JP4400232B2 - Method for producing cyclic olefin-based addition polymer - Google Patents

Description

  The present invention relates to a method for producing a cyclic olefin addition polymer. More specifically, the present invention produces a cyclic olefin-based addition polymer that is suitably used for optical applications and the like by addition polymerization of a cyclic olefin compound in the presence of a specific catalyst containing a palladium compound having excellent polymerization activity. Regarding the method.

  In recent years, due to demands for lighter weight, smaller size, and higher density, liquid crystal display element parts such as lenses, sealing parts and other optical parts conventionally used with inorganic glass, backlights, light guide plates, TFT substrates, touch panels, etc. Replacement with optically transparent resin is progressing in such fields. As such an optically transparent resin, a norbornene (bicyclo [2.2.1] hept-2-ene) -based addition polymer having high transparency, high heat resistance, and low water absorption has attracted attention.

  In addition to the above properties, norbornene (bicyclo [2] is a transparent resin having a small coefficient of linear expansion, excellent thermal dimensional stability, chemical resistance, and excellent adhesion and adhesion to other members. 2.2.1] Hept-2-ene) and an addition polymer of a hydrolyzable silyl group-containing cyclic olefin and a crosslinked product thereof have been proposed.

  A cyclic olefin addition polymer represented by norbornene has been obtained by addition polymerization of a cyclic olefin monomer using a catalyst using a transition metal compound such as Ni, Pd, Ti, Zr, and Cr. (For example, refer nonpatent literature 1).

  In addition, addition copolymers of a cyclic olefin compound having a polar substituent and a nonpolar cyclic olefin compound have excellent heat resistance and transparency, as well as improved adhesion and adhesion, dimensional stability, and chemical resistance. As a polymerization catalyst that can be cross-linked to improve the properties, a multi-component catalyst containing a single complex of Ni, Pd as a late transition metal or a Ni, Pd compound is used as a polymerization catalyst for obtaining these copolymers. It has been mainly used (see Non-Patent Documents 2 to 11 and Patent Document 1).

  Among these catalysts, in order to omit a complicated catalyst synthesis step, a multi-component palladium catalyst is often used industrially rather than a single catalyst. Further, as a catalyst having excellent polymerization activity, a phosphine compound or an amine compound is used as a neutral donor as a ligand of a Pd cation, and a super strong acid anion is known as a weak counter anion ligand (Patent Documents 2 to 6). And Non-Patent Document 12).

These prior art multi-component catalysts are obtained by preparing any of the following components.
<Catalyst system I>
1) Pd compound 2) Neutral phosphine or amine compound 3) Ionic compound or Lewis acidic boron or aluminum compound that can be weak counter anion of Pd cation 4) Organoaluminum compound <Catalyst system II>
1) Pd compound having neutral phosphine or amine compound as ligand 2) Ionic compound or Lewis acidic boron or aluminum compound that can be weak counter anion of Pd cation 3) Organoaluminum compound <Catalyst system III>
1) Pd compounds having a neutral donor having a Pd-C bond such as σ-alkyl, σ-aryl, and π-allyl as ligands 2) Ionic compounds that can be weak counter anions of Pd cations <catalyst systems IV>
1) Pd compounds having a neutral donor having a Pd-C bond such as σ-alkyl, σ-aryl, π-allyl, etc. as ligands 2) Lewis acid compounds These catalysts are all neutral donors Phosphine or amine compounds. However, Pd compounds having a neutral donor having a Pd-C bond, such as σ-alkyl, σ-aryl, and π-allyl, as ligands are complex, and it is not necessarily advantageous industrially. Absent.

  These multi-component catalysts containing Pd compounds are more resistant to water, methanol, etc. than multi-component catalysts containing Ti and Zr compounds in the previous period, but neutral donor phosphine added to improve polymerization activity May be easily oxidized to phosphine oxide when oxygen is present during storage, leading to a decrease in polymerization activity. In particular, in the polymerization with a small amount of catalyst, the catalyst components are different even in the presence of a small amount of oxygen, and the influence is great.

  For this reason, in industrial production, there is a demand for a catalyst system with little variation in the polymerization rate and the quality of the produced polymer even when a small amount of oxygen is present in the polymerization system.

  In the case of producing a cyclic olefin addition polymer crosslinked product having adhesion / adhesion, solvent resistance, and chemical resistance, polar substituents such as hydrolyzable silyl groups and ester groups which become crosslinking groups It usually has a step of producing a copolymer to be a precursor of a crosslinked product by subjecting a cyclic olefin compound having a non-cyclic cycloolefin compound to an addition polymerization reaction, which is formed by such an addition polymerization reaction. In many cases, it is difficult to remove palladium atoms from the resulting copolymer. For this reason, when there is much residual palladium of this copolymer, there exists a problem of causing the fall of optical transparency.

  For this reason, there is a demand for a catalyst that can be polymerized with a small amount of palladium catalyst and that is highly active even if it contains polar groups such as hydrolyzable silyl groups, ester groups, imide groups, and acid anhydride groups.

As a result of diligent research in view of such a situation, the present inventors have found that when a novel catalyst using a complex of a phosphine compound and an organoaluminum compound is used as a neutral donor component of a multicomponent catalyst, Addition polymerization of olefinic compounds can be carried out with high activity, and addition (co) polymerization with high activity is possible even with monomers containing cyclic olefinic compounds having polar substituents such as hydrolyzable silyl groups. The present invention has been completed by finding out what can be done.
U.S. Pat. No. 3,330,815 JP-A-5-262821 International Publication No. 00/20472 US Pat. No. 6,455,650 JP-A-10-130323 JP 2001-98035 A Christoph Janiak, Paul G. Lassahn, Macromol. Rapid Commun. 22, p479 (2001) R. G. Schultz, Polym. Lett. VOL. 4, p541, (1966) Stefan Breunig, Wilhelm Risse, Makromol. Chem. 193,2915 (1992) Adam L. Safir, Bruce M.M. Novak Macromolecules, 1995,28,5396 Joice P. Mathew et al. Macromolecules 1996,29,2755 Annette Reinmuth et al. Macromol. Rapid Commun. 17,173 (1996) B. S. Heinz, Acta Polymer 48,385 (1997) B. S. Heinz et al. Macromol. Rapid Commun. 19,251 (1998) Nicole R. Grove et al. J. et al. Polym. Sci. Part B, 37,3003 (1999) April D.D. Hennis et al. Organometallics 2001,20,2802 Seung UK Son et al. J. et al. Polym. Sci. Part A Polym. Chem. 41,76 (2003) Macromolecules 35, p8969-8977 (2002)

  This invention makes it a subject to provide the manufacturing method of the cyclic olefin type addition polymer which can manufacture the addition (co) polymer of a cyclic olefin type compound with high activity. Further, the present invention provides a cyclic olefin compound having a polar group, particularly a hydrolyzable silyl group, which has little influence on polymerization activity even in the presence of a small amount of oxygen in the (co) polymerization reaction of the cyclic olefin compound. It is an object of the present invention to provide a method for producing a cyclic olefin-based addition polymer, which is capable of addition copolymerization with high polymerization activity even when a monomer composition containing the copolymer is copolymerized.

The method for producing the cyclic olefin addition polymer of the present invention comprises:
(A) a palladium compound,
(B) a compound selected from ionic boron compounds, ionic aluminum compounds and Lewis acidic aluminum or Lewis acidic boron compounds, and
(C) Addition complex of a phosphine compound having a cone angle of 170 to 200 and an organoaluminum compound, which is a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group. In the presence of a multi-component catalyst containing
It is characterized by addition polymerization of a monomer containing a cyclic olefin compound represented by the following general formula (1);

(In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aryl group, an ester group, an oxetanyl group, an alkoxy group, or a trialkylsilyl group. An atom or group selected from the group consisting of a group and a hydroxyl group, these having 0 to 10 carbon atoms containing at least one atom selected from an alkylene group having 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom; The linking group may be connected to the ring structure.
Further, A ¹ and A ² may form an alkylidene group having 1 to 5 carbon atoms, a substituted or unsubstituted alicyclic or aromatic ring having 5 to 20 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms. In addition, A ¹ and A ³ may form a substituted or unsubstituted alicyclic or aromatic ring or aromatic ring having 5 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms. m is 0 or 1. ).

