JP2011084681A - Highly gas-permeable cyclic olefin addition polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly gas-permeable cyclic olefin addition polymer which is readily industrially producible, and has excellent gas permeability, and high thermal stability and mechanical strength, and further excellent solubility in combination, and to provide a method for producing the polymer. <P>SOLUTION: The cyclic olefin addition polymer of a specific structure is obtained by carrying out addition polymerization of a cyclic olefin functional siloxane, or the cyclic olefin functional siloxane with a cyclic olefin compound using a multicomponent system catalyst containing (A) a β-diketone compound of palladium, (B) an ionic boron compound, and (C) a phosphine compound having a substituent selected from among 3-6C alkyl, cycloalkyl, and aryl. In the cyclic olefin addition polymer, the ratio of structural units derived from the cyclic olefin functional siloxane is 40-100 mol% in the addition polymer, and the number-average molecular weight (Mn) in terms of polystyrene measured by GPC (gel permeation chromatography) is 200,000-1,500,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cyclic olefin addition polymer, and more particularly to a high gas permeable cyclic olefin addition polymer having a specific organosiloxane as a pendant and a method for producing the same.

  In recent years, air conditioners (hereinafter abbreviated as air conditioners) that provide comfortable living and working spaces have become indispensable facilities for office buildings, houses, automobiles, and the like. Usually, the environment in which an air conditioner is used has a high hermeticity in order to increase energy efficiency. Therefore, when a human continues working in such a sealed space, oxygen is insufficient and work efficiency is reduced. Particularly in the case of a passenger car, safety problems such as drowsiness may occur. Opening the window can prevent the oxygen concentration from decreasing, but it leads to energy loss and allows the invasion of pollen, yellow sand, dust, etc., and the built comfortable environment is damaged. Under such circumstances, air conditioners using oxygen-enriched membranes that selectively allow oxygen to pass through have been developed, but satisfactory performance has not yet been obtained.

  Organopolysiloxane is known as a material excellent in oxygen permeability. However, since organopolysiloxane itself has low mechanical strength and has problems in practical use, it is a copolymer with polycarbonate (Patent Document 1: Japanese Patent Publication No. 4-001652), polysiloxane-aromatic polyamide block. Copolymers (Patent Document 2: Japanese Patent Laid-Open No. 5-285216) have been proposed. However, in addition to the extremely complicated synthesis, there are problems such as lack of long-term stability such as hydrolyzability.

  In addition, various polymers having an organosilicon group as a substituent, for example, a silicon-containing styrene derivative (Patent Document 3: Japanese Patent Laid-Open No. 4-88004), a silicon-containing stilbene derivative (Patent Document 4: Japanese Patent Laid-Open No. 8-198881) Silicon-containing cellulose (Patent Document 5: Japanese Patent Application Laid-Open No. 2001-79375) has been proposed, but a material satisfying oxygen permeability, thermal stability and mechanical strength has not yet been obtained.

  Patent Document 6 (Japanese Patent Application Laid-Open No. 2007-291150) proposes a ring-opening polymer of a cyclic olefin compound having an organosiloxane pendant and a hydride thereof. However, there are many problems in heat resistance and film strength, and there is also a problem that long-term stability is lacking such as depolymerization.

  There have been many proposals regarding addition polymerization of cyclic olefin compounds (Patent Documents 7 to 22: JP-A-4-63807, JP-A-8-198919, JP-A-9-508649, JP-A-3476466). Publication, JP-A-7-196736, International Publication No. 97/20871, International Publication No. 98/20394, Japanese Patent No. 3801018, International Publication No. 02/062859, Japanese Unexamined Patent Publication No. 2003-252881 German Patent Application No. 4128932, Japanese Patent Application Laid-Open No. 2007-77252, Japanese Patent Application Laid-Open No. 2007-70337, Japanese Patent No. 4075789, International Publication No. 07/0669518, Japanese Patent Application Laid-Open No. 2008-202003. ), Especially in Patent Documents 20 to 22, There is described a multi-component catalyst. However, there is no description regarding the use of a cyclic olefin functional siloxane as a monomer for an addition polymerization reaction. Naturally, polymerization is carried out using a palladium multicomponent catalyst, and this is included as a repeating unit in the structure. There are no reports of addition polymers.

  In addition, in Patent Documents 7 to 22, the cyclic olefin addition polymer is described in detail with respect to the development of optical and electronic components using its thermal, mechanical, optical, and electrical properties, There has been no report regarding the use focused on gas permeability as described above.

Japanese Patent Publication No. 4-001652 Japanese Patent Laid-Open No. 5-285216 JP-A-4-88004 JP-A-8-198881 JP 2001-79375 A JP 2007-291150 A JP-A-4-63807 JP-A-8-198919 Japanese National Patent Publication No. 9-508649 Japanese Patent No. 3476466 JP-A-7-196736 International Publication No. 97/20871 Pamphlet International Publication No. 98/20394 Pamphlet Japanese Patent No. 3801018 International Publication No. 02/062859 Pamphlet JP 2003-252881 A German Patent Application Publication No. 4128932 JP 2007-77252 A JP 2007-70337 A Japanese Patent No. 4075789 International Publication No. 07/0669518 Pamphlet JP 2008-202003 A

  The present invention has been made in view of the above circumstances, is easy to industrially produce, has excellent gas permeability, and has high thermal stability and mechanical strength, and also has high solubility. It aims at providing a permeable cyclic olefin addition polymer and its manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventor is represented by the following formula (1) using a multi-component catalyst containing the following compounds (A), (B), and (C). The cyclic olefin functional siloxane or the cyclic olefin functional siloxane of the formula (1) and the cyclic olefin compound represented by the following formula (2) are obtained by addition polymerization, and represented by the following formula (1). The proportion of the structural unit derived from the cyclic olefin functional siloxane is 40 to 100 mol% in the addition polymer, and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is 200,000 to 1,500. The present inventors have found that a cyclic olefin addition polymer having a specific structure of 1,000 is a material having excellent oxygen permeability, heat resistance, mechanical strength, and solubility, and has completed the present invention.

