。24時間後、反応溶液を1M塩酸メタノール溶液100ml中に投入し、ポリエチレンを得た (収量：801 mg)。Mn = 21,700 ; Mw / Mn = 1.86。 Example 28
Polymerization of ethylene using (o-Tolyl) 3 PPd (Me) Cl Toluene (10 ml) was charged into a 100 mL Schlenk flask purged with argon, and (o-Tolyl) 3 PPd (Me) Cl (23.1 mg, 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, and the mixture was stirred at room temperature for 24 hours while blowing ethylene gas (1 atm) therein. After 24 hours, the reaction solution was poured into 100 ml of 1M hydrochloric acid methanol solution to obtain polyethylene (yield: 801 mg). M n = 21,700; M w / M n = 1.86.

実施例２９
(tBu)3PPd(Me)Clを用いた１−ヘキセンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10ml）を装入し、 (tBu)3PPd(Me)Cl (18.0 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらに１−ヘキセン（13.5mL, 108 mmol）を加えて、室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100ml中に投入し、クロロホルムで生成物を抽出し、ポリ（１−ヘキセン）を得た (収量：2.96 g、収率：32.6%)。Mn = 450 ; Mw / Mn = 1.03。 Example 29
Polymerization of 1-hexene using (tBu) 3 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (tBu) 3 PPd (Me) Cl (18.0 mg, 0.05 mmol) And methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, 1-hexene (13.5 mL, 108 mmol) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M aqueous hydrochloric acid, and the product was extracted with chloroform to obtain poly (1-hexene) (yield: 2.96 g, yield: 32.6%). Mn = 450; Mw / Mn = 1.03.

実施例３０
(biphenyl)(tBu)2PPd(Me)Clを用いたスチレンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10ml）を装入し、(biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにスチレン (10.0 mL) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100ml中に投入し、クロロホルムで生成物を抽出し、ポリスチレンを得た (収量：9.08 g, 収率： 99.9 %)。Mn = 4,300 ; Mw / Mn = 1.95。 Example 30
Polymerization of styrene using (biphenyl) (tBu) 2 PPd (Me) Cl Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and (biphenyl) (tBu) 2 PPd (Me) Cl (22.8 mg , 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, styrene (10.0 mL) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of a 0.1 M aqueous hydrochloric acid solution, and the product was extracted with chloroform to obtain polystyrene (yield: 9.08 g, yield: 99.9%). Mn = 4,300; Mw / Mn = 1.95.

実施例３１
(biphenyl)(tBu)2PPd(Me)Clを用いたスチレン／MMA（メタクリル酸メチル）の重合
アルゴン置換した100 mLシュレンクフラスコにクロロホルム（１ml）を装入し、(biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにスチレン(5.72 mL, 50.0 mmol) 、MMA（5.34 mL, 50.0 mmol）を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、スチレン／MMA共重合体を得た (収量：7.1 g, 収率：69.6 %)。Mn = 5,700 ; Mw / Mn = 2.70。 Example 31
Polymerization of styrene / MMA (methyl methacrylate) using (biphenyl) (tBu) 2 PPd (Me) Cl Chloroform (1 ml) was charged into a 100 mL Schlenk flask purged with argon, and (biphenyl) (tBu) 2 PPd (Me) Cl (22.8 mg, 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, styrene (5.72 mL, 50.0 mmol) and MMA (5.34 mL, 50.0 mmol) were further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain a styrene / MMA copolymer (yield: 7.1 g, yield: 69.6%). Mn = 5,700; Mw / Mn = 2.70.

実施例３２
(biphenyl)(tBu)2PPd(Me)Clを用いたイソプレンの重合
アルゴン置換した100 mLシュレンクフラスコにクロロホルム（１ml）を装入し、(biphenyl)(tBu)2PPd(Me)Cl (22.8 mg, 0.05 mmol) とメチルアルミノキサン (アルミニウム原子換算で 2.00 mmol) を加え、さらにイソプレン(10.8 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を0.1M塩酸水溶液100 ml中に投入し、クロロホルムで生成物を抽出し、ポリイソプレンを得た (収量：426 mg, 収率：5.8 %)。Mn = 3,000 ; Mw / Mn = 1.60。 Example 32
Polymerization of isoprene using (biphenyl) (tBu) 2 PPd (Me) Cl Chloroform (1 ml) was charged into an argon-substituted 100 mL Schlenk flask, and (biphenyl) (tBu) 2 PPd (Me) Cl (22.8 mg , 0.05 mmol) and methylaluminoxane (2.00 mmol in terms of aluminum atom) was added, and isoprene (10.8 mL, 108 mmol) was further added, followed by stirring at room temperature for 24 hours. After 24 hours, the reaction solution was poured into 100 ml of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyisoprene (yield: 426 mg, yield: 5.8%). Mn = 3,000; Mw / Mn = 1.60.