In such a method for producing a cyclic olefin addition polymer of the present invention,
It is preferable that the addition complex (C) of the phosphine compound and the organoaluminum compound is in contact with air.
Further, the multi-component catalyst contains (D) an organoaluminum compound in addition to (A), (B), and (C), and the content of the organoaluminum compound (D) is palladium of the palladium compound (A). It is preferably 0.1 to 200 mol per gram atom.

  In the method for producing a cyclic olefin addition polymer of the present invention, the multi-component catalyst is a polycyclic monoolefin or non-conjugated diene having a bicyclo [2.2.1] hept-2-ene structure, or a monocyclic non-cyclic diene. The catalyst is preferably prepared in the presence of at least one compound selected from the group consisting of conjugated dienes and linear non-conjugated dienes.

In the method for producing a cyclic olefin addition polymer of the present invention,
Multi-component catalyst
In the presence of a bicyclo [2.2.1] hept-2-ene and / or a bicyclo [2.2.1] hept-2-ene derivative having one or more hydrocarbon groups having 1 to 15 carbon atoms, After forming (C),
A catalyst prepared by adding (A) and (B) and, if necessary, (D) an organoaluminum compound is preferable.

In the method for producing the cyclic olefin addition polymer of the present invention,
It is preferable that the monomer contains a cyclic olefin compound represented by the following general formula (2) -1 or (2) -2.

(In Formula (2) -1 and Formula (2) -2, R ¹ and R ² are substituents selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group;
X is an alkoxy group having 1 to 5 carbon atoms or a halogen atom,
Y is a hydroxyl group residue of an aliphatic diol having 2 to 4 carbon atoms,
k is an integer of 0 to 2, and n is 0 or 1. )

  According to the production method of the present invention, a cyclic olefin-based addition polymer can be produced with high productivity by addition (co) polymerization of a cyclic olefin-based compound with high polymerization activity. Further, according to the method for producing a cyclic olefin addition polymer of the present invention, even when a trace amount of oxygen is present in the polymerization system, the influence on the polymerization activity is small, and polar groups, particularly hydrolyzable silyl groups. Even when a monomer composition containing a cyclic olefin-based compound having a copolymer is copolymerized, addition copolymerization can be performed with high polymerization activity.

  Hereinafter, the present invention will be specifically described.

In the method for producing a cycloolefin addition polymer of the present invention, a cycloolefin compound is subjected to addition polymerization in the presence of a specific multicomponent catalyst. In the present invention, addition polymerization means addition polymerization or addition copolymerization, and polymer means a homopolymer or a copolymer.
<Multi-component catalyst>
The multi-component catalyst used in the present invention is
(A) a palladium compound,
(B) a compound selected from ionic boron compounds, ionic aluminum compounds and Lewis acidic aluminum or Lewis acidic boron compounds, and
(C) Addition complex of a phosphine compound having a cone angle of 170 to 200 and an organoaluminum compound, which is a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group. Including, if necessary,
(D) contains an organoaluminum compound.
(A) Palladium Compound Examples of the palladium compound (A) include palladium organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds, halides, and the like. An organic carboxylate of palladium or a β-diketone compound is preferable because it is easily dissolved in a hydrocarbon solvent and has high polymerization activity.

Specific examples of these compounds include palladium acetate, propionate, maleate, fumarate, butyrate, adipate, 2-ethylhexanoate, naphthenate, oleate, and dodecanoate. , Neodecanoate, 1,2-cyclohexanedicarboxylate, 5-norbornene-2-carboxylate, benzoate, phthalate, terephthalate, naphthoate, etc., palladium organic carboxylate, palladium acetate Triphenylphosphine complex of palladium, tri (m-tolyl) phosphine complex of palladium acetate, organic carboxylic acid complex of palladium such as tricyclohexylphosphine complex of palladium acetate, dibutyl phosphite of palladium, dibutyl phosphate, dioctyl phosphate Salts, phosphites such as dibutyl phosphate, phosphates, para Palladium organic sulfonates such as um dodecylbenzenesulfonate, p-toluenesulfonate, bis (acetylacetonato) palladium, bis (hexafluoroacetylacetonato) palladium, bis (ethylacetoacetate) palladium, bis (Phenylacetoacetate) palladium β-diketone compounds such as palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis [tri (m-tolylphosphine)] palladium, dibromobis [tri (m-tolylphosphine)] palladium, dichlorobis [tri (M-xylylphosphine)] palladium, dibromobis [tri (m-xylylphosphine)] palladium, an imidazole complex represented by [C ₃ H ₅ N ₂ ] ₂ [PdCl ₄ ], [Ph ₃ PCH ₂ C (O) CH ₃ ] ₂ [Pd ₂ Cl ₆ ]
Palladium halide complexes such as acetonyltriphenylphosphonium complex represented by the formula: Furthermore, dibenzylideneacetone palladium [Pd ₂ (dba) ₃ ], tetra [triphenylphosphine] palladium [Pd (P (Ph) ₃ ) ₄ ], aryl chloride, benzyl chloride, bromobenzene, chlorobenzene, bromonaphthalene, etc. Also included are zero-valent palladium compounds that form aryl or allyl palladium halides in the presence of the phosphine compounds shown in c) below in combination with halides.
(B) Compound selected from ionic boron compound, ionic aluminum compound, Lewis acidic aluminum and Lewis acidic boron compound Examples of the ionic boron compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri Phenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (penta Fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) bore DOO, N, N-diphenyl tetrakis (pentafluorophenyl) borate, and lithium tetrakis (pentafluorophenyl) borate.

  Examples of the ionic aluminum compound include triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] aluminate, triphenylcarbenium tetrakis (2 , 4,6-trifluorophenyl) aluminate, triphenylcarbenium tetraphenylaluminate and the like.

  Examples of Lewis acidic aluminum compounds include aluminum trifluoride ether complex, ethyldifluoroaluminum, ethoxydifluoroaluminum, tris (pentafluorophenyl) aluminum, tris (3,5-difluorophenyl) aluminum, tris (3,5- Ditrifluoromethylphenyl) aluminum, and the like.

  Examples of Lewis acidic boron compounds include tris (pentafluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (3,5-ditrifluoromethylphenyl) boron, boron trifluoride / ether complex, and the like. Is mentioned.

Of these, ionic boron compounds are most preferred from the viewpoint of polymerization activity.
(C) Addition complex / phosphine compound of phosphine compound and organoaluminum compound The phosphine compound forming the addition complex of component (C) is a substitution selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group and an aryl group. Cone angle (Cone
Angle; θdeg) is a phosphine compound having 170 to 200.

  In the present invention, it is an important technical requirement to use such a specific phosphine compound as a raw material for the component (C). If other phosphine compounds are used, the resulting cyclic olefin addition polymer may have a significantly high molecular weight, and the polymer solution may become solidified and swollen or the polymer may precipitate. In some cases, it is difficult to form a film, a sheet and a thin film by the solution casting method.

The phosphine compound used as a raw material for the component (C) is a trivalent electron-donating phosphorus compound (tertiary phosphine compound) having an alkyl group, a cycloalkyl group or an aryl group as a substituent. Here, the cone angle (θdeg) of the tertiary phosphine compound
) Is C.I. A. Calculated by Tolman (Chem. Rev. Vol. 77, 313 (1977)), a model formed by three substituents of a metal and a phosphorus atom, assuming that the bond distance between the metal atom and the phosphorus atom is 2.28 mm. The cone angle θ to be measured.

