JP5353043B2 - Cyclic olefin addition polymer and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cycloolefin addition polymer which uses a cycloolefin-functional siloxane as a monomer and has both functions of polycycloolefin and siloxane, and to provide a production method of the cycloolefin addition polymer. <P>SOLUTION: The cycloolefin addition polymer is obtained by additionally polymerizing the cycloolefin-functional siloxane represented by the formula (1), wherein R<SP>1</SP>are monovalent organic groups having no aliphatic unsaturated bonds, which are equal to each other or are different from each other, s denotes an integer of 0 to 2 and j denotes 0 or 1. According to the invention, by using the cycloolefin-functional siloxane as the monomer, the cycloolefin addition polymer excellent in transparency, heat resistance, solubility into organic solvent and polysiloxane solvent, storage stability and handleability can be obtained. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a cyclic olefin addition polymer containing a siloxane structure and a method for producing the same.

  Polycycloolefins have attracted attention as functional plastics for optical materials, gas separation membrane materials, and film-forming materials because they have excellent transparency, thermal stability, strength, gas permeability, and good film-forming properties. Yes. On the other hand, organopolysiloxane has been put into practical use in a wide range of fields as a functional polymer excellent in heat resistance, water resistance and chemical resistance. A resin having such a polycycloolefin structure and a polysiloxane structure can be a highly functional polymer having both characteristics.

  To date, as materials having excellent transparency and heat resistance, the following ring-opening polymers of cyclic olefin compounds and their hydrides or addition polymers of cyclic olefin compounds have been proposed.

  Japanese Patent Application Laid-Open No. 60-26024 (Patent Document 1), Japanese Patent No. 3050196 (Patent Document 2), Japanese Patent Application Laid-Open No. 1-132625 (Patent Document 3), Japanese Patent Application Laid-Open No. 5-214079 (Patent Document 4). JP-A 61-292601 (Patent Document 5), JP-A 2006-117077 (Patent Document 6) and Makromol. Chem. Macromol. Symp. Vol 47, 83 (1991) (Non-Patent Document 1) is a ring-opening polymer of a cyclic olefin compound and a hydride thereof, or an addition polymer of a cyclic olefin compound and a linear olefin, Excellent processability and solubility. However, the glass transition temperature is often less than 170 ° C. and is often insufficient in terms of heat resistance. In addition, the ring-opening polymer has a production problem that a double bond must be hydrogenated in order to improve heat resistance.

  JP-A-4-63807 (Patent Document 7), JP-A-8-198919 (Patent Document 8), JP-T-9-508649 (Patent Document 9), JP-A-3476466 (Patent Document 10) JP-A-7-196736 (patent document 11), WO 97/20871 pamphlet (patent document 12), WO 98/20394 pamphlet (patent document 13), JP 3801018 (patent document 1). 14) and Am. Chem. Soc. Polymers described in Polymer Preprints Vol 40 (2), 782 (1999) (Non-Patent Document 2) are addition polymers of norbornene compounds and have transparency and heat resistance. However, these polymers are soluble in polar organic solvents such as aromatic hydrocarbon solvents such as toluene, benzene and xylene, and halogenated hydrocarbon solvents such as dichloromethane, tetrachloroethylene and chlorobenzene. It is poorly soluble in aliphatic hydrocarbon solvents such as hexane, octane and decane, and polysiloxane solvents such as hexamethyldisiloxane, methyltris (trimethylsiloxy) silane, and decamethylcyclopentasiloxane. ing.

JP 60-26024 A Japanese Patent No. 3050196 Japanese Patent Laid-Open No. 1-132625 Japanese Patent Laid-Open No. 5-214079 JP 61-292601 A JP 2006-117077 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 JP 2007-291150 A Makromol. Chem. Macromol. Symp. Vol 47, 83 (1991) Am. Chem. Soc. Polymer Preprints Vol 40 (2), 782 (1999)

  The present invention has been made in view of the above circumstances, and aims to provide a cyclic olefin addition polymer having a cyclic olefin functional siloxane as a monomer and having both functions of polycycloolefin and siloxane, and a method for producing the same. To do.

  As a result of intensive studies to achieve the above object, the present inventors have obtained at least one siloxane selected from cyclic olefin functional siloxanes represented by formulas (1), (2), and (3). The present inventors have found that a cyclic olefin addition polymer having a specific structure obtained by addition polymerization becomes a material having excellent transparency, heat resistance, solubility in organic solvents, storage stability, and handleability. It came to be completed.

