JP5585508B2 - Cyclic olefin addition polymer and process for producing the same - Google Patents

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.

  Air conditioners (hereinafter abbreviated as "air conditioners") that provide comfortable living and working spaces are essential equipment for transportation vehicles such as office buildings, public facilities, hospitals, and houses, as well as automobiles, railways, ships, and aviation. It has become. 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. In particular, in the case of a transporting machine, safety problems such as drowsiness may occur. Opening the window can prevent a decrease in oxygen concentration, but it leads to energy loss and allows the invasion of pollen, yellow sand, dust, etc., and the built comfortable environment is damaged. In some work environments such as high-rise buildings and aviation, it may not be possible to open the windows. 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, organopolysiloxane itself has a low mechanical strength and has a problem in practical use. In order to improve this, a copolymer with a polycarbonate (Patent Document 1: Japanese Patent Publication No. 4-001652), a polysiloxane-aromatic polyamide block copolymer (Patent Document 2: Japanese Patent Laid-Open No. 5-285216) Etc. 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.

  Recently, Patent Document 7 (Japanese Patent Laid-Open No. 2009-173824) and Patent Document 8 (Japanese Patent Laid-Open No. 2009-249610) have reported addition polymers containing cyclic olefin functional siloxane as a repeating unit in the structure. It was.

Patent Document 9 (Japanese Patent Application Laid-Open No. 2010-174099) reports a high molecular weight addition polymer containing a cyclic olefin functional siloxane as a repeating unit in the structure. However, satisfactory performance has not yet been achieved.
As prior art documents related to the present invention, the following documents can be cited in addition to the above-mentioned Patent Documents 1 to 9.

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 2009-173824 A JP 2009-249610 A JP 2010-174099 A

Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 3982-3989 (2009) Polymer Journal, Vol. 41, 643-649 (2009)

  The present invention has been made in view of the above circumstances, and has high productivity, excellent gas permeability, thermal stability, solubility, and mechanical strength, in particular, a high gas permeability ring having excellent flexibility. An object of the present invention is to provide an olefin addition polymer and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventor has obtained a cyclic olefin functional siloxane represented by the following formula (1), or a cyclic olefin functional siloxane of the formula (1) and the following formula: The ratio of the structural unit obtained by addition polymerization of the cyclic olefin compound represented by (2) and derived from the cyclic olefin functional siloxane represented by the following formula (1) is 5 to 100 in the addition polymer. The cyclic olefin addition weight having a specific structure, which is mol% and has a polystyrene-equivalent number average molecular weight (Mn) measured by GPC using tetrahydrofuran (hereinafter abbreviated as THF) as a solvent. It has been found that the coalescence has excellent oxygen permeability, heat resistance, mechanical strength and solubility, and further has excellent productivity, 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炭素数１〜１０の非置換又はハロゲン原子置換の一価のアルキル基であり、ｓは０〜２の整数であり、ｉは０又は１であり、ｊは１〜４の整数を示す。）

（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共に脂環構造、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。ｋは０又は１を示す。）
〔請求項２〕
式（１）中のＲ¹がメチル基であり、ｓが０であり、ｊが２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１であり、ｊが２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４〕
式（１）中のＲ¹がメチル基であり、ｓが２であり、ｊが２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５〕
式（２）中のＡ¹〜Ａ⁴がいずれも水素原子であり、ｋ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〕
下記化合物（Ａ）、（Ｂ）及び（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）〕
ビス（ジベンジリデンアセトン）パラジウム、トリス（ジベンジリデンアセトン）ジパラジウム、（エテン）ビス（トリシクロヘキシルホスフィン）パラジウム、カルボニルトリス（トリフェニルホスフィン）パラジウム、ビス（ｔ−ブチルイソシアニド）パラジウムから選ばれる０価のパラジウム化合物。
〔化合物（Ｂ）〕
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、トリフェニルカルベニウムテトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、リチウムテトラキス（ペンタフルオロフェニル）ボレート−エチルエーテルコンプレックスから選ばれるイオン性ホウ素化合物。
〔化合物（Ｃ）〕
トリイソプロピルホスフィン、トリｔ−ブチルホスフィン、トリシクロペンチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン、ジｔ−ブチルフェニルホスフィンから選ばれ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炭素数１〜１０の非置換又はハロゲン置換の一価のアルキル基であり、ｓは０〜２の整数であり、ｉは０又は１であり、ｊは１〜４の整数を示す。）

