JP2003040930A - Production method of cyclic olefin addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a cyclic olefin addition polymer, wherein a monomer component containing a cyclic olefin having a polar group is addition-polymerized in a hydrocarbon solvent, using a catalyst component easy to obtain and without using a lot of aluminoxane. SOLUTION: A cyclic olefin addition polymer is obtained by polymerizing, in a hydrocarbon solvent, a cyclic olefin containing a cyclic olefin having a specific polar group, using a polymerization catalyst composed of (i) a strong Bronsted acid modified compound, shown by formula (2): [Ln NiX][A] [In formula (2), L is a neutral legand or a solvent molecule, n is 0-3, X is a β-diketonato anion or a carboxylic acid anion having the 1-12C straight chain or branched alkyl, and Al is a non-coordinating anion or a weak-coordinating anion], of a compound selected from a Ni compound or a β-diketonatoNi or a carboxylate of Ni having a 1-12C straight chain or branched alkyl group, (ii) a Lewis acid compound and (iii) an alkyl aluminoxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cycloolefin addition polymer. More specifically, it is possible to carry out addition polymerization of a monomer component containing at least one polar group-containing cyclic olefin in a hydrocarbon solvent using a specific polymerization catalyst without requiring a large amount of alkylaluminoxane. The present invention relates to a method for producing a cycloolefin addition polymer, which is characterized.

[0002]

2. Description of the Related Art Polymers of cyclic olefins such as norbornene are known as plastic materials having extremely high transparency and thermal stability. So far, metathesis polymerization, metallocene catalysts and late transition metal catalysts have been used. Addition polymerization and the like have been reported.

For example, JP-A-60-26024,
Japanese Patent No. 3050196, JP-A-1-132625
Japanese Unexamined Patent Publication No. Hei 1-132626 discloses hydrides of metathesis polymers of cyclic olefins. However, it is difficult to manufacture these materials having a glass transition temperature of 200 ° C. or higher, and they are not always satisfactory in terms of heat resistance. In addition, a small amount of unhydrogenated double bonds often remain in the molecular chain, and there is a drawback in thermal stability such as coloring at high temperature.

On the other hand, addition polymers of cyclic olefins can be produced with a glass transition temperature of more than 200 ° C. and can be suitably used in applications requiring extremely high heat resistance. Further, it is possible to control the glass transition temperature and impart a function by selecting the monomer component.

On the other hand, as one means for imparting good dispersibility, adhesiveness, adhesion, etc. for the purpose of forming a composite with another material, or introducing a cross-linking point for the purpose of improving the strength. It is required to introduce a polar group into the addition polymer of cyclic olefin. However, in general, a polar group often becomes a catalyst poison when carrying out addition polymerization with a transition metal catalyst and remarkably reduces the polymerization activity. Therefore, it has been very difficult to introduce a polar group in the past.

Regarding the addition polymerization using a metallocene catalyst such as zirconium, see W. Kaminsky et al.
For example, Makromol. Chem. Macromo
l. Symp. Vol. 47, 83 (1991) and the like, it is reported that an insoluble and infusible addition polymer can be obtained. However, since the metallocene catalyst has an extremely low polymerization ability with respect to a monomer containing a polar group, it is difficult to introduce the polar group. Further, in order to obtain high polymerization activity, the transition metal catalyst component used such as zirconium is required to have a complicated structure, and accordingly, a multi-step synthetic route is required. Further, there is a problem that a large amount of aluminoxane cocatalyst is required, and as a result, the cost of the catalyst becomes high, and a complicated step is required for decatalyzing.

On the other hand, Japanese Patent Application Laid-Open No. 4-63807 discloses that
A method for producing a norbornene-based polymer using a catalyst containing a transition metal compound component and an aluminoxane component as main components is disclosed. In this publication, as the substituent of the norbornene-based monomer, those containing an oxygen atom or a nitrogen atom in addition to the hydrocarbon group are defined. However, in the examples, although polymerization using a nickel compound is illustrated, such a monomer is not used, and therefore, the method of the publication gives a polymer containing a cyclic olefin having a polar group as a structural unit. There is no description. Further, it is clear from the examples in the publication that a large amount of aluminoxane component is required also by this method.

Japanese Unexamined Patent Publication (Kokai) No. 8-198919 proposes an addition type copolymer of norbornene and a substituted norbornene, but the substituent is limited to a hydrocarbon group, and a substituted norbornene having a polar group has a structure. No mention is made of polymers containing units.