（式（１）中のＲ¹は互いに同一又は異種の脂肪族不飽和結合を有さない一価の有機基であり、ｓは０〜２の整数であり、ｊは０又は１を示す。）

（式（２）中のＡ¹〜Ａ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アリーロキシ基及びハロゲン化炭化水素基から選ばれる置換基、又はオキセタニル基及びアルコキシカルボニル基から選ばれる極性を有する置換基である。また、Ａ¹とＡ²又はＡ¹とＡ³とが、それぞれが結合する炭素原子とともに脂環構造、芳香環構造、カルボンイミド基又は酸無水物基を形成してもよい。ｉは０又は１を示す。）
〔請求項２〕
化合物（Ａ）がビス（アセチルアセトナート）パラジウム、化合物（Ｂ）がトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、化合物（Ｃ）がトリシクロヘキシルホスフィンである請求項１記載の高気体透過性環状オレフィン付加重合体。
〔請求項３〕
式（１）中のＲ¹がメチル基であり、ｓが０である請求項１又は２記載の高気体透過性環状オレフィン付加重合体。
〔請求項４〕
式（１）中のＲ¹がメチル基であり、ｓが１である請求項１又は２記載の高気体透過性環状オレフィン付加重合体。
〔請求項５〕
式（２）中のＡ¹〜Ａ⁴がいずれも水素原子であり、ｉが０である請求項１〜４のいずれか１項記載の高気体透過性環状オレフィン付加重合体。
〔請求項６〕
ポリスチレン換算の数平均分子量（Ｍｎ）と重量平均分子量（Ｍｗ）の比（分散度：Ｍｗ／Ｍｎ）が１．０〜４．０である請求項１〜５のいずれか１項記載の高気体透過性環状オレフィン付加重合体。
〔請求項７〕
ガラス転移温度が２００〜４００℃である請求項１〜６のいずれか１項記載の高気体透過性環状オレフィン付加重合体。
〔請求項８〕
差圧法により計測される高気体透過性環状オレフィン付加重合体キャストフィルムの酸素透過係数が４０Ｂａｒｒｅｒ（１Ｂａｒｒｅｒ＝１０^-10ｃｍ³（ＳＴＰ）・ｃｍ／ｃｍ²・ｓ・ｃｍＨｇ）以上である請求項１〜７のいずれか１項記載の高気体透過性環状オレフィン付加重合体。
〔請求項９〕
イソドデカン、メチルトリス（トリメチルシロキシ）シラン又はデカメチルシクロペンタシロキサン溶媒に１０質量％溶液以上で溶解性を示す請求項１〜８のいずれか１項記載の高気体透過性環状オレフィン付加重合体。
〔請求項１０〕
下記化合物（Ａ）、（Ｂ）、（Ｃ）を含む多成分系触媒の存在下、下記式（１）で表される環状オレフィン官能性シロキサン、又はこの式（１）の環状オレフィン官能性シロキサンと、下記式（２）で表される環状オレフィン化合物とを付加重合することを特徴とする請求項１記載の高気体透過性環状オレフィン付加重合体の製造方法。
〔化合物（Ａ）〕
パラジウムのβ−ジケトン化合物。
〔化合物（Ｂ）〕
イオン性ホウ素化合物。
〔化合物（Ｃ）〕
炭素数３〜６のアルキル基、シクロアルキル基、アリール基から選ばれる置換基を有するホスフィン化合物。

（式（１）中のＲ¹は互いに同一又は異種の脂肪族不飽和結合を有さない一価の有機基であり、ｓは０〜２の整数であり、ｊは０又は１を示す。）

（式（２）中のＡ¹〜Ａ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アリーロキシ基及びハロゲン化炭化水素基から選ばれる置換基、又はオキセタニル基及びアルコキシカルボニル基から選ばれる極性を有する置換基である。また、Ａ¹とＡ²又はＡ¹とＡ³とが、それぞれが結合する炭素原子とともに脂環構造、芳香環構造、カルボンイミド基又は酸無水物基を形成してもよい。ｉは０又は１を示す。）
〔請求項１１〕
化合物（Ａ）がビス（アセチルアセトナート）パラジウム、化合物（Ｂ）がトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、化合物（Ｃ）がトリシクロヘキシルホスフィンである請求項１０記載の高気体透過性環状オレフィン付加重合体の製造方法。
〔請求項１２〕
式（１）中のＲ¹がメチル基であり、ｓが０である請求項１０又は１１記載の高気体透過性環状オレフィン付加重合体の製造方法。
〔請求項１３〕
式（１）中のＲ¹がメチル基であり、ｓが１である請求項１０又は１１記載の高気体透過性環状オレフィン付加重合体の製造方法。
〔請求項１４〕
式（２）中のＡ¹〜Ａ⁴がいずれも水素原子であり、ｉが０である請求項１０〜１３のいずれか１項記載の高気体透過性環状オレフィン付加重合体の製造方法。
〔請求項１５〕
不活性ガス雰囲気下、−２０〜１００℃で１〜７２時間付加重合する請求項１０〜１４のいずれか１項記載の高気体透過性環状オレフィン付加重合体の製造方法。 Accordingly, the present invention provides the following highly gas-permeable cyclic olefin addition polymer and method for producing the same.
[Claim 1]
Using a multi-component catalyst containing the following compounds (A), (B), and (C), a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane of the formula (1) And a cyclic olefin compound represented by the following formula (2) is obtained by addition polymerization, and the proportion of structural units derived from the cyclic olefin functional siloxane represented by the following formula (1) is an addition polymer. A high gas-permeable cyclic olefin addition polymer having a polystyrene-reduced number average molecular weight (Mn) of 200,000 to 1,500,000 as measured by GPC.
[Compound (A)]
A β-diketone compound of palladium.
[Compound (B)]
Ionic boron compounds.
[Compound (C)]
A phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group.

(Formula (1) R ¹ in is a monovalent organic group having no aliphatic unsaturated bonds of the same or different from each other, s is an integer of 0 to 2, j is 0 or 1. )

(A ^{1 to} A ⁴ in the formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and A substituent selected from a halogenated hydrocarbon group, or a substituent having a polarity selected from an oxetanyl group and an alkoxycarbonyl group, and A ¹ and A ² or A ¹ and A ³ are bonded to each other. (An alicyclic structure, an aromatic ring structure, a carbonimido group, or an acid anhydride group may be formed together with an atom. I represents 0 or 1.)
[Claim 2]
The high gas-permeable cyclic structure according to claim 1, wherein the compound (A) is bis (acetylacetonato) palladium, the compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and the compound (C) is tricyclohexylphosphine. Olefin addition polymer.
[Claim 3]
The highly gas-permeable cyclic olefin addition polymer according to claim 1 or 2, wherein R ¹ in formula (1) is a methyl group and s is 0.
[Claim 4]
The highly gas-permeable cyclic olefin addition polymer according to claim 1 or 2, wherein R ¹ in formula (1) is a methyl group and s is 1.
[Claim 5]
The high gas-permeable cyclic olefin addition polymer according to any one of claims 1 to 4, wherein A ^{1 to} A ⁴ in formula (2) are all hydrogen atoms and i is 0.
[Claim 6]
The high gas according to any one of claims 1 to 5, wherein the ratio (dispersity: Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene is 1.0 to 4.0. A permeable cyclic olefin addition polymer.
[Claim 7]
Glass transition temperature is 200-400 degreeC, The high gas permeability cyclic olefin addition polymer of any one of Claims 1-6.
[Claim 8]
2. The oxygen permeability coefficient of a high gas permeable cyclic olefin addition polymer cast film measured by a differential pressure method is 40 Barrer (1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg) or more. The high gas-permeable cyclic olefin addition polymer of any one of -7.
[Claim 9]
The highly gas-permeable cyclic olefin addition polymer according to any one of claims 1 to 8, which exhibits solubility in a solvent of isododecane, methyltris (trimethylsiloxy) silane or decamethylcyclopentasiloxane at 10% by mass or more.
[Claim 10]
In the presence of a multi-component catalyst containing the following compounds (A), (B), (C), a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane of the formula (1) And a cyclic olefin compound represented by the following formula (2) is addition-polymerized. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 1.
[Compound (A)]
A β-diketone compound of palladium.
[Compound (B)]
Ionic boron compounds.
[Compound (C)]
A phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group.