（式中、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炭化水素基であり、ｓは０〜２の整数であり、ｊは０又は１を示す。）
〔請求項２〕
下記式（２）で表される環状オレフィン官能性シロキサンを付加重合することで得られる環状オレフィン付加重合体。

（式中、Ｒ²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炭化水素基であり、ｔは２〜５の整数であり、ｋは０又は１を示す。）
〔請求項３〕
下記式（３）で表される環状オレフィン官能性シロキサンを付加重合することで得られる環状オレフィン付加重合体。

（式中、Ｒ³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炭化水素基であり、Ｒ⁰はアルキレン基であり、Ｒ’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炭化水素基である。ｘは０又は１を示す。ｍ１，ｍ２，ｍ３，ｍ５，ｍ６，ｍ７は０又は１であり、ｍ４は１以上の整数を示す。）
〔請求項４〕
請求項１，２，３にそれぞれ記載の式（１），（２），（３）で表される環状オレフィン官能性シロキサンから選ばれる少なくとも２種を付加重合することで得られる環状オレフィン付加重合体。
〔請求項５〕
上記式（１），（２），（３）で表される環状オレフィン官能性シロキサンから選ばれる１種又は２種以上を、重合触媒であるビス（アセチルアセテート）ニッケルと、トリス（ペンタフルオロフェニル）ボランを用いて付加重合することを特徴とする環状オレフィン付加重合体の製造方法。 Therefore, this invention provides the cyclic olefin addition polymer shown below and its manufacturing method.
[Claim 1]
The cyclic olefin addition polymer obtained by addition-polymerizing the cyclic olefin functional siloxane represented by following formula (1).

(In the formula, R ¹ is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, s is an integer of 0 to 2, and j is 0 or 1.)
[Claim 2]
A cyclic olefin addition polymer obtained by addition polymerization of a cyclic olefin functional siloxane represented by the following formula (2).

(In the formula, R ² is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, t is an integer of 2 to 5, and k is 0 or 1.)
[Claim 3]
A cyclic olefin addition polymer obtained by addition polymerization of a cyclic olefin functional siloxane represented by the following formula (3).

(Wherein R ³ is a monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond, R ⁰ is an alkylene group, and R ′ is the same or different aliphatic unsaturated bond) (X represents 0 or 1. m1, m2, m3, m5, m6, m7 are 0 or 1, and m4 represents an integer of 1 or more.)
[Claim 4]
Cyclic olefin addition weight obtained by addition polymerization of at least two kinds selected from the cyclic olefin functional siloxanes represented by the formulas (1), (2) and (3) described in claims 1, 2 and 3, respectively. Coalescence.
[Claim 5]
One or more selected from the cyclic olefin functional siloxanes represented by the above formulas (1), (2), and (3) are mixed with bis (acetylacetate) nickel as a polymerization catalyst and tris (pentafluorophenyl ). ) A process for producing a cyclic olefin addition polymer, characterized by addition polymerization using borane .

  According to the present invention, a cyclic olefin having excellent transparency, heat resistance, solubility in organic solvents and polysiloxane solvents, storage stability, and handleability by using the above cyclic olefin functional siloxane as a monomer. An addition polymer is obtained.

（式中、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。）

（式中、Ｒ²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、ｔは２〜５の整数であり、ｋは０又は１を示す。）

（式中、Ｒ³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炭化水素基であり、Ｒ⁰はアルキレン基であり、Ｒ’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炭化水素基である。ｘは０又は１を示す。ｍ１，ｍ２，ｍ３，ｍ５，ｍ６，ｍ７は０又は１であり、ｍ４は１以上の整数を示す。） The cyclic olefin addition polymer of the present invention can be obtained by addition polymerization of at least one of cyclic olefin functional siloxanes represented by the following formulas (1), (2) and (3).

(In the formula, R ¹ is a monovalent organic group not having the same or different aliphatic unsaturated bond, s is an integer of 0 to 2, and j is 0 or 1.)

(In the formula, R ² is a monovalent organic group that does not have the same or different aliphatic unsaturated bond, t is an integer of 2 to 5, and k is 0 or 1.)

(Wherein R ³ is a monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond, R ⁰ is an alkylene group, and R ′ is the same or different aliphatic unsaturated bond) (X represents 0 or 1. m1, m2, m3, m5, m6, m7 are 0 or 1, and m4 represents an integer of 1 or more.)

In the above formulas (1) to (3), R ¹ , R ² and R ³ are monovalent organic groups having no aliphatic unsaturated bond, which may be the same or different from each other, preferably having 1 to 1 carbon atoms. 20, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, butyl group, pentyl group, phenyl group, tolyl group, xylyl group Aryl groups such as 2-phenylethyl group, 3-phenylpropyl group and the like, and groups in which one or more of these hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine atoms, etc. Is mentioned.

In the above formula (3), examples of the alkylene group represented by R ⁰ include those having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms, and this alkylene group is linear or branched. Examples of the monovalent hydrocarbon group having no aliphatic unsaturated bond as R ′ include those having 1 to 20 carbon atoms, particularly those having 1 to 10 carbon atoms, similar to R ¹ , R ² and R ³ .