On the other hand, many studies have so far been made on the polymerization of cyclic olefins having a polar group, and those which exhibit a polymerization activity are described, for example, in W. Ri
sse et al. [Makromol. Chem. 193,2
915 (1992), Macromolecules
29, 2755 (1996)], and M. Novak
Et al. [Macromolecules 28, 5396
(1995), etc.], and some palladium compounds have been proposed. In addition, special table flat 11-5058
Japanese Patent Publication No. 80 also discloses a method for polymerizing a norbornene-type monomer having a functional substituent, which uses a palladium compound component. However, in general, it is difficult to completely remove the palladium compound from the mixture after the reaction by a simple method, and sometimes there is a problem that the produced polymer is colored. In addition, the fact that the palladium compound is very expensive also hinders industrialization. In particular, many of the effective catalyst systems are active only after undergoing a multi-step synthetic route or by combining expensive chemicals such as silver compounds, and the cost of the catalyst becomes very high. . Furthermore, when a palladium compound is used, the solubility of the catalyst component in a hydrocarbon solvent is low and sufficient polymerization activity cannot be obtained. Therefore, the solvent is a halogenated hydrocarbon such as dichloromethane or chlorobenzene, nitromethane or tetrahydrocarbon. Methyl urea etc. are used. However, these solvents are expensive,
It is not industrially practical because there is concern about adverse effects on the human body and the environment.

On the other hand, the international application patent WO97 / 3
According to Japanese Patent Publication No. 3198 and Japanese Patent Publication No. 99/14635, a cyclic olefin having a polar group such as an ester group can be polymerized by a single-component catalyst system composed of a bis (perfluorophenyl) nickel complex. However, the nickel compounds used in these publications also require multiple steps in the synthesis, so the final yield is not high, and as a result, the cost of the catalyst is high.

That is, it has hitherto been required to obtain an addition polymer containing a structural unit derived from a cyclic olefin having a polar group, by using a catalyst which is more available and inexpensive, and without using a large amount of aluminoxane cocatalyst. However, as is clear from the above description, the conventional technique is insufficient.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and uses a readily available catalyst component in a hydrocarbon solvent, and without using a large amount of aluminoxane, It is an object of the present invention to provide a method for producing a cycloolefin addition polymer, which comprises subjecting a monomer component containing a cycloolefin having a polar group to addition polymerization.

[0013]

According to the present invention, a cyclic olefin containing a cyclic olefin having a specific polar group is (i) a specific nickel compound, (ii) in a hydrocarbon solvent.
The present invention relates to a method for producing a cyclic olefin addition polymer, which comprises polymerizing using a Lewis acid compound and a polymerization catalyst component containing (iii) alkylaluminoxane.

An object of the present invention is to provide a cyclic olefin containing at least one polar group-containing cyclic olefin, (i) a nickel compound represented by the following formula (2), (ii) a Lewis acid compound, and (iii) ) It is achieved by addition polymerization in a hydrocarbon solvent using a polymerization catalyst component containing an alkylaluminoxane. [L _n NiX] [A] (2) [In the formula (2), L is a neutral ligand or a solvent molecule, n is 0 to 3, and X is a β-diketonate anion. Or a carboxylic acid anion having a linear or branched alkyl group having 1 to 12 carbon atoms, and A is a non-coordinating or weakly coordinating anion. ]

Another object of the present invention is to provide a cyclic olefin containing at least one specific polar group-containing cyclic olefin by (i) a nickel β-diketonate compound or a nickel straight chain having 1 to 12 carbon atoms. Or a strong Bronsted acid-modified compound of a compound selected from carboxylic acid salts having a branched alkyl group, (ii) a Lewis acid compound,
It can also be achieved by polymerizing in a hydrocarbon solvent using a polymerization catalyst component containing (iii) alkylaluminoxane.

As described above, in Japanese Unexamined Patent Publication (Kokai) No. 4-63807, those containing an oxygen atom or a nitrogen atom in addition to a hydrocarbon group are specified as the substituent of the norbornene-based monomer. However, when a catalyst containing a nickel compound and an alkylaluminoxane as shown in the examples of the publication is used, as a result of the study by the present inventors, a polar group such as an ester group or an alkoxysilyl group is formed. It was found that even if a small amount of the cyclic olefin contained therein was present in the polymerization system, the polymerization activity was not shown or was significantly reduced. Moreover, in the method of the examples in the publication, the alkylaluminoxane needs to be added in an amount exceeding 100 times the amount of nickel atoms in terms of aluminum atoms.