(Formula (1) R ¹ in is a monovalent organic group having no aliphatic unsaturated bonds of the same or different from each other, s is an integer of 0 to 2, j is 0 or 1. )

(A ^{1 to} A ⁴ in the formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and A substituent selected from a halogenated hydrocarbon group, or a substituent having a polarity selected from an oxetanyl group and an alkoxycarbonyl group, and A ¹ and A ² or A ¹ and A ³ are bonded to each other. (An alicyclic structure, an aromatic ring structure, a carbonimido group, or an acid anhydride group may be formed together with an atom. I represents 0 or 1.)
[Claim 11]
The high gas-permeable cyclic structure according to claim 10, wherein compound (A) is bis (acetylacetonato) palladium, compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and compound (C) is tricyclohexylphosphine. A method for producing an olefin addition polymer.
[Claim 12]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 10 or 11, wherein R ¹ in formula (1) is a methyl group, and s is 0.
[Claim 13]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 10 or 11, wherein R ¹ in formula (1) is a methyl group and s is 1.
[Claim 14]
A < ¹ > -A < ⁴ > in Formula (2) is a hydrogen atom, and i is 0, The manufacturing method of the highly gas-permeable cyclic olefin addition polymer of any one of Claims 10-13.
[Claim 15]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 10 to 14, wherein the addition polymerization is carried out at -20 to 100 ° C for 1 to 72 hours in an inert gas atmosphere.

  The polymer of the present invention can be produced by vinyl addition polymerization of a cyclic olefin using the multicomponent catalyst. The polymer of the present invention is excellent in gas permeability, particularly oxygen permeability, and at the same time has high thermal stability (heat resistance), film strength (mechanical strength), and excellent solubility in an organic solvent.

2 is a ¹ H-NMR chart of polymer P (1) obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of polymer P (4) obtained in Example 4. FIG.

The highly gas-permeable cyclic olefin addition polymer of the present invention uses a multi-component catalyst containing the following compounds (A), (B), and (C), and the cyclic olefin functionality represented by the formula (1) described later. It is obtained by addition polymerization of a functional siloxane or a cyclic olefin functional siloxane of the formula (1) and a cyclic olefin compound represented by the formula (2) described later.
[Compound (A)]
A β-diketone compound of palladium.
[Compound (B)]
Ionic boron compounds.
[Compound (C)]
A phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group.

  Conventional cycloolefin compound addition polymerization catalysts are selected from Group 8 elements, Group 9 elements and Group 10 elements of the periodic table, for example, iron (Fe), cobalt (Co), nickel (Ni) , Transition metal complexes having ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt) and the like as a central metal. However, in order to obtain the cyclic olefin addition polymer of the present invention having both excellent physical properties, the reactivity to the cyclic olefin functional siloxane represented by the formula (1) is high, and further, the resulting polymer is high. A molecular weight is essential, and from this point, a compound (A), an ionic boron compound (B), and a phosphine compound (C) having a specific ligand with palladium as a central metal are used together. There is a need.

[Compound (A)]
Compound (A) is a β-diketone compound of palladium which is a Group 10 element of the Periodic Table. Specific examples thereof include bis (acetylacetonato) palladium, bis (hexafluoroacetylacetonato) palladium, and bis (ethylacetoacetonato) palladium. Among these, bis (acetylacetonato) palladium is preferable in view of handling properties and easy availability.

[Compound (B)]
Compound (B) is an ionic boron compound. Specific examples thereof include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate or lithium tetrakis (pentafluorophenyl) borate-ethyl ether complex. Among these, triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferable in consideration of solubility in an organic solvent.

[Compound (C)]
The compound (C) is a phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group. Specific examples thereof include triisopropylphosphine, tri-t-butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, di-t-butylphenylphosphine and the like. Of these, tricyclohexylphosphine is preferable from the viewpoint of both the activity and stability of the catalyst.

  In the present invention, bis (acetylacetonato) palladium is used as the compound (A), triphenylcarbenium tetrakis (pentafluorophenyl) borate is used as the compound (B), and tricyclohexylphosphine is used as the compound (C). It is one of preferred embodiments to produce a cyclic olefin addition polymer.

  The highly gas-permeable cyclic olefin addition polymer of the present invention includes a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane represented by the formula (1) and the following formula (2): ) Represented by addition polymerization using a multi-component catalyst composed of the above-mentioned compounds (A), (B), and (C).

（式（１）中のＲ¹は互いに同一又は異種の脂肪族不飽和結合を有さない一価の有機基であり、ｓは０〜２の整数であり、ｊは０又は１を示す。）

(Formula (1) R ¹ in is a monovalent organic group having no aliphatic unsaturated bonds of the same or different from each other, s is an integer of 0 to 2, j is 0 or 1. )

（式（２）中のＡ¹〜Ａ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アリーロキシ基及びハロゲン化炭化水素基から選ばれる置換基、又はオキセタニル基及びアルコキシカルボニル基から選ばれる極性を有する置換基である。また、Ａ¹とＡ²又はＡ¹とＡ³とが、それぞれが結合する炭素原子とともに脂環構造、芳香環構造、カルボンイミド基又は酸無水物基を形成してもよい。ｉは０又は１を示す。）

(A ^{1 to} A ⁴ in the formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and A substituent selected from a halogenated hydrocarbon group, or a substituent having a polarity selected from an oxetanyl group and an alkoxycarbonyl group, and A ¹ and A ² or A ¹ and A ³ are bonded to each other. (An alicyclic structure, an aromatic ring structure, a carbonimido group, or an acid anhydride group may be formed together with an atom. I represents 0 or 1.)

In the above formula (1), R ¹ is a monovalent organic group that does not have an aliphatic unsaturated bond that may be the same or different from each other, and preferably an unsubstituted or substituted monovalent carbon group having 1 to 10 carbon atoms. Hydrogen group, for example, alkyl group such as methyl group, ethyl group, n-propyl group, butyl group and pentyl group, aryl group such as phenyl group, tolyl group and xylyl group, 2-phenylethyl group, 3-phenylpropylene And an aralkyl group such as a ru group, or a group in which one or more hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Examples of the cyclic olefin functional siloxane represented by the formula (1) include the following compounds, but the present invention is not limited to these specific examples. Here, Me represents a methyl group and Ph represents a phenyl group (hereinafter the same).