  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.

  Examples of the cyclic olefin functional siloxane represented by the formula (2) include the following compounds, but the present invention is not limited to these specific examples. Here, Me represents a methyl group.

  As the cyclic olefin functional siloxane represented by the formula (3), groups represented by the following formulas (5) and (6) are particularly preferable.

In the above formulas (5) and (6), m4 is an integer of 1 or more, preferably an integer of 2 to 80, more preferably an integer of 2 to 60. R ³ , R ⁰ , R ′ and x are as described above.

  Examples of the cyclic olefin functional siloxane represented by the above formulas (3), (5), and (6) include the following compounds, but the present invention is not limited to these specific examples. Here, Me represents a methyl group and Bu represents a butyl group.

  The cyclic olefin functional siloxanes represented by the formulas (1) to (3) may be used singly or in combination of two or more. Here, when two or more kinds are used in combination, for example, the compound of formula (1) may be used in combination of two or more kinds. For example, the compounds of formula (1) and formula (2) are used in combination. In some cases.

  In the present invention, a cyclic olefin represented by the following formula (4) is added to at least one of the cyclic olefin functional siloxanes represented by the formulas (1), (2) and (3) for copolymerization. Thus, the heat resistance, solubility in organic solvent, storage stability, and handleability of the obtained cyclic olefin addition polymer of the present invention can be adjusted according to the purpose of use.

In formula (4), 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, a propyl group, or 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, cyclohexyl group and other cycloalkyl groups, phenyl group, tolyl group and xylyl Group, aryl group such as naphthyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, A group selected from halogenated hydrocarbon groups such as 2- (perfluorooctyl) ethyl group and p-chlorophenyl group, or oxetanyl , Methoxycarbonyl group, preferably such as tert- butoxycarbonyl group which is a substituent having a polar number of carbon atoms in the alkoxy group is selected from 1 to 10, especially 1 to 6 alkoxycarbonyl group. A ¹ and A ² or A ¹ and A ³ may form an alicyclic structure, a carbonimide group or an acid anhydride group together with the carbon atoms to which they are bonded. i represents 0 or 1;

  In this case, examples of the alicyclic structure include those having 4 to 10 carbon atoms. Examples of these structures are as follows. In the following examples, Me represents a methyl group and Ph represents a phenyl group.

Although the following compounds can be illustrated as a cyclic olefin compound represented by Formula (4), 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-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [ 2.2.1] Hept-2-ene, 5-chloro-bicyclo [2.2.1] Put-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] butyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] methyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2. 1] Ethyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] propyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] Trifluoroethyl hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] ethyl hept-2-enyl acetate, 2-methyl-bicyclo [2.2.1] hept-acrylate 5-enyl, 2-methyl methacrylate [2.2.1] hept-5-enyl, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid dimethyl, 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.

  Cyclic olefin functional siloxanes represented by the formulas (1) to (3) can be produced by the method shown below (WO02 / 062859 pamphlet (Patent Document 15), JP2003-252881A). Gazette (patent document 16), German Patent Application Publication No. 4128932 (patent document 17), JP 2007-77252 A (patent document 18), JP 2007-70337 (patent document 19), JP, 2007-291150, A (patent documents 20) refer).

  As a first method, it can be synthesized by a Diels-Alder reaction between a siloxane having a terminal olefin and dicyclopentadiene. Here, Me represents a methyl group, and Ph represents a phenyl group.

  As a second method, it can be synthesized by addition reaction of norbornadiene and the corresponding SiH functional polysiloxane in the presence of a platinum catalyst. Here, Me represents a methyl group and Bu represents a butyl group.

  When the cyclic olefin represented by the formula (4) is used, the charge ratio with the cyclic olefin functional siloxane represented by the formulas (1), (2), and (3) is the cyclic olefin addition weight of the present invention to be obtained. Considering the physical properties of the coalescence (transparency, heat resistance, solubility, storage stability, handleability, etc.), it is arbitrarily adjusted according to the purpose of use, but the formulas (1) to (1)-( It is preferable to use the structure derived from 3) in a total amount of 50 mol% or more, preferably 70 mol% or more. When the structure derived from the cyclic olefin represented by the formula (4) is 50 mol% or more in the cyclic olefin addition polymer of the present invention, the solubility in an organic solvent may be lowered.

  The cyclic olefin addition polymer of the present invention comprises at least one cyclic olefin functional siloxane represented by formulas (1), (2) and (3) in the presence of an addition polymerization catalyst depending on the purpose. It is produced by addition polymerization to a cyclic olefin represented by As the addition polymerization catalyst, the following single component catalyst (A) or multicomponent catalyst (B) can be used, but the present invention is not limited thereto.

  (A) As a single component catalyst, the compound of (A-1)-(A-3) shown below can be illustrated.