However, surprisingly, by polymerizing using the catalyst component described in the present invention, even if a cyclic olefin having a polar group is present in the polymerization system, polymerization is performed while maintaining practical activity. It was confirmed that sufficient activity was expressed only by using about 10 times as many aluminum aluminoxane per nickel atom as alkyl aluminoxane. As a result of further detailed study, it is possible to control the molecular weight distribution of the addition polymer by controlling the amount of alkylaluminoxane used.

In the method of the present invention, a nickel compound represented by the following formula (2) [L _n NiX] [A] (2) can be used. Here, in the formula (2), L is a neutral ligand or a solvent molecule, for example, aromatic hydrocarbon such as benzene, toluene, xylene, mesitylene, cyclic polyene such as 1,5-cyclooctadiene, It is an ether compound such as diethyl ether, dibutyl ether, or tetrahydrofuran, and n is 0 to 3. X is a β-diketonate anion or a carboxylic acid anion having a linear or branched alkyl group having 1 to 12 carbon atoms. A is a noncoordinating or weakly coordinating anion, SbF ₆ ^-, P
Those selected from F ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ and CF ₃ COO ⁻ are preferably used. The nickel compound of the formula (2) may be synthesized by appropriately using a known method, may be used as an isolated one, or may be used without being isolated in advance.

The nickel compound (i) represented by the formula (2) is selected from a nickel β-diketonate compound and a carboxylic acid salt of nickel having a linear or branched alkyl group having 1 to 12 carbon atoms. The compound can be obtained by modifying the compound with a strong Bronsted acid compound. As a result of this modification operation, one of the β-diketonate anion and the carboxylate anion coordinated to the nickel atom is bonded to the hydrogen ion supplied from the strong Bronsted acid compound to be released, and Compound (2) is produced. As a modification method, a β-diketonate compound or carboxylate of nickel and a strong Bronsted acid compound are mixed in a hydrocarbon solvent with 3
A method of mixing and reacting at a temperature of 0 ° C. or lower is used. At that time, the presence of the neutral ligand represented by L or the coordinating solvent can enhance the uniformity of the reaction and the stability of the product. A compound in which all anions are replaced by strong Bronsted acid anions, which are by-produced when a strong Bronsted acid compound is added in excess,
Since it is usually insoluble in a hydrocarbon solvent, it can be removed by a method such as filtration.

Specific examples of the nickel β-diketonate compound include nickel bisacetylacetonate and nickel bisacetoacetate, and examples of the nickel carboxylate include nickel acetate and propionic acid. Nickel, nickel 2-ethylhexanoate (nickel octylate), nickel 3,5,5-trimethylhexanoate (nickel isononanoate), nickel octanoate, nickel naphthenate, nickel neodecanoate, nickel cyclohexylcarboxylate, nickel laurate , Nickel stearate, and particularly preferably nickel bisacetylacetonate, nickel 2-ethylhexanoate, nickel 3,5,5-trimethylhexanoate, nickel octanoate, nickel naphthenate, nickel neodecanoate. Le, cyclohexyl carboxylic acid nickel, lauric acid, nickel stearate.

The strong Bronsted acid compound is preferably selected from hexafluoroantimonic acid, hexafluorophosphoric acid, tetrafluoroboric acid, trifluoromethanesulfonic acid and trifluoroacetic acid. These may be used alone or in combination of two or more, and are used in a molar ratio of 0.5 to 10 times, preferably 1 to 2 times, with respect to 1 gram atom of nickel, If it is added in a large amount exceeding this range, the nickel compound is decomposed, or the β-diketonate or alkylcarboxylic acid anion is completely replaced with a strong Bronsted acid anion to generate a large amount of insoluble components, which is unsuitable for polymerization. It will be appropriate.

On the other hand, in the addition polymerization, (ii)
The Lewis acid compound exhibits a particularly remarkable effect on the polymerization activity and copolymerizability of a cyclic olefin having an ester group or a substituent of an acid anhydride. In particular, in the copolymerization of cyclic olefin having an acid anhydride as a substituent, not only the polymerization activity becomes extremely low in the absence of Lewis acid, but the acid anhydride is hardly introduced into the obtained addition polymer. On the other hand, according to the method of the present invention, it was revealed that the copolymerization proceeds while maintaining good activity. (Ii) The Lewis acid compound is preferably boron trifluoride, aluminum trifluoride, titanium tetrachloride, antimony pentafluoride, tris (pentafluorophenyl) boron, tris (3,5-bistrifluoromethylphenyl) boron. A material selected from the group consisting of boron trifluoride, aluminum trifluoride, titanium tetrachloride and antimony pentafluoride is particularly preferably used. These alone or 2
The above compounds can be used in combination, and (i) per gram atom of nickel constituting the nickel compound,
It is preferably used in a molar ratio range of 1 to 10 times.