  The cyclic olefin functional siloxane represented by the formula (1) may be used alone or in combination of two or more.

The cyclic olefin functional siloxane represented by the formula (1) can be produced by, for example, the following method when R ¹ is a methyl group, j = 0, s = 0 in the formula (1).

  As a first method, as shown in the following reaction formula, it can be synthesized by a Diels-Alder reaction between a siloxane having a terminal olefin and dicyclopentadiene.

  As a second method, it can be synthesized by subjecting norbornadiene and the corresponding SiH group-containing functional siloxane to an addition reaction in the presence of a platinum catalyst.

On the other hand, in formula (2), A ^{1 to} A ⁴ are each independently a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a methyl group having 1 to 10 carbon atoms, an ethyl group or a propyl group. Group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group and other alkyl groups, vinyl group, allyl group, butenyl group, hexenyl group, etc. Alkenyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, aryloxy groups such as phenoxy groups, 3, 3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, p-chloro A group selected from a halogenated hydrocarbon group such as an phenyl group, or an alkoxycarbonyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, preferably an alkoxy group such as an oxetanyl group, a methoxycarbonyl group, and a tert-butoxycarbonyl group. A substituent having a selected polarity. A ¹ and A ² or A ¹ and A ³ may form an alicyclic structure, an aromatic ring structure, a carbonimide group, or an acid anhydride group together with the carbon atoms to which they are bonded.

  In this case, examples of the alicyclic structure in the formula (2) include those having 4 to 10 carbon atoms, and examples of the aromatic ring structure include those having 6 to 12 carbon atoms. Examples of these structures are as follows.

  Examples of the state in which these are bonded to the norbornene ring are as follows. In the formula (2), a case where i = 0 is shown.

  Although the following compounds can be illustrated as a cyclic olefin compound represented by Formula (2), This invention is not limited to these specific examples.

Bicyclo [2.2.1] hept-2-ene, 5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-propyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-pentyl-bicyclo [2.2.1] hept- 2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-decyl-bicyclo [2.2. 1] Hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-allyl-bicyclo [ 2.2.1] Hept-2-ene, 5-isopropylidene-bicyclo [2.2.1] Put-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-chloro-bicyclo [2. 2.1] hept-2-ene, methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, Bicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methyl-bicyclo [ 2.2.1] ethyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] propyl propyl-5-ene-2-carboxylate, 2-methyl-bicyclo [2. 2.1] Trifuro of hept-5-ene-2-carboxylic acid Ethyl, 2-methyl-bicyclo [2.2.1] hept-2-enyl acetate, 2-methyl-bicyclo [2.2.1] hept-5-enyl acrylate, 2-methyl-bicyclo methacrylate [ 2.2.1] Hept-5-enyl, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, tricyclo [4.3.0.1 ^2,5 ] deca-3 -Ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like. These may be used alone or in combination of two or more.

  The cyclic olefin compound represented by the formula (2) preferably has no unsaturated bond in the structure from the viewpoint of heat resistance and oxidative degradation of the resulting polymer, and 5-vinyl-bicyclo [2.2 .1] When addition polymerization is performed using a compound containing an unsaturated bond such as hept-2-ene, hydrogenation or hydrosilylation of the carbon-carbon double bond in the side chain of the polymer is It is preferable at the point which can improve oxidation deterioration property.

  In addition, in the cyclic olefin compound represented by the formula (2), when a polar group such as an ester group is contained, the adhesion of the resulting polymer to the adherend and the solubility in an organic solvent are enhanced, Since gas permeation performance tends to decrease, it is preferable to select appropriately according to the purpose.

  The charge ratio of the cyclic olefin functional siloxane represented by the above formula (1) and the cyclic olefin compound represented by the above formula (2) takes into consideration the gas permeation characteristics of the obtained cyclic olefin addition polymer of the present invention. The total amount of structural units derived from the formula (1) in the obtained polymer is preferably 40 to 100 mol%, and more preferably 45 to 100 mol%.

The compounds (A), (B) and (C) constituting the multi-component catalyst are used in the following ranges.
The compound (A) preferably has from 1 / 1,000,000 to 1 / 100,000, more preferably from 1 / 1,000,000 to 1 / 1,000,000 per 1 mol of the total of the monomers represented by the formulas (1) and (2) One mole atom per minute. If the amount of the compound (A) used is too large, a polymer having the desired molecular weight may not be obtained, and if it is too small, the polymerization activity may decrease.
Moreover, 1.0-2.0 mol is preferable with respect to 1 mol of compounds (A), and, as for a compound (B), More preferably, it is 1.0-1.5 mol. If the amount of the compound (B) used is too large, it may remain in the polymer and color, and if it is too small, the polymerization activity may decrease.
0.25-2.0 mol is preferable with respect to 1 mol of compounds (A), and, as for a compound (C), More preferably, it is 0.5-1.5 mol. If the amount of the compound (C) used is too large, the polymerization activity may decrease, and if it is too small, the stability of the catalyst may decrease.

  The highly gas-permeable cyclic olefin addition polymer of the present invention uses a multicomponent catalyst comprising the above compounds (A), (B), and (C), an alicyclic hydrocarbon solvent such as cyclohexane and cyclopentane, hexane , Aliphatic hydrocarbon solvents such as octane, aromatic hydrocarbon solvents such as toluene, benzene and xylene, halogenated hydrocarbon solvents such as dichloromethane, tetrachloroethylene and chlorobenzene, and cyclic such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane It can manufacture by superposing | polymerizing in the 1 type, or 2 or more types of solvent chosen from a polysiloxane solvent etc.

  The amount of the solvent used is such that the mass ratio (S / M) of the solvent (S) and the cyclic olefin monomer (the total amount of the compounds represented by the above formulas (1) and (2)) (M) is 1 It is preferable to set it as the range of -30, especially the range of 1-20. When the amount of the solvent used is less than the above mass ratio, the solution viscosity is high and handling properties may be difficult, and when it is more than the above mass ratio, the polymerization activity may be inferior.

  When the multi-component catalyst comprising the compounds (A), (B), and (C) is contact-mixed with the cyclic olefin monomer, (Operation procedure 1) Compound (B), (C), cyclic olefin monomer The solution comprising the compound and the solvent may be mixed with a solution prepared by dissolving the compound (A) in the solvent. (Procedure 2) To the solution comprising the compound (B), the cyclic olefin monomer and the solvent, A solution in which the compounds (A) and (C) are dissolved in the above solvent may be added and mixed. (Operation Procedure 3) A solution composed of a cyclic olefin monomer and a solvent is added to the compounds (A), (B), ( A solution prepared by dissolving C) in the above solvent may be added and mixed. Among these, the operation procedure 3 is more preferable from the viewpoint of efficient generation of catalytically active species.