(A-1) Compound represented by the following formula (a) [L ¹ L ² ML ³ ] ⁺ [A] ⁻ (a)
(M in the formula (a) represents nickel (Ni), cobalt (Co), or palladium (Pd). L ¹ , L ² , and L ³ represent ligands of M, and one of them represents a σ bond. And all ligands have 1 to 3 π bonds, A represents a counter anion, L ¹ , L ² , and L ³ represent cyclodiene having 6 to 12 carbon atoms, norbornadiene, and 10 to 10 carbon atoms. Selected from 20 cyclotrienes and aromatic compounds having 6 to 20 carbon atoms, and the counter anions of A include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₅ SO ₃ F ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ CO ₂ ⁻ , C ₂ F ₅ CO ₂ ⁻ , B [C ₆ F ₅ ] ₄ ⁻ , and B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄ ⁻ are preferable.
Specific examples of the compound represented by the formula (a) include
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [PF ₆ ],
[(6-methoxy-bicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) Pd (cycloocta-1,5-diene)] [SbF ₆ ],
[(Η ³ −ally) Pd] [BF ₄ ],
[(Cycloocta-1,5-diene) Pd (CH ₃ ) Cl] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ]
Etc.

(A-2) A compound represented by the following formula (b) [Pd (II) (L ⁴ ) ₄ ] [A] ₂ (b)
(Here, A is a counter anion and is the same as described in (A-1). L ⁴ is selected from a nitrile compound, a tertiary amine compound, and a triarylphosphine compound.)
Specific examples of the compound represented by the formula (b) include
[Pd (C ₆ H ₅ CN) ₄ ] [BF ₄ ] ₂ ,
[Pd (C ₆ H ₅ CN) ₄ ] [SbF ₆ ] ₂ ,
[Ph ₃ PdCH ₃ ] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ]
(Here, Ph represents a phenyl group.)
Etc.

(A-3) Ni (C ₆ F ₅ ) ₂ or Ni (SiCl ₃ ) ₂ arene complex As specific examples, toluene · Ni (C ₆ F ₅ ) ₂ , xylene · Ni (C ₆ F ₅ ) ₂ , Toluene · Ni (SiCl ₃ ) _{2 and the} like.

  Examples of (B) multi-component catalysts include (B-1) to (B-3) shown below.

(B-1) Transition metal compound As a transition metal compound, at least 1 sort (s) of compound chosen from the group mentioned below is mentioned.
a) A compound selected from nickel (Ni), cobalt (Co) and palladium (Pd) organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds and the like. Specifically, nickel acetate, nickel octoate, nickel 2-ethylhexanoate, nickel oleate, nickel stearate, nickel dibutyl phosphate, nickel dioctylate, nickel dodecylbenzenesulfonate, bis (acetyl acetate) nickel, bis ( Acetylacetonato) nickel, cobalt 2-ethylhexanoate (II), cobalt 2-ethylhexanoate (III), cobalt (II) dodecanoate, tris (acetylacetonato) cobalt (III), palladium acetate, 2-ethyl Examples include palladium hexanoate and bis (acetylacetonato) palladium.
b) Modified compounds of the above-mentioned organic carboxylates of nickel (Ni), cobalt (Co) and palladium (Pd) and super strong acids. Specific examples of the super strong acid include hexafluoroacetone, hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid and the like.
c) Nickel diene or nickel triene complex.
In particular,
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ],
[Bis (bicyclo [2.2.1] hept-2,5-diene) Ni],
[(Cyclododec-1,5,9-triene) Ni]
Etc.
d) A complex in which a ligand having an atom such as phosphorus (P), nitrogen (N), oxygen (O) or the like is coordinated to nickel.
In particular,
(PPh ₃ ) ₂ NiCl ₂ , (PPh ₃ ) ₂ NiBr ₂ , (PPh ₃ ) ₂ CoCl ₂ ,
Bis [N- (3-tert-butylsalicylidene) phenylaminato] Ni,
Ni (OC (O) (C 6 H 4) PPh 2) (H) (PCy 3),
Ni (OC (O) (C 6 H 4) PPh 2) (H) (PPh 3),
Reaction product of Ni (COD) ₂ and Ph ₃ P═CHC (O) Ph (where Ph represents a phenyl group, Cy represents a cyclohexyl group, and COD represents 1,5-cyclooctadiene)
Etc.

(B-2) Organoaluminum compound Specifically, methylalumoxane, butylalumoxane, trimethylaluminum partially mixed methylmethylalumoxane, trimethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, etc. Can be mentioned.

(B-3) Compound added to improve polymerization activity Specifically, boron trifluoride or aluminum trifluoride ether, amine, phenol complex, tri (pentafluorophenyl) borane, tri (3, Examples include boron compounds and aluminum compounds exhibiting Lewis acidity such as 5-di-trifluoromethylphenyl) borane and tri (pentafluorophenyl) aluminum, and triphenylcarbenium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis. (Pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis ( And ionic boron compounds such as 2,4,6-trifluorophenyl) aluminate and ionic aluminum compounds.