比較例１
ラジカル重合開始剤を用いたアクリル酸メチルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに室温でアクリル酸メチル (10.0 mL,111 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を濃縮し、ポリアクリル酸メチルを得た (収量：126 mg, 収率： 13.2 %)。Mn = 47,000 ; Mw / Mn = 2.15。 Comparative Example 1
Polymerization of methyl acrylate using radical polymerization initiator Argon-substituted 100 mL Schlenk flask was charged with toluene (10 ml), and Wako Pure Chemical Industries, Ltd. V-70 (15.4 mg, 0.05 mmol) was added. Further, methyl acrylate (10.0 mL, 111 mmol) was added at room temperature, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated to obtain methyl polyacrylate (yield: 126 mg, yield: 13.2%). Mn = 47,000; Mw / Mn = 2.15.

比較例２
ラジカル重合開始剤を用いたメタクリル酸メチルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに室温でメタクリル酸メチル (10.0 mL, 93.5 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を濃縮し、ポリメタクリル酸メチルを得た (収量：1.01 g, 収率：10.8 %)。Mn = 31,700 ; Mw / Mn = 2.01。 Comparative Example 2
Polymerization of methyl methacrylate using radical polymerization initiator Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask, and V-70 (15.4 mg, 0.05 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added. Further, methyl methacrylate (10.0 mL, 93.5 mmol) was added at room temperature, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated to obtain polymethyl methacrylate (yield: 1.01 g, yield: 10.8%). M n = 31,700; M w / M n = 2.01.

比較例３
ラジカル重合開始剤を用いたイソブチルビニルエーテルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに室温でイソブチルビニルエーテル(14.1 mL, 108 mmol) を加えて24時間撹拌した。24時間後、反応溶液を濃縮したがポリマーは得られなかった。 Comparative Example 3
Polymerization of isobutyl vinyl ether using radical polymerization initiator Argon-substituted 100 mL Schlenk flask was charged with toluene (10 ml), and Wako Pure Chemical Industries, Ltd. V-70 (15.4 mg, 0.05 mmol) was added. Further, isobutyl vinyl ether (14.1 mL, 108 mmol) was added at room temperature, and the mixture was stirred for 24 hours. After 24 hours, the reaction solution was concentrated, but no polymer was obtained.

比較例４
ラジカル重合開始剤を用いた酢酸ビニルの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を濃縮し、ポリ酢酸ビニルを得た (収量：626 mg, 収率：6.7 %)。Mn = 22,400 ; Mw / Mn = 1.92 Comparative Example 4
Polymerization of vinyl acetate using radical polymerization initiator Argon-substituted 100 mL Schlenk flask was charged with toluene (10 ml), Wako Pure Chemical Industries, Ltd. V-70 (15.4 mg, 0.05 mmol) was added, Further vinyl acetate (10.0 mL, 108 mmol) was added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated to obtain polyvinyl acetate (yield: 626 mg, yield: 6.7%). M n = 22,400; M w / M n = 1.92

また、アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに酢酸ビニル(10.0 mL, 108 mmol) を加えて50℃で24時間撹拌した。24時間後、反応溶液を濃縮しポリ酢酸ビニルを得た (1.88 g, 20.1 %)。Mn = 12,400 ; Mw / Mn = 2.12 Into a 100 mL Schlenk flask purged with argon, toluene (10 ml) was charged, V-70 (15.4 mg, 0.05 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added, and vinyl acetate (10.0 mL, 108 mmol) was added. ) Was added and stirred at 50 ° C. for 24 hours. After 24 hours, the reaction solution was concentrated to obtain polyvinyl acetate (1.88 g, 20.1%). M n = 12,400; M w / M n = 2.12

比較例５
ラジカル重合開始剤を用いたエチレンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、そこにエチレンガス（１atm）を 吹き込みながら室温で24時間撹拌した。24時間後、反応溶液を濃縮したがポリマーは得られなかった。 Comparative Example 5
Ethylene polymerization using radical polymerization initiator Argon-substituted 100 mL Schlenk flask was charged with toluene (10 ml), and V-70 (15.4 mg, 0.05 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added. The mixture was stirred at room temperature for 24 hours while blowing ethylene gas (1 atm). After 24 hours, the reaction solution was concentrated, but no polymer was obtained.