Examples of the phosphine compound having a cone angle of θdeg of 170 to 200 used in the present invention include tricyclohexylphosphine, di-t-butylphenylphosphine, trineopentylphosphine, tri (t-butyl) phosphine, and tri (pentafluorophenyl). ) Phosphine, tri (o-tolyl) phosphine and the like are preferable. Di-t-butyl-2-biphenylphosphine, di-t-butyl-2′-dimethylamino-2-biphenylphosphine, dicyclohexyl-2-biphenylphosphine, dicyclohexyl-2′-i-propyl-2-biphenylphosphine And so on.
-Organoaluminum compound The organoaluminum compound that forms the addition complex of component (C) is a compound that acts as a Lewis acid and forms an addition complex with the phosphine compound, and has at least one aluminum-alkyl bond. is there. As such an organoaluminum compound,
When xanthone is coordinated to an organoaluminum compound by the method described in the document “Saegusa et al., Catalyst, Vol. 7, p43 (1965)”, the carbonyl of xanthone (C═O) measured by infrared spectrum is obtained. An organoaluminum compound having an acidity with a shift value (Δν _{c = o} ) of the absorption spectrum of stretching vibration of 50 cm ⁻¹ or more is preferable.

Examples of such organoaluminum compounds include methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, sesquiethylaluminum chloride, diethylaluminum chloride, diethylaluminum fluoride, diethylaluminum bromide, dibutylaluminum chloride, triethylaluminum, trimethylaluminum, tributyl. Aluminum, trihexyl aluminum,
Preferred examples include dibutylaluminum hydride. In addition, alkylaluminum alkoxide compounds such as diethylaluminum ethoxide, diethylaluminum methoxide, and ethylaluminum diethoxide are not preferable in terms of acidity.
Addition Complex The above-mentioned addition complex of the specific phosphine compound and the organoaluminum compound is usually a complex in which the composition ratio of the specific phosphine compound and the organoaluminum compound is 1: 1 by molar ratio. Such an addition complex is formed, for example, by adding 1 to 10 mol of organoaluminum in a range of 0 to 100 ° C. and reacting with 1 mol of a specific phosphine compound. For the formation of the complex, 1.0 mol of the organoaluminum compound is sufficient for 1 mol of the specific phosphine compound, and the excess organoaluminum compound acts as (D) organoaluminum, which is a promoter component described later. To do.

Such an addition complex used in the present invention has higher oxidation resistance to oxygen than a phosphine compound not forming a complex, and is stable even when stored in a solution state for a long period of time. When such an addition complex is used, the decrease in polymerization activity is small even when oxygen is present in the polymerization system.
(D) Organoaluminum compound The multi-component catalyst according to the present invention contains an organoaluminum compound (D) as a co-catalyst in addition to the components (A), (B) and (C) described above. You may go out.

The organoaluminum compound (D) is an aluminum compound having at least one aluminum-alkyl group, and examples thereof include alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutyl. Trialkylaluminum compounds such as aluminum, diisobutylaluminum hydride and di, alkylaluminum hydride compounds and alkylalumoxane compounds are preferably used.
Preparation of multi-component catalyst The multi-component catalyst according to the present invention is formed from the above-mentioned components (A), (B), (C) and, if necessary, the component (D).

  Such a multi-component catalyst may be prepared by simply mixing the respective components or adding them to the polymerization system, but preferably has a bicyclo [2.2.1] hept-2-ene structure. It can be prepared in the presence of a polycyclic monoolefin compound, a non-conjugated diene thereof, a monocyclic and linear conjugated diene and a compound selected from non-conjugated dienes (hereinafter also referred to as compounds such as diene). . When the multi-component catalyst is prepared in the presence of a linear and / or monocyclic monoolefin compound, the polymerization activity of the catalyst may not be sufficient. In addition, when the multi-component catalyst is prepared in the presence of a linear conjugated or non-conjugated polyene of triene or higher, the catalyst becomes insoluble in the solvent or the resulting polymer is gelled. Sometimes.

Examples of the polycyclic monoolefin compound having a bicyclo [2.2.1] hept-2-ene structure that can be used when preparing a multicomponent catalyst include, for example, a specific monomer (1) described later. Bicyclo [2.2.1] hept-2-ene, which can also be used as
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
And alkyl, cycloalkyl, and aryl substituents having 1 to 15 carbon atoms of these compounds.

As a polycyclic non-conjugated diene compound having a bicyclo [2.2.1] hept-2-ene structure, for example,
Bicyclo [2.2.1] hepta-2,5-diene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4,9-diene,
Pentacyclo [9.2.0 ^2,10 . 0 ^3,8 . 1 ^1,11 . 1 ^4,7 ] pentadeca-5,12-diene,
1,4-bis (2-bicyclo [2.2.1] hept-5-enyl) butane,
1,4-bis (2-bicyclo [2.2.1] hept-5-enyl) hexane,
1,4-bis (2-bicyclo [2.2.1] hept-5-enylmethyl) benzene,
Dimethylbis (2-bicyclo [2.2.1] hept-5-enylmethyl) silanemethyltris (2-bicyclo [2.2.1] hept-5-enylmethyl) silane 5-vinylbicyclo [2.2.1] ] Hept-2-ene,
5-vinylidenebicyclo [2.2.1] hept-2-ene,
5-isopropylidenebicyclo [2.2.1] hept-2-ene,
Etc.

As the linear conjugated diene compound, for example,
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Is mentioned.

  Examples of the monocyclic conjugated diene compound include 1,3-cyclohexadiene and 1,3-cyclooctadiene.

  Examples of the linear non-conjugated diene compound include 1,4-hexadiene and 1,5-hexadiene.

  Examples of the monocyclic non-conjugated diene compound include 1,4-cyclohexadiene and 1,5-cyclooctadiene.

  Among these, the preparation of the multicomponent catalyst according to the present invention includes a polycyclic monoolefin having a bicyclo [2.2.1] hept-2-ene structure, a non-conjugated diene thereof, and a monocyclic non-conjugated diene compound. From the viewpoint of polymerization activity, the reaction is preferably carried out in the presence of a compound selected from the group consisting of:

  The catalyst formed from the components (A), (B), (C) and, if necessary, the component (D) may have low solubility in a hydrocarbon solvent. Depending on the type of the polymerization solvent, the polymerization system may be used. In some cases, when it is added to the catalyst, the polymerization activity may decrease and the polymerization activity may decrease, but when the preparation of the multi-component catalyst according to the present invention is carried out in the presence of such a compound such as a diene, The problem of decreased polymerization activity can be reduced or eliminated. In addition, when such a multi-component catalyst is prepared in the presence of a compound such as diene as described above, such an effect is considered to result from the formation of a complex between the compound such as diene and the catalyst. It is done. In addition, when the complex formed between the compound such as diene and the catalyst becomes the starting point of the polymerization reaction, the polymer chain extends in two directions during the polymerization, and a polymer having a wide molecular weight distribution is obtained. Is also possible.

  In the multicomponent catalyst of the present invention, each catalyst component can usually be used in an amount in the following range.

  The palladium compound (A) is used in the range of 0.0005 to 0.05 mmol Pd atoms with respect to 1 mol of the monomer. By using a compound such as an organic carboxylate of palladium or a β-diketone compound, addition polymerization can be carried out at 0.01 mg or less per mole of monomer and per palladium atom of the palladium salt compound.

The compound selected from the ionic boron compound, ionic aluminum compound and Lewis acidic aluminum compound or boron compound of (B) is usually in the range of 0.2 to 20 mol per gram atom of Pd of the palladium compound (A). And preferably in the range of 0.5 to 5 mol.

The addition complex of the specific phosphine compound (C) and organoaluminum (C) is usually 0.1 to 10 mol, preferably 0.5 to 3. mol per gram atom of Pd of the palladium compound (A).
Used in the range of 0 mole.