  Among these, a transition metal compound selected from nickel, cobalt and palladium and a modified compound of the transition metal compound and a super strong acid are used as one component of a polymerization catalyst, and a Lewis acidic aluminum compound, a Lewis acidic boron compound, an ion It is preferable to add at least one compound selected from a functional aluminum compound and an ionic boron compound in order to improve the polymerization activity.

These catalyst components are used in amounts used within the following ranges.
Transition metal compounds such as nickel compounds, cobalt compounds and palladium compounds are 0.01 to 100 mmol atoms per mole of monomer, and organoaluminum compounds are 1 to 1,000 mol per mole of transition metal compounds. In addition, the Lewis acidic boron compound and aluminum compound, or the ionic boron compound and aluminum compound is 0.5 to 100 mol with respect to 1 mol atom of nickel or cobalt.

  The cyclic olefin addition polymer of the present invention uses the above single-component catalyst or multi-component catalyst, alicyclic hydrocarbon solvents such as cyclohexane and cyclopentane, aliphatic hydrocarbon solvents such as hexane and octane, toluene, benzene , One or more selected from aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as dichloromethane, tetrachloroethylene and chlorobenzene, cyclic polysiloxane solvents such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane It can obtain by superposing | polymerizing in said solvent.

  The amount of the solvent used is such that the mass ratio (S / M) of the monomer (compound represented by the above formulas (1) to (4)) (M) consisting of the solvent (S) and the cyclic olefin is 1 to 1. A range of 30 is preferable, and a range of 1 to 20 is particularly preferable. 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.

As a polymerization method, in a nitrogen or argon atmosphere, the above-described solvent, the monomer composed of the cyclic olefin, and the addition polymerization catalyst are charged into a reaction vessel, and polymerization is performed at a temperature in the range of −20 ° C. to 100 ° C. To do.
The polymerization reaction is preferably performed in a temperature range of -20 ° C to 100 ° C, particularly 0 to 80 ° C. 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. Molecular weight regulators include hydrogen, α-olefins such as ethylene, butene, hexene, aromatic vinyl compounds such as styrene, 3-methylstyrene, divinylbenzene, tris (trimethylmethoxy) vinylsilane, divinyldihydrosilane, vinylcyclotetrasiloxane. And vinyl silicon compounds.

  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 remarkably influenced by the catalyst used, the monomer structure, and the like, and therefore it is difficult to limit them in a general manner. It is necessary to use properly according to 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. In this step, catalyst residues and unreacted monomers remaining in the polymer solution are also removed.

  The thus obtained cyclic olefin addition polymer of the present invention is formed by addition polymerization using a cyclic olefin functional siloxane represented by the formulas (1), (2) and (3) as a monomer. Any one or more of the repeating units represented by the following formulas (7), (8) and (9) are included.

（式中、Ｒ¹、ｓ及びｊは式（１）と同じ。）

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

（式中、Ｒ²、ｔ及びｋは式（２）と同じ。）

(In the formula, R ² , t and k are the same as in formula (2).)

（式中、Ｒ³、Ｒ⁰、Ｒ'、ｍ１〜ｍ７は式（３）と同じ。）

(In the formula, R ³ , R ⁰ , R ′, and m1 to m7 are the same as in formula (3).)

  Moreover, the cyclic olefin addition polymer of this invention may also contain the repeating unit shown by following formula (10) formed by addition polymerization using the cyclic olefin represented by Formula (4) as a monomer.

（式中、Ａ¹〜Ａ⁴、ｉは式（４）と同じ。）

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

  Here, the repeating units represented by the formulas (7) to (10) represent 2,3 additional structural units, but the cyclic olefin functional siloxanes represented by the formulas (1) to (3) and the formula What is used as the 2,7 addition structural unit by addition-polymerizing the cyclic olefin compound represented by (4) as a monomer may be contained.

  In the cyclic olefin functional siloxane addition polymer of this invention, when the structural unit represented by Formula (10) is included, the ratio of the sum total is 50 mol% or less normally, Preferably it is 30 mol% or less. When the total proportion of the structural units represented by the formula (10) exceeds 50 mol%, aliphatic hydrocarbon solvents such as hexane, octane and decane, polysiloxanes such as hexamethyldisiloxane and decamethylcyclopentasiloxane The solubility in a solvent may be reduced. The structural unit represented by the formula (10) may be present randomly in the cyclic olefin functional siloxane addition polymer, or may be unevenly distributed in a block shape.