（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共に脂環構造、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。ｋは０又は１を示す。）
〔請求項７〕
化合物（Ａ）が０価のパラジウム１個にジベンジリデンアセトン２個が配位した錯体であるビス（ジベンジリデンアセトン）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６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８〕
式（１）中のＲ¹がメチル基であり、ｓが０であり、ｊが２である請求項６又は７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９〕
式（１）中のＲ¹がメチル基であり、ｓが１であり、ｊが２である請求項６又は７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１０〕
式（１）中のＲ¹がメチル基であり、ｓが２であり、ｊが２である請求項６又は７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１１〕
式（２）中のＡ¹〜Ａ⁴がいずれも水素原子であり、ｋが０である請求項６〜１０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１２〕
不活性ガス雰囲気下、０〜１５０℃で１〜７２時間付加重合する請求項６〜１１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]
It is obtained by addition polymerization of 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). The ratio of the structural unit derived from the cyclic olefin functional siloxane represented by the following formula (1) is 5 to 100 mol% in the addition polymer, and the number in terms of polystyrene measured by GPC using THF as a solvent. A high gas-permeable cyclic olefin addition polymer having an average molecular weight (Mn) of 10,000 to 2,000,000.

(R ¹ in Formula (1) is an unsubstituted or halogen-substituted monovalent alkyl group having 1 to 10 carbon atoms that does not have the same or different aliphatic unsaturated bond, and s is 0 to 2 I is 0 or 1, and j is an integer of 1 to 4.)

(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, and k represents 0 or 1.)
[Claim 2]
The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 0, and j is 2.
[Claim 3]
The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 1, and j is 2.
[Claim 4]
The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 2, and j is 2.
[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 k is 0.
[Claim 6 ]
In the presence of 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) The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein addition polymerization is performed with a cyclic olefin compound represented by the following formula (2):
[Compound (A)]
Zero-valent selected from bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, (ethene) bis (tricyclohexylphosphine) palladium, carbonyltris (triphenylphosphine) palladium, bis (t-butylisocyanide) palladium Palladium compounds.
[Compound (B)]
Triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, lithium tetrakis ( An ionic boron compound selected from pentafluorophenyl) borate-ethyl ether complex .
[Compound (C)]
Triisopropyl phosphine, tri t- butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, selected from di-t- butylphenyl phosphine sulfo Sufin compound.

(R ¹ in Formula (1) is an unsubstituted or halogen-substituted monovalent alkyl group having 1 to 10 carbon atoms that does not have the same or different aliphatic unsaturated bond, and s is 0 to 2 (It is an integer, i is 0 or 1, and j represents an integer of 1 to 4.)

(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, and k represents 0 or 1.)
[Claim 7 ]
Compound (A) is a complex in which two dibenzylideneacetones are coordinated to one zero-valent palladium, bis (dibenzylideneacetone) palladium, compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, compound The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 , wherein (C) is tricyclohexylphosphine.
[Claim 8 ]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 0, and j is 2.
[Claim 9 ]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 1, and j is 2.
[Claim 10 ]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 2, and j is 2.
[Claim 11 ]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 6 to 10 , wherein A ^{1 to} A ⁴ in formula (2) are all hydrogen atoms and k is 0.
[Claim 12 ]
The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 6 to 11 , wherein the addition polymerization is carried out at 0 to 150 ° C for 1 to 72 hours in an inert gas atmosphere.

  The polymer of the present invention has excellent gas permeability, thermal stability and solubility, and further has excellent mechanical strength, particularly flexibility. The polymer of the present invention can be easily and efficiently produced by vinyl addition polymerization of a cyclic olefin using a specific multicomponent catalyst.

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.

（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、ｉは０又は１であり、ｊは１〜４の整数を示す。）

（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共に脂環構造、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。ｋは０又は１を示す。） 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): And a cyclic olefin compound represented by the following formula:

(R ¹ in Formula (1) is a monovalent organic group that does not have the same or different aliphatic unsaturated bond, s is an integer of 0 to 2, i is 0 or 1, j represents an integer of 1 to 4.)