Further, the organoaluminum compound (D) that can be added is used as a catalyst component, thereby removing impurities existing in the polymerization system and improving the polymerization activity. The organoaluminum compound (D) as a cocatalyst is based on 1 gram atom of Pd of the palladium compound (A),
Usually, it is used in the range of 0.1 to 200 mol, preferably in the range of 0.5 to 20 mol.

During preparation of the multi-component catalyst, a polycyclic monoolefin having a bicyclo [2.2.1] hept-2-ene structure, its non-conjugated diene, monocyclic and linear conjugated dienes and non-conjugated dienes are selected. When these compounds are used, these compounds such as dienes can usually be used in the range of 0.5 to 1000 mol per gram atom of Pd in the palladium compound (A).

  In the present invention, a polycyclic monoolefin having a bicyclo [2.2.1] hept-2-ene structure is used as a monomer, and each catalyst component is introduced into a polymerization system in which the monomer exists. When the polymerization is carried out, the multi-component catalyst need not be prepared separately using a compound such as a diene other than the polymerization monomer.

As a method for preparing a multi-component catalyst in the presence of a compound such as diene, for example,
a) Catalyst components (A) to (C) or (A) to (D) are mixed in advance in the presence of the above-described compound such as diene to prepare a catalyst, and then added to the mixture of the monomer and the polymerization solvent. Method b) Catalyst preparation by directly adding each component of catalyst components (A) to (C) or (A) to (D) sequentially to a mixture of a monomer, a polymerization solvent and the above-described compound such as diene. And the like. In these methods, there is no particular limitation regarding the order of addition of the catalyst components.

As a method for preparing a multi-component catalyst,
c) After forming an addition complex (C) of a specific phosphine compound and an organoaluminum compound for complex formation in the presence of a mixture of a monomer and a hydrocarbon solvent, catalyst components (A) and (B) are added. A method of adding (D) an organoaluminum compound as necessary is also mentioned. In such a method, among the organoaluminum compounds used when forming the addition complex (C), an excess amount of the organoaluminum compound in excess of 1 mol with respect to 1 mol of the specific phosphine compound is Since it acts as an organoaluminum compound as component (D), which is a promoter used in the above, the amount of organoaluminum compound added as the last (D) promoter can be reduced or omitted.
<Monomer>
In the present invention, a monomer containing a cyclic olefin compound is subjected to addition polymerization in the presence of the multi-component catalyst as described above.

  The monomer includes a monomer containing a cyclic olefin compound represented by the following general formula (1).

(In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aryl group, an ester group, an oxetanyl group, an alkoxy group, or a trialkylsilyl group. An atom or group selected from the group consisting of a group and a hydroxyl group, these having 0 to 10 carbon atoms containing at least one atom selected from an alkylene group having 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom; In addition, A ¹ and A ² may be linked to a ring structure by an alkylidene group having 1 to 5 carbon atoms, a substituted or unsubstituted alicyclic or aromatic ring having 5 to 20 carbon atoms, may form a heterocyclic ring having 2 to 20 carbon atoms, a ¹ and a ³ is a substituted or unsubstituted alicyclic or aromatic ring having 5 to 20 carbon atoms, a heterocyclic ring having 2 to 20 carbon atoms M may be formed. 0 or 1)
Specific examples of the cyclic olefin compound represented by the general formula (1) (hereinafter also referred to as the specific monomer (1)) include the following compounds, but the present invention includes these specific examples. It is not limited.
Bicyclo [2.2.1] hept-2-ene,
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5- (1-butenyl) bicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-ene,
5-octylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-dodecylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-vinylbicyclo [2.2.1] hept-2-ene,
5-allylbicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5,6-dimethylbicyclo [2.2.1] hept-2-ene,
5-methyl-6-ethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-bicyclo [2.2.1] hept-2-ene,
5-chloro-bicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
Bicyclo [2.2.1] hept-5-ene-2,3-carboxylic anhydride,
Bicyclo [2.2.1] hept-5-ene-N-cyclohexyl-2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-N-phenyl-2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-2-spiro-3'-exo-succinic anhydride,
Methyl bicyclo [2.2.1] hept-5-ene-2-methylcarboxylate-2-methyl carboxylate,
Bicyclo [2.2.1] hept-5-ene-2-spiro-butyrolactone,
Bicyclo [2.2.1] hept-5-ene-2-spiro-N-cyclohexyl-succinimide,
Bicyclo [2.2.1] hept-5-ene-2-spiro-N-phenyl-succinimide,
9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
5-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene,
5-[(3-oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene,
Spiro-5- (3-oxetanyl) bicyclo [2.2.1] hept-2-ene,
And compounds such as bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the present invention, a monomer represented by the following general formula (2) -1 and / or formula (2) -2 (hereinafter referred to as “specific monomer (2)”) is further used. The resulting cyclic olefin-based addition polymer is preferable because it can impart crosslinkability.

  That is, by using the specific monomer (2), a hydrolyzable silyl group can be introduced into the molecule of the cyclic olefin addition polymer, and the hydrolyzable silyl group acts as a crosslinking site by a siloxane bond. To do. In addition, since the hydrolyzable silyl group also acts as a site for adhesion / adhesion with other members, it also contributes to improvement in adhesion / adhesion with other members of the cyclic olefin addition polymer. I can expect that.

(In Formula (2) -1 and Formula (2) -2, R ¹ and R ² are substituents selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group;
X is an alkoxy group having 1 to 5 carbon atoms or a halogen atom,
Y is a hydroxyl group residue of an aliphatic diol having 2 to 4 carbon atoms,
k is an integer of 0 to 2, and n is 0 or 1. )
Specific examples of the specific monomer (2) include the following compounds, but the present invention is not limited to these specific examples.

Examples of the specific monomer (2) represented by the general formula (2) -1 include the following compounds.
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilyl-bicyclo [2.2.1] hept-2-ene,
9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-triethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-cyclohexyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-phenyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dimethylmethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-trichlorosilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-dichloromethylsilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethylsilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dichloromethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chloromethylmethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene.

  These may be used alone or in combination of two or more.

Examples of the specific monomer (2) represented by the general formula (2) -2 include the following compounds.
5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
9- [1′-Methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9- [1′-Phenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene.

  These may be used alone or in combination of two or more. Moreover, as a specific monomer (2), 1 or more types of the compound represented by the said General formula (2) -1 and 1 or more types of the compound represented by the said General formula (2) -2 are included. You may use it in combination.

Among these specific monomers (2),
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl - bicyclo [2.2.1] hept-2-ene 9-trimethoxysilyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-triethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
5- [1′-methyl-2 ′, 6′-dioxa-4 ′, 4′-dimethyl-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-4′-methyl-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene is preferred.

  When using a specific monomer (2), it is 2-30 mol% in all the monomers, Preferably it is used in 5-20 mol%. When the monomer used in the present invention contains the specific monomer (2) in such an amount, the copolymer becomes a cyclic olefin-based addition copolymer containing a hydrolyzable silyl group. When the obtained copolymer is formed into a crosslinked film, it can be a film having adhesion / adhesion with small solvent resistance / chemical resistance and heat shrinkage. When the ratio of the specific monomer (2) in all the monomers exceeds 30 mol%, there may be a problem of a decrease in polymerization activity and an increase in water absorption of the formed addition polymer. Moreover, when the ratio of a specific monomer (2) is less than 2 mol%, the effect of a crosslinkability or the improvement of adhesion and adhesiveness with another member may not be acquired.

Although it does not specifically limit in this invention, It is preferable that a monomer does not contain monomers other than a specific monomer (1) and a specific monomer (2).
<Production of cyclic olefin addition polymer>
Addition Polymerization In the production method of the present invention, the above monomer is subjected to addition polymerization in the presence of a multicomponent catalyst comprising the above components.

  The addition polymerization according to the present invention is usually carried out in a polymerization solvent. In the present invention, examples of the solvent that can be used for addition polymerization include alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, toluene, and benzene. Aromatic hydrocarbon solvents such as xylene, ethylbenzene and mesitylene, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene and dichlorobenzene, but non-halogen type It is preferable to use a solvent in terms of environmental measures.