  As for the molecular weight of the cyclic olefin addition polymer of the present invention, the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography using toluene as a solvent is 10,000 to 1,000,000, preferably 30 ,. The weight average molecular weight (Mw) is 20,000 to 2,000,000, preferably 40,000 to 1,600,000. When the number average molecular weight is less than 10,000 or the weight average molecular weight is less than 20,000, the thin film, film and sheet may be brittle and easily broken. On the other hand, when the number average molecular weight exceeds 1,000,000 or the weight average molecular weight exceeds 2,000,000, the moldability may be lowered, the solution viscosity may be increased, and the handleability may be lowered. .

  In the present invention, a cyclic olefin addition polymer having a relatively narrow molecular weight distribution in which the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 2.0 to 5.0. Easy to get. 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 a differential scanning calorimeter (DSC). The glass transition temperature of the cyclic olefin addition polymer of the present invention evaluated in this way is not particularly limited, but when it is too low, heat deformation or the like during processing or use of the molded product containing the cyclic olefin addition polymer of the present invention. May cause problems. Moreover, when the glass transition temperature is too high, when performing heat processing, the processing temperature is too high, and the molded product containing the cyclic olefin addition polymer of the present invention may be thermally deteriorated. Therefore, the glass transition temperature of the cyclic olefin addition polymer of the present invention is preferably adjusted in the range of 170 to 350 ° C. according to the purpose.

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), absorption of 7.8 to 6.5 ppm of —Si—C ₆ H ₅ , —O—Si (C ₆ H ₅ ) —O— by C ₆ H ₅ , Absorption derived from 0.6 to 3.0 ppm alicyclic hydrocarbon, 0.0 to 0.6 ppm —Si—CH ₂ —, —Si—CH ₃ , —O—Si—CH ₃ absorption, In the absorption of −0.1 to 0.0 ppm of —O—Si (CH ₃ ) —O— and ²⁹ Si-NMR (in heavy benzene), the M unit (R ⁴ : absorption derived from a methyl group, a 10.0~5.0ppm), D units (R ^4: methyl, -15.0~-25.0ppm, R ^4: phenyl, -35.0~-55.0ppm ), Absorption derived from T unit (R ⁴ : alkyl group, −65.0 to −70.0) and its integral ratio Can be confirmed.

（式中、Ｒ⁴は、式（１）中のＲ¹、式（２）中のＲ²及び式（３）中のＲ³と同じ。）

(Wherein, R ⁴ is, R ¹ in the formula (1), the same as R ² and R ³ in the formula (3) in the formula (2).)

  The cyclic olefin functional siloxane addition polymer of the present invention is preferably used as a thin film, sheet or film. 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 100 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. Formed by solution casting method (cast method) in which the solution is dissolved and then dried, and then the solvent is dried, or by the water surface spreading thin film method in which the polymer solution of the present invention is dropped onto the water surface and then scraped off with the support. It is preferable to do this.

  The solvent used in the solution casting method or the water surface development thin film 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 and decane, aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene, and halogenated hydrocarbon solvents such as dichloromethane and chloroform. It can be dissolved in a polysiloxane solvent such as 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. In consideration of the influence on the human body and the burden on the environment, a highly safe polysiloxane solvent such as methyltris (trimethylsiloxy) silane, decamethylcyclopentasiloxane, or the like is preferred.

  The solution containing the 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 and Comparative Examples of the present invention are shown below, but the present invention is not limited by these Examples.

Molecular weight, total light transmittance, refractive index, glass transition temperature, and solubility in organic solvents were evaluated by the following methods.
(1) Molecular weight (weight average molecular weight, number average molecular weight):
Using a gel permeation chromatography apparatus manufactured by Tosoh Corporation (HLC-8220GPC), measurement was performed at 40 ° C. using toluene as a solvent. The obtained molecular weight is a standard polystyrene conversion value.
(2) Total light transmittance:
Using a spectrophotometer device (H-3310) manufactured by Hitachi High-Technologies Corporation, the total light transmittance was measured with a film and plate having a predetermined thickness (100 μm).
(3) Refractive index:
Using an Atago Co., Ltd. (DR-M2 / 1550) multiwavelength Abbe refractometer, the refractive index n ²⁵ _D of D line (589 nm) at 25 ° C. was measured.
(4) Glass transition temperature:
Using a Mettler DSC (DSC820) apparatus, the temperature was raised from room temperature at 10 ° C./min and measured.
(5) Solubility in organic solvents:
As a solvent, toluene, xylene, decane, cyclohexane, hexane, dichloromethane, hexamethyldisiloxane, methyltris (trimethylsiloxy) silane, and decamethylcyclopentasiloxane were prepared and evaluated so as to be a 10% by mass solution.