(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, and k 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) is produced by the following method when, for example, R ¹ is a methyl group, i = 0, j = 2, s = 2 in the formula (1). Can do.
As shown in the following reaction formula, 5-vinyl-bicyclo [2.2.1] hept-2-ene and the corresponding SiH group-containing functional siloxane can be synthesized by addition reaction in the presence of a platinum catalyst.

Here, j which is an important structural element of the cyclic olefin functional siloxane represented by the formula (1) will be described. j is an integer of 1 to 4, preferably 1 or 2.
In general, the addition polymerization reaction of cyclic olefins is strongly influenced by substituents. Non-Patent Document 1 (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 3982-3898 (2009)) shows the effect of polar substituents on Non-Patent Document 2 (Polymer Journal, Vol. 41, 643). -649 (2009)) shows the effect of bulky substituents. When a bulky substituent such as a silyl group is adjacent to a cyclic olefin, it occupies the periphery of the metal that is the active center and prevents other monomers from approaching the central metal, thus reducing the polymerization activity. It has been known. Therefore, if the position of the bulky structural portion of the substituent can be moved away from the cyclic olefin, it is possible to prevent a decrease in activity. One method of keeping away is the selective synthesis of exo isomers, which are structural isomers, but this method is not necessarily universal. Therefore, in the present invention, an alkyl chain is introduced as a spacer to keep the bulky structure portion and the cyclic olefin away. As will be described later, the problem of productivity has been solved by the influence of the alkyl chain. Furthermore, it has been found that the mechanical strength, particularly flexibility, of the highly gas-permeable cyclic olefin addition polymer of the present invention is significantly increased by the influence of the alkyl chain.

On the other hand, in the above 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 equation (2), a case where k = 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.

  When the cyclic olefin compound represented by the formula (2) contains a polar group such as an ester group, the adhesion of the resulting polymer to the adherend and the solubility in an organic solvent are enhanced, but gas permeation is achieved. Since 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. In addition, the structural units derived from the formula (1) in the obtained polymer are preferably used in a total amount of 5 to 100 mol%, more preferably 10 to 100 mol%.

The highly gas-permeable cyclic olefin addition polymer of the present invention is a cyclic olefin functional siloxane represented by the formula (1) using a multicomponent catalyst containing the following compounds (A), (B) and (C): Alternatively, it can be obtained by addition polymerization of the cyclic olefin functional siloxane of the formula (1) and the cyclic olefin compound represented by the formula (2).
[Compound (A)]
Zero-valent palladium compound.
[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. From this point, it is necessary to use a compound (A) having a specific ligand with palladium as a central metal, an ionic boron compound (B), and a phosphine compound (C). There is.
Furthermore, the compound (A) having palladium as a central metal is preferably a zero-valent palladium complex from the viewpoint of polymerization activity, molecular weight controllability, and handleability.

[Compound (A)]
The compound (A) is a compound having palladium as a central metal of Group 10 element of the periodic table, particularly a zero-valent palladium compound. Specific examples thereof include bis (dibenzylideneacetone) palladium, which is a complex in which two dibenzylideneacetones are coordinated to one zero-valent palladium, and a complex in which three dibenzylideneacetones are coordinated to two zerovalent palladiums. Tris (dibenzylideneacetone) dipalladium, (ethene) bis (tricyclohexylphosphine) palladium, which is a complex in which one ethylene and one tricyclohexylphosphine are coordinated to one zerovalent palladium, zerovalent palladium Carbonyltris (triphenylphosphine) palladium, which is a complex in which one carbon monoxide and three triphenylphosphines are coordinated to each other, a complex in which two t-butylisocyanides are coordinated to one zerovalent palladium And bis (t-butylisocyanide) palladium. Of these, bis (dibenzylideneacetone) palladium and tris (dibenzylideneacetone) dipalladium are preferable in view of handling, availability, and stability of the complex.

[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. Of these, triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferred in consideration of solubility in organic solvents and easy availability.

[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 (dibenzylideneacetone) palladium or tris (dibenzylideneacetone) dipalladium as compound (A), triphenylcarbenium tetrakis (pentafluorophenyl) borate as compound (B), and tricyclohexyl as compound (C) It is one of preferred embodiments to produce a highly gas permeable cyclic olefin addition polymer using phosphine.