  In the present invention, a mixed solvent using two or more of these solvents can also be used.

  In the addition polymerization according to the present invention, the polymerization temperature can be usually in the range of −20 to 120 ° C., preferably 20 to 100 ° C., and the temperature can be changed with time.

  In the present invention, it is possible to adopt a method of charging monomers at once or a method of sequentially adding monomers. When two or more types of monomers are used, the resulting copolymer is controlled from random copolymers with no composition distribution to copolymers with a composition distribution, depending on the difference in copolymerization reactivity and the monomer preparation method. can do. As the polymerization process method, either a batch polymerization method or a continuous polymerization method using a tank reactor, a column reactor, a tube reactor or the like can be employed.

  In this invention, the structural unit represented by following General formula (3) is formed by addition-polymerizing the monomer containing the above-mentioned specific monomer (1). In addition, the structural unit represented by the general formula (3) may be formed by hydrogenating the resulting polymer after the addition polymerization as described later.

(In formula (3), A ^{1 to} A ⁴ and m are the same as defined in general formula (1).)
When the monomer contains the specific monomer (2) -1 and / or (2) -2, the specific monomer (1) and the specific monomer (2) are subjected to addition polymerization. Thus, in addition to the structural unit represented by the general formula (3), the structural unit represented by the general formula (4) -1 or (4) -2 is formed.

(In Formula (4) -1 and Formula (4) -2, R ¹ , R ² , X, Y, k, and n are the same as defined in Formula (2) -1 and Formula (2) -2). .)
In the present invention, addition polymerization is stopped by adding an organic carboxylic acid compound, alcohol compound, primary to tertiary amine compound, hydroxyamine compound, ammonia, hydrogen, allyl halide compound, methyl halide to the polymer solution. A compound selected from an aryl compound, a tertiary alkyl halide compound, an acyl halide compound, a silane compound having a Si—H bond, and the like is added.

In the present invention, the molecular weight of the cyclic olefin-based addition polymer is controlled by, for example, ethylene, propylene, 1-butene, 1-hexene, trimethylsilylethylene, trimethoxyethylene, triethoxyethylene, styrene or other olefins, cyclopentene, cyclohexadiene. , Triethylsilane, diethylsilane, phenylsilane, diphenylsilane, and other silane compounds, isopropanol, water, hydrogen, etc., but the molecular weight can be controlled with a small amount, and there is no effect on the polymerization activity. preferable.
In the present invention, when an olefinically unsaturated bond is present in the obtained addition polymer, such as when the specific monomer (1) having an olefinically unsaturated bond is used, coloring by heat or light It is preferable to hydrogenate (hydrogenate) such olefinically unsaturated bonds. The higher the hydrogenation rate, the better. Usually, it is desirable to be 90% or more, preferably 95% or more, and more preferably 99% or more.

The hydrogenation method is not particularly limited, and can be performed by applying a method for hydrogenating a normal olefinically unsaturated bond. In general, hydrogenation is performed in an inert solvent at a hydrogen gas pressure of 0.5 to 15 MPa and a reaction temperature of 0 to 200 ° C. in the presence of a hydrogenation catalyst. In addition, when an aromatic ring exists in a polymer, since the aromatic ring concerned may contribute to an optical characteristic and heat resistance, it does not necessarily need to be hydrogenated.

  Examples of the inert solvent that can be used for the hydrogenation reaction include aliphatic hydrocarbons having 5 to 14 carbon atoms such as hexane, heptane, octane, and dodecane, and carbon atoms such as cyclohexane, cycloheptane, cyclodecane, and methylcyclohexane. -14 alicyclic hydrocarbons may be mentioned, but when hydrogenating under conditions where the aromatic ring is not hydrogenated, aromatic hydrocarbons having 6 to 14 carbon atoms such as benzene, toluene, xylene, ethylbenzene, etc. are also used. be able to.

As the hydrogenation catalyst, a solid catalyst in which a group VIII metal such as nickel, palladium, platinum, cobalt, ruthenium, rhodium or a compound thereof is supported on a porous carrier such as carbon, alumina, silica, silica alumina, diatomaceous earth, or A homogeneous catalyst such as a group IV-VIII organic carboxylate such as cobalt, nickel or palladium, a combination of a β-diketone compound and organoaluminum or organolithium, or a complex such as ruthenium, rhodium or iridium is used.
Decatalyst In the production method of the present invention, the catalyst used in the polymerization reaction and the catalyst used in the hydrogenation reaction to be carried out as necessary are preferably removed in the decatalysis step. The method applied in the decatalysis step is not particularly limited, and is appropriately selected according to the properties and shape of the catalyst used.

  In the present invention, a solution of a polymer obtained by stopping polymerization or a hydrogenated product thereof is added to oxycarboxylic acid such as lactic acid, glycolic acid, β-methyl-β-oxypropionic acid, γ-oxybutyric acid, The catalyst is removed by treatment with an aqueous solution of ethanolamine, dialkylethanolamine, ethylenediaminetetraacetate or the like, or treatment with an adsorbent such as diatomaceous earth, silica, alumina, activated carbon or the like.

  In addition, the solvent can be removed directly from the decatalyzed solution, or it can be coagulated with alcohols such as methanol, ethanol and propanol, or ketones such as acetone and methyl ethyl ketone, and then dried. To obtain a cyclic olefin-based addition polymer.

By such a method, the addition polymer obtained in the present invention can be adjusted to 5 ppm or less, preferably 2 ppm or less, more preferably 0.5 ppm or less, as Pd atoms and Al atoms, respectively.
Recovery In the production method of the present invention, the cyclic olefin addition polymer produced through steps such as polymerization and decontacting is obtained from a solution containing the polymer using a known method, for example, heating or decompression. It can be recovered by a method of directly removing the solvent, a method of coagulating and separating the polymer by mixing a solution containing the polymer and a poor solvent of the polymer such as alcohol or ketone. Moreover, the said solution can be used as a raw material as it is, and it can also collect | recover by shape | molding into a film and a sheet | seat by the solution casting method (cast method).
<Cyclic olefin addition polymer>
The glass transition temperature (Tg) of the cyclic olefin addition polymer obtained by the production method of the present invention is determined by the kind and amount of the monomer used for the polymerization, and can be appropriately selected according to the use in which the polymer is used. Usually, it is 150-450 degreeC, Preferably it is 200-400 degreeC. When the glass transition temperature of the polymer is less than 150 ° C., there may be a problem in heat resistance. On the other hand, when it exceeds 450 ° C., the polymer becomes stiff and the toughness may be lowered, and it may be easily cracked.

  In the present invention, the molecular weight of the cyclic olefin-based addition polymer is measured by gel permeation chromatography method using o-dichlorobenzene as a solvent at 120 ° C., and the number average molecular weight (Mn) in terms of polystyrene is 10,000. ~ 300,000, weight average molecular weight (Mw) is 30,000 to 500,000, preferably number average molecular weight (Mn) is 30,000 to 200,000, and weight average molecular weight (Mw) is 50,000 to 300,000. 000.

  When the number average molecular weight (Mn) is less than 10,000 and the weight average molecular weight (Mw) is less than 30,000, the film or sheet may be easily broken. On the other hand, when the number average molecular weight (Mn) is more than 300,000 and the weight average molecular weight (Mw) is more than 500,000, the solution viscosity of the polymer is reduced when a film or sheet is produced by the casting method (solution casting method). It may be too high and difficult to handle.

  In the cyclic olefin addition polymer according to the present invention, 0.01 to 5 parts by weight of an antioxidant selected from phenol, phosphorus, thioether, and lactone is added per 100 parts by weight of the addition polymer. Further, the heat deterioration resistance can be improved.