比較例６
ラジカル重合開始剤を用いた１−ヘキセンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらに１−ヘキセン（13.5 mL, 108 mmol）を加えて、室温で24時間撹拌した。24時間後、反応溶液を濃縮したが、ポリマーは得られなかった。 Comparative Example 6
Polymerization of 1-hexene using radical polymerization initiator Toluene (10 ml) was charged into an argon-substituted 100 mL Schlenk flask and V-70 (15.4 mg, 0.05 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added. Further, 1-hexene (13.5 mL, 108 mmol) was added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated, but no polymer was obtained.

比較例７
ラジカル重合開始剤を用いたスチレンの重合
アルゴン置換した100 mLシュレンクフラスコにトルエン（10 ml）を装入し、和光純薬製V-70 (15.4 mg, 0.05 mmol) を加え、さらにスチレン(10.0 mL) を加えて室温で24時間撹拌した。24時間後、反応溶液を濃縮しポリスチレンを得た (収量：2.27 g, 収率：12.5 %)。Mn = 12,300 ; Mw / Mn = 2.01。 Comparative Example 7
Polymerization of styrene using radical polymerization initiator Charge 100 ml Schlenk flask substituted with argon with toluene (10 ml), add Wako Pure Chemicals V-70 (15.4 mg, 0.05 mmol), and then add styrene (10.0 mL). ) Was added and stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated to obtain polystyrene (yield: 2.27 g, yield: 12.5%). M n = 12,300; M w / M n = 2.01.

比較例８
ラジカル重合開始剤を用いたイソプレンの重合
アルゴン置換した100 mLシュレンクフラスコにクロロホルム（１ml）を装入し、和光純薬工業（株）製V-70 (15.4 mg, 0.05 mmol) を加え、さらにイソプレン(10.8 mL, 108 mmol) を加えて室温で24時間撹拌した。24時間後、反応溶液を濃縮し、ポリイソプレンを得た (収量：213 mg, 収率：2.9 %)。Mn = 1,000 ; Mw / Mn = 1.60。 Comparative Example 8
Polymerization of isoprene using radical polymerization initiator Chloroform (1 ml) was charged into an argon-substituted 100 mL Schlenk flask, V-70 (15.4 mg, 0.05 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added, and isoprene was further added. (10.8 mL, 108 mmol) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction solution was concentrated to obtain polyisoprene (yield: 213 mg, yield: 2.9%). Mn = 1,000; Mw / Mn = 1.60.

実施例１〜３と比較例１、実施例４〜５と比較例２、実施例６〜９と比較例３、実施例１０〜２６と比較例４、実施例２７〜２８と比較例５、実施例２９と比較例６、実施例３０〜３１と比較例７、実施例３２と比較例８との比較から明らかなように、本発明の重合用触媒組成物を用いた方が得られるポリマーの収率が高く、生産性に優れていることがわかる。   Examples 1-3 and Comparative Example 1, Examples 4-5 and Comparative Example 2, Examples 6-9 and Comparative Example 3, Examples 10-26 and Comparative Example 4, Examples 27-28 and Comparative Example 5, As apparent from the comparison between Example 29 and Comparative Example 6, Examples 30 to 31 and Comparative Example 7, and Example 32 and Comparative Example 8, a polymer obtained by using the polymerization catalyst composition of the present invention is obtained. It can be seen that the yield is high and the productivity is excellent.