  As a polymerization method, the reaction vessel was charged in an inert gas atmosphere such as nitrogen or argon by the above-described operation procedure, and the temperature was in the range of -20 to 100 ° C, particularly 0 to 80 ° C, for 1 to 72 hours, particularly 2 It is preferred to polymerize for ~ 48 hours. If the reaction temperature is too low, the polymerization activity may be inferior, and if it is too high, gelation may occur or it may be difficult to adjust the molecular weight.

  Moreover, you may add a molecular weight modifier in a polymerization system as needed. Examples of the molecular weight regulator include hydrogen, α-olefins such as ethylene, butene, 1-hexene and 1-octene, cycloalkenes such as cyclopentene and cyclooctene, aromatic vinyl compounds such as styrene, 3-methylstyrene and divinylbenzene, Examples thereof include vinyl silicon compounds such as tris (trimethylmethoxy) vinylsilane, divinyldihydrosilane, and vinylcyclotetrasiloxane.

  In addition, since the ratio of the solvent and the monomer, the polymerization temperature, the polymerization time, and the amount of the molecular weight regulator described above are significantly affected by the catalyst used, the monomer structure, and the like, it is difficult to generally limit them. In order to obtain the polymer having the above specific structure, it is necessary to use properly depending on the purpose.

  The molecular weight of the polymer is controlled by the amount of the polymerization catalyst and the addition amount of the molecular weight regulator, the conversion rate from the monomer to the polymer, or the polymerization temperature.

  The polymerization is stopped by a compound selected from water, alcohol, ketone, organic acid and the like. The catalyst residue can be separated and removed from the polymer solution by adding a mixture of an acid water such as lactic acid, malic acid, and oxalic acid to the polymer solution. For removal of the catalyst residue, adsorption removal using activated carbon, diatomaceous earth, alumina, silica or the like, filtration separation removal using a filter or the like can be applied.

  The polymer can be obtained by putting the polymer solution in alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone, solidifying, and drying under reduced pressure at 60 to 150 ° C. for 6 to 48 hours. In this step, catalyst residues and unreacted monomers remaining in the polymer solution are also removed. In addition, the unreacted monomer containing siloxane used in the present invention can be easily obtained by using a solvent in which a cyclic polysiloxane such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane is mixed with the above alcohols or ketones. Can be removed.

  The cyclic olefin addition polymer of the present invention thus obtained is formed by addition polymerization using the cyclic olefin functional siloxane represented by the above formula (1) as a monomer. Contains the repeat unit indicated.

（式（３）中のＲ¹、ｓ及びｊは式（１）と同じである。）

(R ¹ , s, and j in Formula (3) are the same as in Formula (1).)

  The cyclic olefin addition polymer of the present invention is formed by addition polymerization using the cyclic olefin compound represented by formula (2) as a monomer when the cyclic olefin compound represented by formula (2) is used. The repeating unit shown by following formula (4) is included.

（式（４）中のＡ¹〜Ａ⁴及びｉは式（２）と同じである。）

(A ^{1 to} A ⁴ and i in formula (4) are the same as in formula (2).)

Here, the repeating unit represented by the formula (4) represents a 2,3-addition structural unit when, for example, i is 0 and A ^{1 to} A ⁴ are all hydrogen atoms, the above formula (2) And a cyclic olefin compound represented by the formula (2) may be included as a 2,7 addition structural unit by addition polymerization. This structural unit is the same in the repeating unit represented by the formula (3).

  The ratio of the structural unit represented by Formula (3) in the highly gas-permeable cyclic olefin addition polymer of this invention is 40-100 mol% normally, Preferably it is 45-100 mol%. If the proportion of the structural unit represented by the formula (3) is less than 40 mol%, the gas permeability becomes insufficient. In particular, in terms of gas permeability, solubility in organic solvents, and mechanical strength, the structural unit derived from formula (1) is 45 to 100 mol% in the cyclic olefin compound, and the structural unit derived from formula (2). Is preferably contained in a proportion of 0 to 55 mol%.

  The structural units represented by the formulas (3) and (4) in the highly gas-permeable cyclic olefin addition polymer of the present invention may be present randomly or in a block form.

  The molecular weight of the cyclic olefin addition polymer of the present invention is an important factor involved in the development of excellent physical properties. The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 200,000 to 1,500,000, preferably 200,000 to 900,000, and the weight average molecular weight ( The ratio of Mw) to number average molecular weight (Mn) (dispersion degree: Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.7. When the number average molecular weight is less than 200,000, when it is made into a thin film, a film and a sheet, it becomes brittle and easily broken, and the film strength that can withstand actual use cannot be obtained. On the other hand, when the number average molecular weight exceeds 1,500,000, molding processability and solubility in solvents are lowered, solution viscosity is increased, and handling is difficult. Moreover, when the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) exceeds 4.0, it may be inferior in terms of cracking and brittleness. In the present invention, when a multi-component catalyst comprising the compounds (A), (B), and (C) is used, the number average molecular weight (Mn) is 200,000 to 1,500,000, and the weight average molecular weight. A cyclic olefin addition polymer having a narrow molecular weight distribution in which the ratio (Mw / Mn) of (Mw) to the number average molecular weight (Mn) is in the range of 1.0 to 4.0 can be easily obtained. For this reason, when it is used as a thin film such as a coating film, a film or a sheet, it is excellent in terms of cracking and brittleness.

  The glass transition temperature of the cyclic olefin addition polymer of the present invention is measured using TMA (Thermal Mechanical Analysis). It is preferable that the glass transition temperature of the cyclic olefin addition polymer of this invention evaluated in this way is 200-400 degreeC, More preferably, it is 220-380 degreeC. When the glass transition temperature is less than 200 ° C., problems such as thermal deformation may occur during processing or use of the molded product containing the cyclic olefin addition polymer of the present invention. Moreover, when a glass transition temperature exceeds 400 degreeC, when performing heat processing, processing temperature is too high and the molded object containing the cyclic olefin addition polymer of this invention may deteriorate thermally.

The structure of the cyclic olefin addition polymer of the present invention can be confirmed using a nuclear magnetic resonance spectrum ( ¹ H-NMR, ²⁹ Si-NMR). For example, in ¹ H-NMR (in deuterated chloroform), 7.8 to 6.5 ppm of —O—Si (C ₆ H ₅ ) —O— is absorbed by —C ₆ H ₅ , 0.6 to 3. absorption derived from the alicyclic hydrocarbon 0ppm, -Si-CH ₂ of _{0.0~0.6ppm -, - Si-CH 3} , absorption of _{-O-Si-CH 3, -0.1~0} . -O-Si (CH ₃₎ -O- absorption of 0 ppm, also at ²⁹ Si-NMR (in deutero benzene) is, M units according to the following formula (5) (R ^3: methyl group, 10.0 Absorption derived from 5.0 ppm), absorption derived from D units (R ³ : methyl group, -15.0 to −25.0 ppm, R ³ : phenyl group, −45.0 to −50.0 ppm), T The structure can be confirmed from the absorption derived from the unit (R ³ : alkyl group, −65.0 to −70.0) and its integration ratio.