図１に重合体Ｐ（１）の¹Ｈ−ＮＭＲのチャートを示す。
また、重合体Ｐ（１）のポリスチレン換算の数平均分子量（Ｍｎ）は２９，１００、重量平均分子量（Ｍｗ）は６１，１００で、Ｍｗ／Ｍｎは２．1であった。重合反応の結果を表１に、重合体の有機溶媒への溶解性を表２に示す。
重合体Ｐ（１）をトルエンに溶解し、１０質量％の重合体溶液を調製した。この溶液をキャストして、厚さ１００μｍのフィルムＦ（１）を作製した。このフィルムの各種物性評価結果を表３に示す。 [Example 1]
As a monomer, 500 mmol of Compound A shown below and 522 g of toluene as a solvent were charged in a 1 L reaction vessel under a nitrogen atmosphere. Thereto, 0.50 mmol of bis (acetylacetate) nickel and 2.50 mmol of tri (pentafluorophenyl) borane were charged to carry out polymerization. Polymerization was carried out at 50 ° C. for 24 hours, and the polymerization was stopped with methanol.
The obtained polymer solution was put into 3 L of methanol to solidify the polymer, and unreacted monomers and catalyst residues were removed. The solidified polymer was dried to obtain a polymer P (1).

FIG. 1 shows a ¹ H-NMR chart of the polymer P (1).
The polystyrene equivalent number average molecular weight (Mn) of the polymer P (1) was 29,100, the weight average molecular weight (Mw) was 61,100, and Mw / Mn was 2.1. The results of the polymerization reaction are shown in Table 1, and the solubility of the polymer in the organic solvent is shown in Table 2.
The polymer P (1) was dissolved in toluene to prepare a 10% by mass polymer solution. This solution was cast to produce a film F (1) having a thickness of 100 μm. Table 3 shows the evaluation results of various physical properties of this film.

図２に重合体Ｐ（２）の¹Ｈ−ＮＭＲのチャートを示す。
また、重合体Ｐ（２）のポリスチレン換算の数平均分子量（Ｍｎ）は２９，０００、重量平均分子量（Ｍｗ）は７８，３００で、Ｍｗ／Ｍｎは２．７であった。重合反応の結果を表１に、重合体の有機溶媒への溶解性を表２に示す。
重合体Ｐ（２）をトルエンに溶解し、１０質量％の重合体溶液を調製した。この溶液をキャストして、厚さ１００μｍのフィルムＦ（２）を作製した。このフィルムの各種物性評価結果を表３に示す。 [Example 2]
A polymer P (2) was obtained in the same manner as in Example 1 except that 250 mmol of Compound B shown below was used as a monomer.

FIG. 2 shows a ¹ H-NMR chart of the polymer P (2).
In addition, the number average molecular weight (Mn) in terms of polystyrene of the polymer P (2) was 29,000, the weight average molecular weight (Mw) was 78,300, and Mw / Mn was 2.7. The results of the polymerization reaction are shown in Table 1, and the solubility of the polymer in the organic solvent is shown in Table 2.
The polymer P (2) was dissolved in toluene to prepare a 10% by mass polymer solution. This solution was cast to produce a film F (2) having a thickness of 100 μm. Table 3 shows the evaluation results of various physical properties of this film.

図３に重合体Ｐ（３）の¹Ｈ−ＮＭＲのチャートを示す。
また、重合体Ｐ（３）のポリスチレン換算の数平均分子量（Ｍｎ）は４１，８００、重量平均分子量（Ｍｗ）は８３，６００で、Ｍｗ／Ｍｎは２．０であった。重合反応の結果を表１に、重合体の有機溶媒への溶解性を表２に示す。
重合体Ｐ（３）をトルエンに溶解し、１０質量％の重合体溶液を調製した。この溶液をキャストして、厚さ１００μｍのフィルムＦ（３）を作製した。このフィルムの各種物性評価結果を表３に示す。 [Example 3]
A polymer P (3) was obtained in the same manner as in Example 1 except that 500 mmol of the compound C shown below was used as a monomer.

FIG. 3 shows a ¹ H-NMR chart of the polymer P (3).
The polystyrene equivalent number average molecular weight (Mn) of the polymer P (3) was 41,800, the weight average molecular weight (Mw) was 83,600, and Mw / Mn was 2.0. The results of the polymerization reaction are shown in Table 1, and the solubility of the polymer in the organic solvent is shown in Table 2.
The polymer P (3) was dissolved in toluene to prepare a 10% by mass polymer solution. This solution was cast to produce a film F (3) having a thickness of 100 μm. Table 3 shows the evaluation results of various physical properties of this film.