In addition, the cyclic olefin addition polymers according to the present invention include other cyclic olefin addition polymers, hydrogenated cyclic olefin additions, and the like in order to improve processability and mechanical properties such as toughness. Cyclic polymer, addition copolymer of α-olefin and cyclic olefin, crystalline α-olefin polymer, rubbery ethylene and α-olefin copolymer having 3 or more carbon atoms, hydrogenated butadiene A polymer, a hydrogenated butadiene / styrene block copolymer, a hydrogenated isoprene polymer, and the like can be blended at a ratio of 0.1 to 90% by weight.
Molding The polymer of the present invention or a method of molding the polymer-containing composition is not particularly limited, but the polymer or polymer of the present invention can be reduced in that deterioration of the polymer due to thermal history can be suppressed. A solution casting method (casting method) is preferred in which the composition containing the composition is dissolved or dispersed in a solvent and applied to a support, and then the solvent is dried. In this way, a film, sheet or thin film molded body is obtained.

  The cyclic olefin polymer according to the present invention may be further crosslinked. For example, in the formation of the above-described film or sheet, the cross-linking is performed from the outside in the step before, during or after the drying step after the polymer solution or dispersion containing the acid generator is solution-cast as described above. It can be performed by heating or light irradiation.

  The cyclic olefin addition polymer (hereinafter referred to as “hydrolyzable silyl group-containing polymer”) having the structural unit (4) -1 or (4) -2 obtained by the production method of the present invention is on the side. Since it has a hydrolyzable silyl group as a chain substituent, it can be made into a crosslinked product crosslinked with a siloxane bond by hydrolysis and condensation in the presence of an acid. When such a crosslinked product is formed into a film or sheet, the linear expansion coefficient is greatly reduced, and the solvent resistance, chemical resistance and liquid crystal resistance are also excellent.

  In the present invention, a compound capable of generating an acid by the action of light or heat (acid generator) is blended in a solution of a hydrolyzable silyl group-containing polymer, and the film is cast by a solution casting method (cast method). Or after making into a sheet | seat, it can irradiate with light or heat-process, generate | occur | produce an acid, a crosslinking can be advanced, and the said crosslinked body can be obtained.

Examples of the acid generator used in the present invention include compounds selected from the following groups 1), 2) and 3), and at least one selected from these is a hydrolyzable silyl group-containing polymer. It is preferably used in the range of 0.001 to 5 weights per 100 parts by weight.
1) Diazonium salt, ammonium salt, iodonium salt, sulfonium salt, sulfonium salt or phosphonium salt which is unsubstituted or has an alkyl group, aryl group or heterocyclic group, and the counter anion is sulfonic acid, boronic acid, phosphoric acid, antimony Onium salts that are acids or carboxylic acids, halogen-containing oxadiazoles, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing organic compounds such as halogen-containing benzophenone compounds, 1,2-benzoquinonediazide-4-sulfonic acid esters, 1 Quinonediazide compounds such as 1,2-naphthoquinonediazide-4-sulfonic acid ester, diazo such as α, α′-bis (sulfonyl) diazomethane, α-carbonyl-α′-sulfonyldiazomethane Compounds that generate acid when irradiated with light, such as methane compounds.
2) An aromatic sulfonium salt, aromatic ammonium salt, aromatic pyridinium salt, aromatic phosphonium salt in which the counter anion is selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) ₄ , A compound that generates an acid when heated to 50 ° C. or higher, such as an aromatic iodonium salt, a hydrazinium salt, or an iron salt of a metallocene.
3) Trialkyl phosphites, triaryl phosphites, dialkyl phosphites, alkyl phosphites, hypophosphites, esters of secondary or tertiary alcohols of organic carboxylic acids, Hemiacetal ester of organic carboxylic acid, trialkylsilyl ester of organic carboxylic acid or ester compound of organic sulfonic acid and secondary or tertiary alcohol, etc., at 50 ° C. or higher in the presence of water or in the absence of water The compound which generate | occur | produces an acid by heating is mentioned.

  Among these, the compound 3) is preferable because it has good compatibility with the hydrolyzable silyl group-containing polymer and is excellent in storage stability when mixed in a solution containing the hydrolyzable silyl group-containing polymer.

  The cyclic olefin addition polymer obtained by the production method of the present invention can be used for optical material parts, electronic / electrical parts, medical equipment, electrical insulating materials, packaging materials, and the like.

  For example, as an optical material, a light guide plate, a protective film, a deflection film, a retardation film, a touch panel, a transparent electrode substrate, an optical recording substrate such as CD, MD, DVD, a TFT substrate, a color filter substrate, an optical lens, It can be used as a sealing material. As electronic / electrical parts, it can be used for containers, trays, carrier tapes, separation films, cleaning containers, pipes, tubes and the like. As medical equipment, it can be used for chemical containers, ampoules, syringes, infusion bags, sample containers, test tubes, blood collection tubes, sterilization containers, pipes, tubes and the like. As an electrical insulating material, it can be used as a coating material for electric wires and cables, an insulating material for office automation equipment such as a computer, a printer, and a copying machine, and an insulating material for printed circuit boards. As a packaging material, it can be used for package films of foods and pharmaceuticals.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The molecular weight, glass transition temperature, and composition in the polymer were measured by the following methods.
(1) Molecular weight Using a H type column manufactured by Tosoh Corporation with a 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS, the molecular weight was measured at 120 ° C. using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Glass transition temperature The glass transition temperature is measured at the peak temperature of temperature dispersion of Tan δ (ratio of storage elastic modulus E ′ and loss elastic modulus E ″ Tan δ = E ″ / E ′) measured by dynamic viscoelasticity. did. Measurement of dynamic viscoelasticity using Leo Vibron DDV-01FP (manufactured by Orientec), measuring frequency 10Hz, heating rate 4 ° C / min, excitation mode single waveform, excitation amplitude 2.5μm Was used to measure the peak temperature of Tan δ.
(3) copolymer composition analysis of the polymer in the reaction product copolymer alkoxysilyl group, the ester group and an oxetane group 270 MHz ¹
The content in the resulting copolymer was determined by measuring with an H-NMR (solvent: C ₆ D ₆ ) apparatus.

The methoxy group used 3.5 ppm absorption (CH _{3 of} SiOCH ₃ ), and the ethoxy group used 3.9 ppm absorption (SiOCH ₂ CH ₃ CH ₂ ). The methyl ester group absorbs 3.5 ppm (—C (O) OCH ₃ ), and the ethyl ester group absorbs 3.9 ppm (—C (O) OCH ₂ CH ₃ CH ₂
)It was used. The oxetanyl group used 4.2-4.6 ppm absorption (CH ₂ next to the 4-membered ring O atom).
Reference Example-1
In a 50 ml flask, 1.0 g (3.57 mmol) of tricyclohexylphosphine was dissolved in 10 ml of deuterated benzene under a nitrogen atmosphere to prepare a 0.357 mmol / ml solution.

The ³¹ P-NMR (nuclear magnetic resonance) spectrum of tricyclohexylphosphine was measured with a JEOL-270 type nuclear magnetic resonance apparatus (NMR) manufactured by JASCO Corporation using trimethyl phosphite (140 ppm) as an external standard.

As a result, an absorption spectrum of tricyclohexylphosphine was observed at 9.2 ppm.
Reference example-2
A part of the deuterated benzene solution of Reference Example 1 was collected in a separate flask, and 1 mmol of air in terms of oxygen atom was added to 1 mmol of tricyclohexylphosphine, and contacted at 25 ° C. for 2 days. . ³¹ P-NMR of the tricyclohexylphosphine solution in contact with the air was measured. As a result, there was no 9.2 ppm absorption spectrum of tricyclohexylphosphine, and a new absorption spectrum of tricyclohexylphosphine oxide was observed at 45.7 ppm.
Reference example-3
A part of the deuterated benzene solution of Reference Example 1 was collected in a separate flask, 1 mmol of triethylaluminum was added to 1 mmol of tricyclohexylphosphine, and reacted at 25 ° C. for 30 minutes to give an addition complex. Was synthesized in deuterated benzene.