（式（５）中のＲ³は、式（１）中のＲ¹と同じである。）

(R ³ in formula (5) is the same as R ¹ in formula (1).)

  The highly gas-permeable cyclic olefin addition polymer of the present invention is preferably used as a thin film, sheet or film shape. Although it does not restrict | limit especially as a thin film, a sheet | seat, or film thickness, Usually, it adjusts according to the objective in the range of 10 nm-3 mm. The method of forming a thin film, sheet, or film shape is not particularly limited, and can be formed by any method. However, the polymer of the present invention can be used as a solvent in that the deterioration of the polymer due to thermal history can be suppressed. A solution casting method (casting method) in which the solvent is dissolved and coated and then the solvent is dried, or a water surface spreading thin film method in which the polymer solution of the present invention is dropped onto the water surface and then scrubbed with the support. The polymer of the invention is preferably dissolved in a solvent, applied to a support, and then molded by a dry / wet phase change method in which the polymer is immersed in a poor solvent.

  The solvent used in the solution casting method, the water surface development thin film method, and the dry / wet phase conversion method needs to be a solvent that dissolves the addition polymer of the present invention. Many of the addition polymers according to the present invention include aliphatic hydrocarbon solvents such as cyclopentane, hexane, cyclohexane, decane and isododecane, aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene, and halogenated carbonization such as dichloromethane and chloroform. It can be dissolved in a polysiloxane solvent such as hydrogen solvent, hexamethyldisiloxane, methyltris (trimethylsiloxy) silane, decamethylcyclopentasiloxane, etc., and these solvents can be used alone or as a mixed solvent of two or more. The cyclic olefin addition polymer of the present invention exhibits excellent solubility in any of the above solvents, but depending on the film thickness and coating conditions, the residual solvent may not be removed during drying. For this reason, a solvent having a relatively low boiling point and containing hexane, cyclohexane, toluene or the like as a main component is preferable.

The oxygen permeability coefficient of the cyclic olefin addition polymer cast film of the present invention formed by the above method is measured using a differential pressure method. The oxygen permeability coefficient of the cyclic olefin addition polymer cast film of the present invention thus evaluated is preferably 40 Barrer (1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg) or more. It is preferably 100 Barrer (1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg) or more. When the oxygen permeability coefficient is less than 40 Barrer (1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg), sufficient oxygen transport performance may not be obtained.

  Since the high gas-permeable cyclic olefin addition polymer of the present invention contains a high proportion of the structural unit represented by the above formula (3) which is a structural unit derived from the monomer of the above formula (1), it is an isododecane solvent. And high solubility in polysiloxane solvents such as methyltris (trimethylsiloxy) silane and decamethylcyclopentasiloxane. These solvents are known as highly safe solvents with low impact on the human body and low environmental impact. For this reason, application to the medical / food / cosmetic field, which is often difficult with existing cyclic olefin addition polymers (reference: Patent Documents 7 to 22), is also possible. For applications in these fields, the solubility in an isododecane solvent or a siloxane solvent is preferably 10% by mass or more, more preferably 30% by mass or more. When the amount is less than 10% by mass, the coated film is thin and may be inferior in terms of cracking and brittleness.

  The solution containing the highly gas-permeable cyclic olefin addition polymer of the present invention can be blended with a known antioxidant to improve oxidation stability.

As an antioxidant,
2,6-di-t-butyl-4-methylphenol,
4,4′-thiobis- (6-tert-butyl-3-methylphenol),
1,1′-bis- (4-hydroxyphenyl) cyclohexane,
2,5-di-t-butylhydroquinone,
Phenolic or hydroquinone type such as pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate,
Tris (4-methoxy-3,5-diphenyl) phosphite,
Tris (nonylphenyl) phosphite,
Tris (2,4-di-tert-butylphenyl) phosphite,
Phosphorus compounds such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, thioether compounds, and lactone compounds are also included. Among these compounds, those having a decomposition temperature (5% mass reduction temperature) of 250 ° C. or more are preferable. Moreover, the compounding quantity of these antioxidants is the range of 0.05-5.0 mass parts with respect to 100 mass parts of cyclic olefin addition polymers of this invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the following examples, Me represents a methyl group, Ph represents a phenyl group, and Cy represents a cyclohexyl group.

The molecular weight, molecular weight distribution, monomer composition ratio, solubility, glass transition temperature, breaking strength, breaking elongation and oxygen permeability coefficient of the polymer were evaluated by the following methods.
1) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymers obtained in the examples were determined by polystyrene using polystyrene as a standard substance.
2) The composition ratio of norbornene derivative / norbornene in the copolymer was determined from the integral ratio of the peaks obtained by ¹ H-NMR.
3) Solubility in an organic solvent is such that isododecane, methyltris (trimethylsiloxy) silane (hereinafter referred to as M ₃ T), decamethylcyclopentasiloxane (hereinafter referred to as D ₅ ) is used as a solvent and becomes a 10% by mass solution. Were prepared and evaluated.
4) The glass transition temperature was measured by using a TMA apparatus, fixing a sample having a film thickness of 100 μm, a width of 3 mm, and a length of 20 mm to the probe and raising the temperature from room temperature at 10 ° C./min.
5) The breaking strength and breaking elongation were measured by pulling a film having a thickness of 100 μm into a No. 2 dumbbell shape, fixing it to a probe of a testing machine, and pulling it at a speed of 50 mm / min.
6) The oxygen transmission coefficient was measured by a differential pressure method using a circular sample having a film thickness of 50 μm and a diameter of 4 cm.

[Example 1]
In a glass container purged with nitrogen, 25.3 g (0.065 mol) of monomer A represented by the following formula (6) and 3. monomer B (norbornene) represented by the following formula (7) were used. It was dissolved in 3 g (0.035 mol) toluene 140 ml. Separately prepared catalyst solution (bis (acetylacetonato) palladium [Pd (C ₅ H ₇ O ₂ ) ₂ ] 6 mg (20 μmol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 22 mg (24 μmol) and tricyclohexylphosphine (PCy ₃ ) 3 mg (10 μmol) dissolved in 15 ml of toluene were added, and the polymerization reaction was carried out at room temperature (25 ° C.) for 5 hours. It was.
After the completion of the reaction, the polymer was precipitated by pouring it into a large amount of methanol, washed by filtration and dried under reduced pressure at 120 ° C. for 6 hours to obtain 20.3 g (yield 71%) of polymer P (1).
The polymer P (1) obtained had a molecular weight of Mn = 720,000 and a molecular weight distribution Mw / Mn = 1.41 as measured by GPC. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer A and the structure derived from monomer B in the polymer was A / B = 67/33 (mol / mol). . The ¹ H-NMR chart is shown in FIG. The obtained polymer P (1) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, and then dried at 60 ° C. for 24 hours to prepare a polymer film F (1).