共重合体中の化合物Ｄに由来する構造体の含有量は６１．２モル％であった。測定は、¹Ｈ−ＮＭＲ測定により行った。
また、共重合体Ｐ（４）のポリスチレン換算の数平均分子量（Ｍｎ）は９９，０００、重量平均分子量（Ｍｗ）は１９８，０００で、Ｍｗ／Ｍｎは２．０であった。重合反応の結果を表１に、共重合体の有機溶媒への溶解性を表２に示す。
共重合体Ｐ（４）をトルエンに溶解し、１０質量％の共重合体溶液を調製した。この溶液をキャストして、厚さ１００μｍのフィルムＦ（４）を作製した。このフィルムの各種物性評価結果を表３に示す。 [Comparative Example 1]
As a monomer, 300 mmol of compound C, 200 mmol of compound D shown below, and 522 g of toluene as a solvent were charged in a 1 L reaction vessel under a nitrogen atmosphere. Thereto, 0.50 mmol of bis (acetylacetate) nickel and 2.50 mmol of tri (pentafluorophenyl) borane were charged to carry out polymerization. Polymerization was performed at 25 ° C. for 5 hours, and the polymerization was stopped with methanol.
The obtained copolymer solution was put into 3 L of methanol to coagulate the copolymer, and unreacted monomers and catalyst residues were removed. The coagulated copolymer was dried to obtain a copolymer P (4).

The content of the structure derived from the compound D in the copolymer was 61.2 mol%. The measurement was performed by ¹ H-NMR measurement.
Moreover, the number average molecular weight (Mn) of polystyrene conversion of the copolymer P (4) was 99,000, the weight average molecular weight (Mw) was 198,000, and Mw / Mn was 2.0. The results of the polymerization reaction are shown in Table 1, and the solubility of the copolymer in an organic solvent is shown in Table 2.
Copolymer P (4) was dissolved in toluene to prepare a 10% by mass copolymer solution. This solution was cast to produce a film F (4) having a thickness of 100 μm. Table 3 shows the evaluation results of various physical properties of this film.

評価）○：溶解，△：わずかに溶解，×：ほとんど溶解しない。
ポリシロキサン溶媒）Ｄ５：デカメチルシクロペンタシロキサン，Ｍ３Ｔ：メチルトリス（トリメチルシロキシ）シラン，Ｍ２：ヘキサメチルジシロキサン。

Evaluation) ○: dissolved, Δ: slightly dissolved, ×: hardly dissolved.
Polysiloxane solvent) D5: Decamethylcyclopentasiloxane, M3T: Methyltris (trimethylsiloxy) silane, M2: Hexamethyldisiloxane.

  Since the material containing the cyclic olefin functional siloxane addition polymer of the present invention has excellent optical transparency and heat resistance, a light guide plate, polarizing film, surface protective film, retardation film, antireflection film, optical disk, optical fiber, It is useful for optical parts such as lenses and LED elements, electronic parts, sealants and the like. Furthermore, the cyclic olefin functional siloxane addition polymer of the present invention also has excellent solubility in organic solvents and polysiloxane solvents and film-forming properties. Therefore, application to oxygen-enriched films, contact lenses, cosmetic film forming materials and the like can also be expected.

1 is a ¹ H-NMR chart of a polymer P (1) obtained in Example 1. 2 is a ¹ H-NMR chart of polymer P (2) obtained in Example 2. FIG. 3 is a ¹ H-NMR chart of polymer P (3) obtained in Example 3. FIG.

Claims (5)

The cyclic olefin addition polymer obtained by addition-polymerizing the cyclic olefin functional siloxane represented by following formula (1).

(In the formula, R ¹ is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, s is an integer of 0 to 2, and j is 0 or 1.) A cyclic olefin addition polymer obtained by addition polymerization of a cyclic olefin functional siloxane represented by the following formula (2).

(In the formula, R ² is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, t is an integer of 2 to 5, and k is 0 or 1.) A cyclic olefin addition polymer obtained by addition polymerization of a cyclic olefin functional siloxane represented by the following formula (3).

(Wherein R ³ is a monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond, R ⁰ is an alkylene group, and R ′ is the same or different aliphatic unsaturated bond) (X represents 0 or 1. m1, m2, m3, m5, m6, m7 are 0 or 1, and m4 represents an integer of 1 or more.)   Cyclic olefin addition weight obtained by addition polymerization of at least two kinds selected from the cyclic olefin functional siloxanes represented by the formulas (1), (2) and (3) described in claims 1, 2 and 3, respectively. Coalescence. One or more selected from cyclic olefin functional siloxanes represented by the following formulas (1), (2), and (3), bis (acetylacetate) nickel as a polymerization catalyst, and tris (pentafluorophenyl ) ) A process for producing a cyclic olefin addition polymer, characterized by addition polymerization using borane .

(In the formula, R ¹ is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, s is an integer of 0 to 2, and j is 0 or 1.)

(In the formula, R ² is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, t is an integer of 2 to 5, and k is 0 or 1.)

(Wherein R ³ is a monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond, R ⁰ is an alkylene group, and R ′ is the same or different aliphatic unsaturated bond) (X represents 0 or 1. m1, m2, m3, m5, m6, m7 are 0 or 1, and m4 represents an integer of 1 or more.)

Images