Claims (6)

ビニル系モノマー重合用触媒組成物であって、下記式（ＩＩＩ）：
Figure 0005575702
 （式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基または置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ｘ１ およびＸ ２ はそれぞれ、水素、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基、ハロゲン、アセトキシ基、アミノ基、アミド基、カルボキシル基、ニトロ基、カルボニル、置換基を有してもよいトリフルオロメタンスルホニル基、またはパークロロを表し、Ｍ１およびＭ２はそれぞれ周期律表第１０族の元素を表す。）で示される金属化合物からなる群から選ばれた少なくとも１種の金属化合物を含む成分Ａと、
（ａ）周期律表第１、２、１１、１２、１３、１５および１６族から選ばれた少なくとも１種の元素、（ｂ）置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基および／または置換基を有してもよい炭素数６〜４０の芳香族炭化水素基ならびに（ｃ）過塩素酸基、からなる３つの群のうちの少なくとも２つの群からそれぞれ１種以上選ばれた、元素および／または基を有する化合物であって、有機リチウム化合物、有機マグネシウム化合物、トリフルオロメタンスルホン酸塩、過塩素酸塩、有機亜鉛化合物、有機ホウ素化合物、ホウ酸塩、または有機アルミニウム化合物である成分Ｂと、
を含有する、前記重合用触媒組成物。 A vinyl-based monomer polymerization catalyst composition having the following formula (III):
Figure 0005575702
 (In the formula, each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 has an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent. represents also an aromatic hydrocarbon group having 6 to 20 carbon atoms, X 1 and X 2 are hydrogen, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, have a substituent C6-C20 aromatic hydrocarbon group, halogen, acetoxy group, amino group, amide group, carboxyl group, nitro group, carbonyl, trifluoromethanesulfonyl group which may have a substituent, or perchloro M 1 and M 2 each represent an element of Group 10 of the periodic table.) Component A containing at least one metal compound selected from the group consisting of metal compounds represented by :
(A) at least one element selected from groups 1, 2, 11, 12, 13, 15 and 16 of the periodic table, and (b) an aliphatic having 1 to 20 carbon atoms which may have a substituent. 1 type each from at least two of the three groups consisting of a hydrocarbon group and / or an optionally substituted aromatic hydrocarbon group having 6 to 40 carbon atoms and (c) a perchloric acid group A compound having an element and / or a group selected from the above, an organolithium compound, an organomagnesium compound, a trifluoromethanesulfonate, a perchlorate, an organozinc compound, an organoboron compound, a borate, or an organic Component B which is an aluminum compound;
The said catalyst composition for polymerization containing this. Ｍ１および／またはＭ２の金属がパラジウムである、請求項１に記載の重合用触媒組成物。 The polymerization catalyst composition according to claim 1, wherein the metal of M 1 and / or M 2 is palladium. Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、置換基を有してもよいｔｅｒｔ−ブチル基、置換基を有してもよいシクロヘキシル基、置換基を有してもよいビフェニル基、置換基を有してもよいナフチル基、置換基を有してもよいアントリル基、置換基を有してもよいフェナントリル基、または置換基を有してもよいトリル基である、請求項１または２に記載の重合用触媒組成物。 R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may have a tert-butyl group which may have a substituent, a cyclohexyl group which may have a substituent, or a substituent. A good biphenyl group, a naphthyl group which may have a substituent, an anthryl group which may have a substituent, a phenanthryl group which may have a substituent, or a tolyl group which may have a substituent. The polymerization catalyst composition according to claim 1 or 2 . Ｘ１ およびＸ ２ がそれぞれ、水素、置換基を有してもよいメチル基、臭素、塩素、ヨウ素、置換基を有してもよいフェニル基、置換基を有してもよいトリフルオロメタンスルホニル基、またはパークロロである、請求項１〜３のいずれかに記載の重合用触媒組成物。 X 1 and X 2 are each hydrogen, a methyl group that may have a substituent, bromine, chlorine, iodine, a phenyl group that may have a substituent, or a trifluoromethanesulfonyl group that may have a substituent. Or the catalyst composition for polymerization according to any one of claims 1 to 3, which is perchloro. 請求項１〜４のいずれかに記載の重合用触媒組成物の、ビニル系モノマーの重合への使用。 Use of the polymerization catalyst composition according to any one of claims 1 to 4 for polymerization of a vinyl monomer. ビニル系モノマーが、アクリル酸エステル、メタクリル酸エステル、ビニルエーテル、ビニルエステル、エチレン、α−オレフィン、スチレン誘導体およびジエン誘導体からなる群から選ばれた少なくとも１種である、請求項５に記載のビニル系モノマーの重合への使用 Vinyl monomer is, acrylic acid esters, methacrylic acid esters, vinyl ethers, vinyl esters, ethylene, alpha-olefin, at least one selected from the group consisting of styrene derivatives and dienes derivatives, vinyl system according to claim 5 Use for monomer polymerization
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