[Example 2]
In a glass container substituted with nitrogen, 202.4 g (0.52 mol) of monomer A represented by the above formula (6) and 26. Monomer B (norbornene) represented by the above formula (7) were used. 4 g (0.28 mol) and 1-octene were dissolved in 400 ml of 1.1 g (0.01 mol) of toluene. Separately prepared catalyst solution (bis (acetylacetonato) palladium [Pd (C ₅ H ₇ O ₂ ) ₂ ] 6 mg (20 μmol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 22 mg (24 μmol) and tricyclohexylphosphine (PCy ₃ ) 3 mg (10 μmol) dissolved in 15 ml of toluene were added, and a polymerization reaction was carried out at 60 ° C. for 10 hours.
After the completion of the reaction, the polymer was precipitated by pouring into a large amount of methanol, washed by filtration, and then dried under reduced pressure at 120 ° C. for 6 hours to obtain 160.2 g (yield 70%) of polymer P (2).
The molecular weight of the obtained polymer P (2) as measured by GPC was Mn = 230,000 and the molecular weight distribution Mw / Mn = 2.56. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer A and the structure derived from monomer B in the polymer was A / B = 67/33 (mol / mol). . The obtained polymer P (2) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, followed by drying at 60 ° C. for 24 hours to produce a polymer film F (2).

[Example 3]
In Example 1, 20.5 g (0.065 mol) of the monomer C represented by the following formula (8) is used instead of the monomer A, and the experiment is performed in the same manner except that the reaction time is 2 hours. As a result, 16.6 g (yield 70%) of polymer P (3) was obtained. The molecular weight is Mn = 755,000, the molecular weight distribution Mw / Mn = 1.50, and the composition ratio of the structure derived from the monomer C and the structure derived from the monomer B in the polymer is C / B = 67. / 33 (mol / mol). The obtained polymer P (3) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, followed by drying at 60 ° C. for 24 hours to produce a polymer film F (3).

[Example 4]
The monomer C represented by the above formula (8) was dissolved in 125.9 g (0.40 mol) and 1-octene in 90 mg (0.8 mmol) in 200 ml of toluene in a glass container substituted with nitrogen. Separately prepared catalyst solution (bis (acetylacetonato) palladium [Pd (C ₅ H ₇ O ₂ ) ₂ ] 6 mg (20 μmol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 22 mg (24 μmol) and tricyclohexylphosphine (PCy ₃ ) 3 mg (10 μmol) dissolved in 15 ml of toluene were added, and a polymerization reaction was carried out at 60 ° C. for 10 hours.
After completion of the reaction, the polymer was precipitated by pouring into a large amount of methanol, washed by filtration, and dried under reduced pressure at 120 ° C. for 6 hours to obtain 73.0 g (yield 58%) of polymer P (4).
The obtained polymer P (4) had a molecular weight of Mn = 595,000 and a molecular weight distribution Mw / Mn = 2.49 as measured by GPC. The ¹ H-NMR chart of the obtained polymer P (4) is shown in FIG. The obtained polymer P (4) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, and then dried at 60 ° C. for 24 hours to prepare a polymer film F (4).

[Comparative Example 1]
In a glass container substituted with nitrogen, 7.0 g (0.018 mol) of monomer A represented by the above formula (6) and 14.9 g of monomer B (norbornene) represented by formula (7) ( 0.159 mol) was dissolved in 140 ml of toluene. Separately prepared catalyst solution (bis (acetylacetate) nickel [Ni (acac) ₂ ] 23 mg (89 μmol), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] 228 mg (445 μmol) in toluene 15 ml And the polymerization reaction was carried out at room temperature (25 ° C.) for 2 hours.
After completion of the reaction, the polymer was precipitated by pouring into a large amount of methanol, washed by filtration, and dried under reduced pressure at 120 ° C. for 6 hours to obtain 16.2 g (yield 74%) of polymer P (5). .
The molecular weight of the obtained polymer as measured by GPC was Mn = 253,000 and the molecular weight distribution Mw / Mn = 2.25. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer A and the structure derived from monomer B in the polymer was A / B = 8/92 (mol / mol). . The obtained polymer P (5) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, followed by drying at 60 ° C. for 24 hours to prepare a polymer film F (5).

[Comparative Example 2]
In a glass container substituted with nitrogen, 55.2 g (0.142 mol) of the monomer A represented by the above formula (6) and 3.3 g of the monomer B (norbornene) represented by the formula (7). (0.035 mol) was dissolved in 240 ml of toluene. Separately prepared catalyst solution (bis (acetylacetate) nickel [Ni (acac) ₂ ] 23 mg (89 μmol), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] 228 mg (445 μmol) in toluene 15 ml And the polymerization reaction was carried out at 60 ° C. for 24 hours.
After the reaction was completed, the polymer was precipitated by pouring into a large amount of methanol, washed by filtration, and dried under reduced pressure at 120 ° C. for 6 hours to obtain 29.3 g (yield 50%) of polymer P (6). .
The molecular weight of the obtained polymer as measured by GPC was Mn = 48,000 and the molecular weight distribution Mw / Mn = 2.04. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer A and the structure derived from monomer B in the polymer was A / B = 46/54 (mol / mol). . The obtained polymer P (6) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a polymer film F (6) was produced by a solution casting method, but it was fragile and could not be handled.

[Comparative Example 3]
In a glass container substituted with nitrogen, 5.7 g (0.018 mol) of monomer C represented by the above formula (8) and 14.9 g of monomer B (norbornene) represented by formula (7) ( 0.159 mol) was dissolved in 140 ml of toluene. Separately prepared catalyst solution (bis (acetylacetate) nickel [Ni (acac) ₂ ] 23 mg (89 μmol), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] 228 mg (445 μmol) in toluene 15 ml And the polymerization reaction was carried out at room temperature (25 ° C.) for 2 hours.
After completion of the reaction, the polymer was precipitated by pouring into a large amount of methanol, washed by filtration and dried under reduced pressure at 120 ° C. for 6 hours to obtain 15.7 g (yield 76%) of polymer P (7). .
The molecular weight of the obtained polymer as measured by GPC was Mn = 282,000 and molecular weight distribution Mw / Mn = 2.21. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer A and the structure derived from monomer B in the polymer was C / B = 10/90 (mol / mol). . The obtained polymer P (7) was dissolved in toluene to prepare a 10% by mass polymer solution. Using this solution, a film was formed by a solution casting method, and then dried at 60 ° C. for 24 hours to prepare a polymer film F (7).