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, 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 0 to 150 ° C., particularly 20 to 100 ° C. for 1 to 72 hours, particularly 2 to 2 hours. It is preferable to polymerize for 48 hours. However, if the reaction temperature is too low, the polymerization activity may be inferior, and if it is too high, gelation may occur or the molecular weight may be difficult to adjust.

  In addition, when a multi-component catalyst composed of the above compounds (A), (B), (C) is used, it is not necessary to add a molecular weight regulator in particular. Good. 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.

  It is difficult to generally limit the ratio of the solvent and the monomer, the polymerization temperature, the polymerization time, and the like. In order to obtain the polymer having the above specific structure, it is necessary to use properly depending on the purpose.

  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.

（式（３）中のＲ¹、ｉ、ｊ及びｓは式（１）と同じである。） 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.

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

（式（４）中のＡ¹〜Ａ⁴及びｋは式（２）と同じである。） 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.

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

Here, the repeating unit represented by the formula (4) represents a 2,3-addition structural unit when, for example, k is 0 and A ^{1 to} A ⁴ are all hydrogen atoms, the above-described 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 the formula (3) in the highly gas-permeable cyclic olefin addition polymer of the present invention is usually 5 to 100 mol%, preferably 10 to 100 mol%. When the proportion of the structural unit represented by the formula (3) is less than 5 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 50 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 50 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) using THF as a solvent is 10,000 to 2,000,000, preferably 50,000 to 1,500,000. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (dispersity: Mw / Mn) is preferably 1.0 to 6.0, more preferably 1.0 to 5.5. It is. When the number average molecular weight is less than 10,000, when it is used as a thin film, film or sheet, it becomes brittle and easily cracked, and the film strength that can withstand actual use cannot be obtained. On the other hand, when the number average molecular weight exceeds 2,000,000, molding processability and solubility in solvents decrease, solution viscosity increases, and handling becomes difficult. Moreover, when the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) exceeds 6.0, 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 10,000 to 2,000,000, 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 6.0 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). The glass transition temperature of the cyclic olefin addition polymer of the present invention evaluated in this way is preferably 130 to 400 ° C, more preferably 140 to 350 ° C. When the glass transition temperature is less than 130 ° C., there is a possibility that 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. Preferably, it is 50 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.

  The breaking elongation of the cyclic olefin addition polymer cast film of the present invention formed by the above method is measured by a tensile test. The breaking elongation of the cyclic olefin addition polymer cast film of the present invention thus evaluated is preferably 50% or more, more preferably 60% or more. If the breaking elongation is less than 50%, cracks may occur during the processing process or operation, and the actual use may not be able to be tolerated.

  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. Therefore, it can be applied to the medical, food and cosmetic fields, which are often difficult with existing cyclic olefin addition polymers. For use in these fields, the solubility in an isododecane solvent or a siloxane solvent is preferably 10% by mass or more, particularly 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 using polystyrene as a standard substance by GPC using THF as a solvent. .
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 thickness of 100 μm and a diameter of 3 cm.

[Example 1]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, 214.8 g (0.8 mol) of monomer A represented by the following formula (6) was dissolved in 600 ml of toluene in a glass container substituted with nitrogen. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 70 ° C. for 2.5 hours.
After 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 12 hours to obtain 206 g (yield 96%) of polymer P (1).
The obtained polymer P (1) had a molecular weight of Mn = 558,000 and a molecular weight distribution Mw / Mn = 3.22 as measured by GPC. FIG. 1 shows the ¹ H-NMR spectrum of the polymer P (1).

[Example 2]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, in a glass container substituted with nitrogen, 150.4 g (0.56 mol) of the monomer A represented by the formula (6) and 22.5 g (0) of the monomer B represented by the following formula (7) .24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 70 ° C. for 2.5 hours.
After 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 12 hours to obtain 158 g (yield 91%) of polymer P (2).
The molecular weight of the obtained polymer P (2) as measured by GPC was Mn = 599,000 and the molecular weight distribution Mw / Mn = 3.24. ^{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 = 70/30 (mol / mol). .