³¹ P-NMR of this complex solution of tricyclohexylphosphine and triethylaluminum having a molar ratio of 1: 1 was measured. This resulted in 9.2 p of tricyclohexylphosphine.
There was no absorption spectrum of pm, and an absorption spectrum by tricyclohexylphosphine newly formed as an addition complex with triethylaluminum at -4.0 ppm was observed.
Reference example-4
In Reference Example-2, contact was made with air in the same manner as in Reference Example-2 except that instead of tricyclohexylphosphine, a complex of tricyclohexylphosphine and triethylaluminum having a molar ratio of 1: 1 was used.
Reference Example-5
In Reference Example-3, an addition complex having a molar ratio of cyclohexylphosphine to diethylaluminum chloride of 1: 1 was synthesized in the same manner as Reference Example-3 except that diethylaluminum chloride was used instead of triethylaluminum.

8. Dehydrated toluene with 6 ppm water in a 100 ml glass pressure bottle under nitrogen atmosphere
4 g, 37.6 g of cyclohexane with a water content of 5 ppm, 9-trimethoxysilyltetracyclo [
6.2.1.1 ^3,6 0 ^2,7 ] 10 mmol of dodec-4-ene and 90 mmol of bicyclo [2.2.1] hept-2-ene are charged, and the charging port is sealed with a rubber cap with a crown. Stopped. Further, 30 ml of 0.1 MPa gaseous ethylene was charged as a molecular weight regulator through a rubber cap of a pressure bottle.

A pressure bottle containing a solvent and a monomer was heated to 75 ° C., palladium acetate was used as a Pd atom, 2 × 10 ⁻⁴ milligram atom, and a molar ratio of tricyclohexylphosphine obtained in Reference Example-3 to triethylaluminum 1: Polymerization was carried out by adding 2 × 10 ⁻⁴ mmol of 1 addition complex and 2.4 × 10 ⁻⁴ mmol of triphenylcarbenium tetrakispentafluorophenylborate [Ph ₃ C · B (C ₆ F ₆ ) ₄ ] in this order. Started.

  The polymerization reaction was carried out at 75 ° C. for 3 hours, but the polymer solution was transparent without becoming cloudy. To this solution, 0.1 mmol of triethylsilane was added to terminate the polymerization. From the measurement of the solid content of the polymer solution, the conversion rate to the polymer was 95%.

  The operation of adding 30 ml of water containing 1.0 mmol of triethanolamine to the polymer solution to extract and remove the catalyst residue was performed twice, and the polymer solution was put into 2 liters of isopropanol to solidify the polymer. After solidifying, the polymer A was obtained by drying at 90 ° C. for 17 hours under reduced pressure. The residual metal in polymer A by atomic absorption analysis was 0.5 ppm for Pd atoms and 1.5 ppm for Al atoms.

Moreover, the proportion of the structural units derived from 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7] dodeca-4-ene in the polymer A, obtained from the H-NMR of 270MHz It was. As a result, the proportion of structural units derived from 9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene was 9.7 mol%. The number average molecular weight (Mn) was 74,000, the weight average molecular weight (Mw) was 185,000, and the glass transition temperature (Tg) was 360 ° C.

  Example 1 was carried out in the same manner as in Example 1 except that instead of the tricyclohexylphosphine and triethylaluminum addition complex of Reference Example-3, a complex obtained by contacting the addition complex of Reference Example-4 with air was used. It was.

  The conversion to polymer was 97%.

  The number average molecular weight (Mn) of the polymer B thus obtained was 73,000, the weight average molecular weight (Mw) was 187,000, and the glass transition temperature (Tg) was 365 ° C. Moreover, the ratio of the structural unit derived from 5-triethoxysilylbicyclo [2.2.1] hept-2-ene in the polymer B was 9.8 mol%.

In Example 1, following addition of triphenylcarbenium tetrakispentafluorophenylborate [Ph ₃ C · B (C ₆ F ₆ ) ₄ ] as a catalyst component, 10 × 10 ⁻⁴ mmol of triethylaluminum was added, and 9 -Trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene instead of 10 mmol 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene The same procedure as in Example 1 was carried out, using 10 mmole, adding 5.0 mmole before the start of polymerization and then adding 1.0 mmole 5 times at 20 minute intervals.

  The polymerization system did not become cloudy until the completion of the polymerization in 3 hours, and the conversion rate to the polymer was 98%.

  The number average molecular weight (Mn) of the polymer C thus obtained was 72,000, the weight average molecular weight (Mw) was 177,000, and the glass transition temperature (Tg) was 360 ° C. Moreover, the ratio of the structural unit derived from 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene in the polymer C was 9.7 mol%.

  When polymer C was made into 20% by weight of p-xylene and molded by a solution casting method (cast method), an optically transparent film was obtained. Furthermore, when a film to which cyclohexyl p-toluenesulfonate was added was crosslinked with steam, a crosslinked film having excellent chemical resistance and solvent resistance was obtained.

In Example 1, instead of using 10 mmol of 9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] Dodeca-4-ene The procedure was the same as that of Example 1 except that 10 mmol was used.

  The polymerization system did not become cloudy until the polymerization was completed in 3 hours, and the conversion rate was 91%.

The number average molecular weight (Mn) of the polymer D thus obtained was 62,000, the weight average molecular weight (Mw) was 156,000, and the glass transition temperature (Tg) was 360 ° C. Further, the proportion of structural units derived from 9-methyl, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene in polymer D is 9.2 mol%. Met.

In a 100 ml glass pressure bottle, 37.6 g of cyclohexane as a solvent, 9.4 g of toluene, monomer, and 97 mmol of bicyclo [2.2.1] hept-2-ene as a cyclic olefin, 9- Trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene 3 mmol, cycloocta-1,4-diene 10 × 10 ^-4 mmol as a cyclic non-conjugated diene are charged. Further, 10 × 10 ⁻⁴ mmol of triethylaluminum and 1.4 × 10 ⁻⁴ mmol of tricyclohexylphosphine were charged. The charging port is sealed with a rubber cap with a crown, and after 30 minutes at 30 ° C., an addition complex of triethylaluminum and cyclohexylphosphine is formed. Then, 30 ml of gaseous 0.1 MPa ethylene as a molecular weight regulator is charged, and palladium acetate is further added. 2 × 10 ⁻⁴ mmol (as Pd atom), 2.4 × 10 ⁻⁴ mmol of triphenylcarbenium tetrakispentafluorophenylborate [Ph ₃ C · B (C ₆ F ₆ ) ₄ ] were charged at 75 ° C. Polymerization was started.

  The polymer solution after 3 hours was transparent and the conversion to the polymer was 99%, solidified with isopropanol, and then dried to obtain a polymer E.

The polymer E thus obtained had a number average molecular weight (Mn) of 64,000 and a weight average molecular weight (Mw) of 177,000, and 9-trimethoxysilyltetracyclo [6.2 in the polymer E]. ratio of .1.1 ^3,6 0 ^2,7] dodeca-4-ene-derived structural units is 3.0 mol%, the glass transition temperature (Tg) of 375 ° C..

In Example 1, 100 mmol of 5-n-hexylbicyclo [2.2.1] hept-2-ene having an endo / exo ratio of 20/80 as a monomer and tricyclohexylphosphine as a catalyst component Except that the addition complex of tricyclohexylphosphine and diethylaluminum chloride in the molar ratio of 1: 1 in Reference Example-5 was used instead of 1.5 × 10 ⁻⁴ mmol instead of the addition complex in a molar ratio of 1: 1 and triethylaluminum. The same operation as in Example 1 was performed.

  Polymerization was stopped at a conversion rate to a polymer of 1.5% after 82 hours to obtain a polymer F.

  Since the endo body was not substantially polymerized, the polymer solution was transparent, and the film obtained by casting the polymer F from a 20 wt% cyclohexane solution was also transparent.