[Comparative Example 4]
The monomer C represented by the above formula (8) was dissolved in 125.9 g (0.40 mol) and 1-octene in 90 mg (0.8 mmol) in 200 ml of toluene in a glass container substituted with nitrogen. Separately prepared catalyst solution (bis (acetylacetate) nickel [Ni (acac) ₂ ] 5 mg (20 μmol), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] 51 mg (100 μmol) in 15 ml of toluene And a polymerization reaction was carried out at 60 ° C. for 10 hours, but no polymer was obtained.

Table 1 shows the results of the yield, composition, number average molecular weight and molecular weight distribution of the polymers P (1) to P (7) obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
In Table 2, the evaluation result of the solubility with respect to various solvents of polymer P (1) -P (7) obtained in Examples 1-4 and Comparative Examples 1-3 is shown.
Table 3 shows various evaluation results of the polymer films F (1) to F (7) obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

○：溶解、△：部分溶解、×：不溶
（ポリシロキサン溶媒）
Ｍ₃Ｔ：メチルトリス（トリメチルシロキシ）シラン
Ｄ₅：デカメチルシクロペンタシロキサン

○: dissolved, Δ: partially dissolved, x: insoluble (polysiloxane solvent)
M ₃ T: Methyltris (trimethylsiloxy) silane D ₅ : Decamethylcyclopentasiloxane

１Ｂａｒｒｅｒ＝１０^-10ｃｍ³（ＳＴＰ）・ｃｍ／ｃｍ²・ｓ・ｃｍＨｇ

1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg

  From the above results, the cyclic olefin addition polymer having the organosiloxane of the present invention as a pendant has excellent solubility, film-forming property, gas permeability, heat resistance, mechanical strength, and a multi-component system having a specific structure. It turns out that it can manufacture easily by using a catalyst.

  The highly gas-permeable cyclic olefin addition polymer of the present invention is excellent in film forming properties and has excellent gas permeability, heat resistance, and mechanical strength. The polymer of the present invention is expected to be applied to oxygen-enriched membranes for air conditioners and fuel cells, contact lenses, and the like. Furthermore, the polymer of the present invention has excellent solubility in organic solvents and polysiloxane solvents. Therefore, application to coating agents for pharmaceuticals, foods and cosmetics can be expected.

Claims (15)

Using a multi-component catalyst containing the following compounds (A), (B), and (C), a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane of the formula (1) And a cyclic olefin compound represented by the following formula (2) is obtained by addition polymerization, and the proportion of structural units derived from the cyclic olefin functional siloxane represented by the following formula (1) is an addition polymer. A high gas-permeable cyclic olefin addition polymer having a polystyrene-reduced number average molecular weight (Mn) of 200,000 to 1,500,000 as measured by GPC.
[Compound (A)]
A β-diketone compound of palladium.
[Compound (B)]
Ionic boron compounds.
[Compound (C)]
A phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group.

(Formula (1) R ¹ in is a monovalent organic group having no aliphatic unsaturated bonds of the same or different from each other, s is an integer of 0 to 2, j is 0 or 1. )

(A ^{1 to} A ⁴ in the formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and A substituent selected from a halogenated hydrocarbon group, or a substituent having a polarity selected from an oxetanyl group and an alkoxycarbonyl group, and A ¹ and A ² or A ¹ and A ³ are bonded to each other. (An alicyclic structure, an aromatic ring structure, a carbonimido group, or an acid anhydride group may be formed together with an atom. I represents 0 or 1.)   The high gas-permeable cyclic structure according to claim 1, wherein the compound (A) is bis (acetylacetonato) palladium, the compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and the compound (C) is tricyclohexylphosphine. Olefin addition polymer. The highly gas-permeable cyclic olefin addition polymer according to claim 1 or 2, wherein R ¹ in formula (1) is a methyl group and s is 0. The highly gas-permeable cyclic olefin addition polymer according to claim 1 or 2, wherein R ¹ in formula (1) is a methyl group and s is 1. The high gas-permeable cyclic olefin addition polymer according to any one of claims 1 to 4, wherein A ^{1 to} A ⁴ in formula (2) are all hydrogen atoms and i is 0.   The high gas according to any one of claims 1 to 5, wherein the ratio (dispersity: Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene is 1.0 to 4.0. A permeable cyclic olefin addition polymer.   Glass transition temperature is 200-400 degreeC, The high gas permeability cyclic olefin addition polymer of any one of Claims 1-6. 2. The oxygen permeability coefficient of a high gas permeable cyclic olefin addition polymer cast film measured by a differential pressure method is 40 Barrer (1 Barrer = 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg) or more. The high gas-permeable cyclic olefin addition polymer of any one of -7.   The highly gas-permeable cyclic olefin addition polymer according to any one of claims 1 to 8, which exhibits solubility in a solvent of isododecane, methyltris (trimethylsiloxy) silane or decamethylcyclopentasiloxane at 10% by mass or more. In the presence of a multi-component catalyst containing the following compounds (A), (B), (C), a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane of the formula (1) And a cyclic olefin compound represented by the following formula (2) is addition-polymerized. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 1.
[Compound (A)]
A β-diketone compound of palladium.
[Compound (B)]
Ionic boron compounds.
[Compound (C)]
A phosphine compound having a substituent selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group, and an aryl group.

(Formula (1) R ¹ in is a monovalent organic group having no aliphatic unsaturated bonds of the same or different from each other, s is an integer of 0 to 2, j is 0 or 1. )

(A ^{1 to} A ⁴ in the formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and A substituent selected from a halogenated hydrocarbon group, or a substituent having a polarity selected from an oxetanyl group and an alkoxycarbonyl group, and A ¹ and A ² or A ¹ and A ³ are bonded to each other. (An alicyclic structure, an aromatic ring structure, a carbonimido group, or an acid anhydride group may be formed together with an atom. I represents 0 or 1.)   The high gas-permeable cyclic structure according to claim 10, wherein the compound (A) is bis (acetylacetonato) palladium, the compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and the compound (C) is tricyclohexylphosphine. A method for producing an olefin addition polymer. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 10 or 11, wherein R ¹ in formula (1) is a methyl group, and s is 0. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 10 or 11, wherein R ¹ in formula (1) is a methyl group and s is 1. A < ¹ > -A < ⁴ > in Formula (2) is a hydrogen atom, and i is 0, The manufacturing method of the highly gas-permeable cyclic olefin addition polymer of any one of Claims 10-13.   The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 10 to 14, wherein the addition polymerization is carried out at -20 to 100 ° C for 1 to 72 hours in an inert gas atmosphere.

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