[Example 3]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, in a glass container purged with nitrogen, the monomer C191.9 g (0.56 mol) represented by the formula (8) and the monomer B22.5 g represented by the formula (7) (0. 24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 60 ° C. for 1.5 hours.
After 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 12 hours to obtain 189 g (yield 85%) of polymer P (3).
The obtained polymer P (3) had a molecular weight of Mn = 867,000 and a molecular weight distribution Mw / Mn = 3.24 by GPC measurement. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer C and the structure derived from monomer B in the polymer was C / B = 70/30 (mol / mol). .

[Example 4]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, 233.5 g (0.56 mol) of the monomer D represented by the formula (9) and 22.5 g of the monomer B represented by the formula (7) (0. 24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 55 ° C. for 2.0 hours.
After the 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 12 hours to obtain 192 g (yield 75%) of polymer P (4).
The molecular weight of the obtained polymer P (4) as measured by GPC was Mn = 1330,000 and the molecular weight distribution Mw / Mn = 3.04. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer D and the structure derived from monomer B in the polymer was D / B = 67/33 (mol / mol). . FIG. 2 shows the ¹ H-NMR spectrum of the polymer P (4).

The results of Examples 1 to 4 are shown in Table 1.

[Comparative Example 1]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, the monomer E192.4g (0.8 mol) represented by following formula (10) was melt | dissolved in 600 ml of toluene in the glass container substituted with nitrogen. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 70 ° C. for 16 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 12 hours to obtain 102 g (yield 53%) of polymer P (5).
The molecular weight of the obtained polymer P (5) as measured by GPC was Mn = 620,000 and the molecular weight distribution Mw / Mn = 2.60.

[Comparative Example 2]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, in a glass container substituted with nitrogen, 134.7 g (0.56 mol) of monomer E represented by formula (10) and 22.5 g of monomer B represented by formula (7) (0. 24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 70 ° C. for 12 hours.
After 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 12 hours to obtain 99 g (yield 63%) of polymer P (6).
The molecular weight of the obtained polymer P (6) as measured by GPC was Mn = 421,000 and the molecular weight distribution Mw / Mn = 2.00. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer E and the structure derived from monomer B in the polymer was E / B = 66/34 (mol / mol). .

[Comparative Example 3]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, in a glass container substituted with nitrogen, the monomer F176.2 g (0.56 mol) represented by the formula (11) and the monomer B22.5 g (0. 24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 60 ° C. for 6 hours.
After completion of the reaction, the polymer was precipitated by pouring it into a large amount of methanol, washed by filtration, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain 127 g (yield 64%) of polymer P (7).
The polymer P (7) obtained had a molecular weight of Mn = 666,000 and a molecular weight distribution Mw / Mn = 2.88 as measured by GPC. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from monomer F and the structure derived from monomer B in the polymer was F / B = 67/33 (mol / mol). .

[Comparative Example 4]
Bis (dibenzylideneacetone) palladium [Pd (C ₁₇ H ₁₄ O) ₂ ] 0.0057 g (1.0 × 10 ⁻⁵ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate {[Ph ₃ C] [ B (C ₆ F ₅ ) ₄ ]} 0.0092 g (1.0 × 10 ⁻⁵ mol) and tricyclohexylphosphine (PCy ₃ ) 0.0028 g (1.0 × 10 ⁻⁵ mol) were each dissolved in 10 ml of toluene. To prepare a catalyst solution. Next, in a glass container substituted with nitrogen, 217.7 g (0.56 mol) of the monomer G represented by the formula (12) and 22.5 g of monomer B represented by the formula (7) (0. 24 mol) was dissolved in 600 ml of toluene. The prepared catalyst solution was added thereto, and a polymerization reaction was performed at 55 ° C. for 16 hours.
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 12 hours to obtain 149 g (yield 62%) of polymer P (8).
The molecular weight of the obtained polymer P (8) as measured by GPC was Mn = 554,000 and the molecular weight distribution Mw / Mn = 3.24. ^{From the 1} H-NMR spectrum, it was confirmed that the composition ratio of the structure derived from the monomer G and the structure derived from the monomer B in the polymer was G / B = 67/33 (mol / mol). .

The results of Comparative Examples 1 to 4 are shown in Table 2.

  From the above results, in the production of the cyclic olefin addition polymer of the present invention, high superiority can be confirmed with respect to using the cyclic olefin functional siloxane having the specific structure represented by the above formula (1).