8. Dehydrated toluene with 6 ppm water in a 100 ml glass pressure bottle under nitrogen atmosphere
4 g, 37.6 g of cyclohexane with a water content of 5 ppm, 9-trimethoxysilyltetracyclo [
6.2.1.1 ^3,6 0 ^2,7 ] 10 mmol of dodec-4-ene and 90 mmol of bicyclo [2.2.1] hept-2-ene are charged, and the charging port is sealed with a rubber cap with a crown. Stopped. Furthermore, 35 ml of gaseous ethylene was charged through the rubber cap of the pressure bottle.

In advance, palladium bis (acetylacetonate) as a Pd atom is 3 × 10 ⁻⁴ milligram atom, and an addition complex of 3 × 10 ⁻⁴ mmol of tricyclohexylphosphine and triethylaluminum obtained in Reference Example-3 at a molar ratio of 1: 1. Triphenylcarbenium tetrakispentafluorophenylborate [Ph ₃ C · B (C ₆ F ₆ ) ₄ ] 3.4 × 10 ⁻⁴ mmol and bicyclo [2.2.1] hepta-2,5-diene 15 × A catalyst obtained by aging 10 ^-4 mmol in a solution of 2 ml of toluene at 60 ° C for 30 minutes was charged into a pressure bottle containing a solvent and a monomer heated to 75 ° C, and polymerization was started.

  The polymerization reaction was carried out at 75 ° C. for 3 hours, but the polymer solution was transparent without becoming cloudy. To this solution, 1 ml of dimethylaminoethanol was added to terminate the polymerization. From the measurement of the solid content of the polymer solution, the conversion to polymer was 92%.

Ratio of the resulting polymer G in 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7] dodeca-4-ene-derived structural units is met 9.6 mol% It was.

  Polymer G was a polymer having a number average molecular weight (Mn) of 48,000, a weight average molecular weight (Mw) of 235,000 and a slightly broad molecular weight distribution.

  In Example 1, it carried out like Example 1 except adding 30 ml of air to a pressure bottle after adding 30 ml of gaseous ethylene. The conversion to polymer after 3 hours was 96%.

The proportion of structural units derived from 9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene in the polymer H was 9.8 mol%. The molecular weight was a number average molecular weight (Mn) of 76,000 and a weight average molecular weight (Mw) of 187,000.

Compared to Example 1, even when air was added to the polymerization system, the polymerization activity and molecular weight were not affected.
Reference Example 6
In Example 1, the molar ratio of tricyclohexylphosphine and triethylaluminum 1: Instead of using the addition complex 2.0 × 10 ^-4 mmol of 1, the other for the use of tricyclohexylphosphine 2.0 × 10 ^-4 mmol Was polymerized in the same manner as in Example 1. The conversion rate to the polymer after 3 hours was 95%.
Comparative Example 1
In Example 1, instead of using 2.0 × 10 ⁻⁴ mmol of a 1: 1 addition ratio of tricyclohexylphosphine to triethylaluminum, the amount of tricyclohexylphosphine in contact with air prepared in Reference Example 2 was changed to 2.0. Polymerization was conducted in the same manner as in Example 1 except that × 10 ⁻⁴ mmol was used.

The conversion to polymer after 3 hours was 0%.
Comparative Example 2
In Example 8, the molar ratio of tricyclohexylphosphine and triethylaluminum 1: Instead of the first addition complex 2.0 × 10 ^-4 mmol, other for the use of tricyclohexylphosphine 2.0 × 10 ^-4 mmole Polymerization was conducted in the same manner as in Example 8. The conversion rate to the polymer after 3 hours was 65%, and the conversion rate after 7 hours was 78%.

The proportion of structural units derived from 9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene in the polymer was 9.8 mol%. The molecular weight was a number average molecular weight (Mn) of 56,000, and a weight average molecular weight (Mw) of 137,000. Compared to Example 1 and Example 8, there was a decrease in polymerization activity and a decrease in molecular weight by adding air to the polymerization system.

  The cyclic olefin addition polymer obtained by the method for producing a cyclic olefin addition polymer of the present invention can be used for optical materials, electronic / electric parts, medical equipment, electrical insulation materials, and packaging materials. .

  Examples of the optical material include a light guide plate, a protective film, a deflection film, a retardation film, a touch panel, a transparent electrode substrate, an optical recording substrate such as a CD, MD, and DVD, an optical lens, and a sealing material.

  Examples of the electronic / electric parts include liquid crystal display elements, liquid crystal substrates, containers, trays, carrier tapes, separation films, cleaning containers, pipes, tubes, and the like.

  Examples of medical equipment include chemical containers, ampoules, syringes, infusion bags, sample containers, test tubes, blood collection tubes, sterilization containers, pipes, tubes, and the like.

  Examples of the electrical insulating material include a coating material for electric wires and cables, an insulating material for office automation equipment such as a computer, a printer, and a copying machine, and an insulating material for a printed circuit board.

Claims (6)

(A) a palladium compound,
(B) a compound selected from ionic boron compounds, ionic aluminum compounds and Lewis acidic aluminum or Lewis acidic boron compounds, and
(C) Addition complex of a phosphine compound having a cone angle of 170 to 200 and an organoaluminum compound, which is a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group. In the presence of a multi-component catalyst containing
A method for producing a cyclic olefin addition polymer, which comprises addition polymerization of a monomer containing a cyclic olefin compound represented by the following general formula (1);

(In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aryl group, an ester group, an oxetanyl group, an alkoxy group, or a trialkylsilyl group. An atom or group selected from the group consisting of a group and a hydroxyl group, these having 0 to 10 carbon atoms containing at least one atom selected from an alkylene group having 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom; In addition, A ¹ and A ² may be linked to a ring structure by an alkylidene group having 1 to 5 carbon atoms, a substituted or unsubstituted alicyclic or aromatic ring having 5 to 20 carbon atoms, may form a heterocyclic ring having 2 to 20 carbon atoms, a ¹ and a ³ is a substituted or unsubstituted alicyclic or aromatic ring having 5 to 20 carbon atoms, a heterocyclic ring having 2 to 20 carbon atoms M may be formed. 0 or 1). Addition complex (C) of phosphine compound and organoaluminum compound was brought into contact with air
The method for producing a cyclic olefin addition polymer according to claim 1, wherein the method is a product. The multi-component catalyst includes (D) an organoaluminum compound in addition to (A), (B) and (C), and the content of the organoaluminum compound (D) is 1 gram of palladium of the palladium compound (A). The method for producing a cyclic olefin addition polymer according to claim 1 or 2 , wherein the amount is from 0.1 to 200 mol per atom. The multicomponent catalyst comprises a polycyclic monoolefin or nonconjugated diene having a bicyclo [2.2.1] hept-2-ene structure, a monocyclic nonconjugated diene, and a linear nonconjugated diene. The method for producing a cyclic olefin addition polymer according to any one of claims 1 to 3, wherein the catalyst is prepared in the presence of at least one compound selected from the group. Multi-component catalyst
In the presence of a bicyclo [2.2.1] hept-2-ene and / or a bicyclo [2.2.1] hept-2-ene derivative having one or more hydrocarbon groups having 1 to 15 carbon atoms, After forming (C),
The cyclic structure according to any one of claims 1 to 4 , wherein the catalyst is prepared by adding (A) and (B) and further adding (D) an organoaluminum compound as necessary. A method for producing an olefin addition polymer. The monomer includes a cyclic olefin compound represented by the following general formula (2) -1 or (2) -2, The cyclic olefin based addition weight according to any one of claims 1 to 5 , Manufacturing method of coalescence.

(In Formula (2) -1 and Formula (2) -2, R ¹ and R ² are substituents selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group;
X is an alkoxy group having 1 to 5 carbon atoms or a halogen atom,
Y is a hydroxyl group residue of an aliphatic diol having 2 to 4 carbon atoms,
k is an integer of 0 to 2, and n is 0 or 1. )