  Table 3 shows the solubility of P (1), P (2), P (3) and P (4) described in Examples 1 to 4.

  The obtained polymers P (1), P (2), P (3), and P (4) were dissolved in toluene to prepare a 5% by mass polymer solution. Using this solution, a film was formed by a solution casting method, followed by drying under reduced pressure at 80 ° C. for 12 hours to prepare polymer films F (1), F (2), F (3), and F (4), respectively. Table 4 shows the glass transition temperature and oxygen transmission coefficient of the produced polymer film.

  Polymers P (5), P (6), P (7), and P (8) obtained in Comparative Examples were dissolved in toluene to prepare a 5% by mass polymer solution. Using this solution, a film was formed by a solution casting method, followed by drying under reduced pressure at 80 ° C. for 12 hours to prepare polymer films F (5), F (6), F (7), and F (8), respectively. Table 5 shows the tensile test results of the produced polymer films in comparison with the polymer films F (1), F (2), F (3), and F (4).

  From the above results, it can be seen that the cyclic olefin addition polymer having the organosiloxane of the present invention as a pendant has excellent solubility, heat resistance and gas permeability, and is excellent in mechanical strength, particularly flexibility. Moreover, it turns out that the polymer of this invention can be manufactured easily and highly efficiently by vinyl addition polymerization of a cyclic olefin using a specific multicomponent 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. In addition, the polymer of the present invention is particularly excellent in flexibility, so it is difficult to break, and can be expected to be applied to display devices and semiconductors as films and interface materials.
The highly gas-permeable cyclic olefin addition polymer of the present invention can be easily and highly efficiently produced using a multi-component catalyst having a specific structure.

Claims (12)

It is obtained by addition polymerization of 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). The ratio of the structural unit derived from the cyclic olefin functional siloxane represented by the following formula (1) is 5 to 100 mol% in the addition polymer, and the number in terms of polystyrene measured by GPC using THF as a solvent. A high gas-permeable cyclic olefin addition polymer having an average molecular weight (Mn) of 10,000 to 2,000,000.

(R ¹ in Formula (1) is an unsubstituted or halogen-substituted monovalent alkyl group having 1 to 10 carbon atoms that does not have the same or different aliphatic unsaturated bond, and s is 0 to 2 I is 0 or 1, and j is an integer of 1 to 4.)

(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, and k represents 0 or 1.) The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 0, and j is 2. The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 1, and j is 2. The highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein R ¹ in formula (1) is a methyl group, s is 2, and j is 2. 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 k is 0. In the presence of 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) The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 1, wherein addition polymerization is performed with a cyclic olefin compound represented by the following formula (2):
[Compound (A)]
Zero-valent selected from bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, (ethene) bis (tricyclohexylphosphine) palladium, carbonyltris (triphenylphosphine) palladium, bis (t-butylisocyanide) palladium Palladium compounds.
[Compound (B)]
Triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, lithium tetrakis ( An ionic boron compound selected from pentafluorophenyl) borate-ethyl ether complex .
[Compound (C)]
Triisopropyl phosphine, tri t- butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, selected from di-t- butylphenyl phosphine sulfo Sufin compound.

(R ¹ in Formula (1) is an unsubstituted or halogen-substituted monovalent alkyl group having 1 to 10 carbon atoms that does not have the same or different aliphatic unsaturated bond, and s is 0 to 2 (It is an integer, i is 0 or 1, and j represents an integer of 1 to 4.)

(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, and k represents 0 or 1.) Compound (A) is a complex in which two dibenzylideneacetones are coordinated to one zero-valent palladium, bis (dibenzylideneacetone) palladium, compound (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, compound The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 , wherein (C) is tricyclohexylphosphine. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 0, and j is 2. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 1, and j is 2. The method for producing a highly gas-permeable cyclic olefin addition polymer according to claim 6 or 7 , wherein R ¹ in formula (1) is a methyl group, s is 2, and j is 2. The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 6 to 10 , wherein A ^{1 to} A ⁴ in formula (2) are all hydrogen atoms and k is 0. The method for producing a highly gas-permeable cyclic olefin addition polymer according to any one of claims 6 to 11 , wherein the addition polymerization is carried out at 0 to 150 ° C for 1 to 72 hours in an inert gas atmosphere.

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