Catalyst component [0023] The present invention has the following formula - it has a unit represented by (iii) those comprising alkylaluminoxane ^{- [Al (R 6) -O} ] m. Although its chemical structure is not always clear, it is presumed to be a linear, cyclic or cluster compound, or a mixture of these compounds. Here, R ⁶ is an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group or an isobutyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 to 60. Is an integer in the range. Also,
Modified methylaluminoxane (hereinafter referred to as "MMAO") with improved solubility and storage stability of methylaluminoxane by adding trialkylaluminum, etc.
Alternatively, other modified alkylaluminoxane can be used. The alkylaluminoxane compound is the above R
It can be produced by a known method involving the reaction of an alkylaluminum compound having at least one ^6- group with water, and it can also be produced by contacting an alkylaluminum compound with a trace amount of water in a reaction vessel during polymerization. it can. The alkylaluminoxane is used in a ratio of 1 to 100 times, and most preferably 1 to 50 times, as converted into aluminum atoms, with respect to the nickel atoms constituting the nickel compound (i). At that time, by lowering this ratio, the molecular weight distribution of the obtained addition polymer can be broadened, and by raising it, an addition polymer having a narrower distribution can be obtained. If it is used in excess of the above range, it may be meaningless or the activity of addition polymerization may be reduced.

The monomer component of the cyclic olefin used in addition polymerization in the method of the present invention contains at least one polar group-containing cyclic olefin represented by the following formula (1).

[0025]

[Chemical 3]

[In the formula (1), at least one of A ¹ , A ² , A ³ , and A ⁴ represents a polar group represented by — (CR ¹ R ² ) _q X, and otherwise, the same or Differently, it is a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group, a cycloalkyl group and an aryl group. Where X is —C (O) R ³ ,
^{-OC (O) R 4, C} (O) OR 5 or -SiY ¹ Y ² Y
³ , R ^{1 to} R ⁵ are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and Y ^{1 to} Y ³ are the same or different and are a hydrogen atom or a halogen atom. Represents a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, or an allyloxy group, which may be bonded to each other to form a 5- to 8-membered ring. A ¹
And A ² or A ¹ and A ³ may be ring-closed to form a cyclic ketone, lactone or acid anhydride. p and q represent the integer of 0-3. ]

Specific examples include 5-trimethoxysilyl-2-norbornene and 5-chlorodimethoxysilyl-2.
-Norbornene, 5-dichloromethoxysilyl-2-norbornene, 5-chloromethoxymethylsilyl-2-norbornene, 5-methoxymethylhydrosilyl-2-norbornene, 5-dimethoxyhydrosilyl-2-norbornene, 5-methoxydimethylsilyl-2 -Norbornene, 5-triethoxysilyl-2-norbornene, 5-
Chlorodiethoxysilyl-2-norbornene, 5-dichloroethoxysilyl-2-norbornene, 5-chloroethoxymethylsilyl-2-norbornene, 5-diethoxyhydrosilyl-2-norbornene, 5-ethoxydimethylsilyl-2-norbornene, 5-ethoxydiethylsilyl-2-norbornene, 5-tripropoxysilyl-2-norbornene, 5-triisopropoxysilyl-
2-norbornene, 5-triphenoxysilyl-2-norbornene, 5-diphenoxymethylsilyl-2-norbornene, 5-trifluorosilyl-2-norbornene, 5-trichlorosilyl-2-norbornene, 5-tribromosilyl- 2-norbornene, 5- (2 ',
6 ', 7'-trioxa-1'-silabicyclo [2.
2.2] octyl) bicyclo [2.2.1] hept-2
-Ene, 5- (4'-methyl-2 ', 6', 7'-trioxa-1'-silabicyclo [2.2.2] octyl)
Bicyclo [2.2.1] hept-2-ene, 5- (1 '
-Methyl-2 ', 5'-dioxa-1'-silacyclopentyl) bicyclo [2.2.1] hept-2-ene, 5
-Trimethoxysilylmethyl-2-norbornene, 5-
(1-Trimethoxysilyl) ethyl-2-norbornene, 5- (2-trimethoxysilyl) ethyl-2-norbornene, 5- (1-chlorodimethoxysilyl) ethyl-2-norbornene, 5- (2-chlorodimethoxy) (Silyl) ethyl-2-norbornene, 5-triethoxysilylmethyl-2-norbornene, 5- (1-triethoxysilyl) ethyl-2-norbornene, 5- (2-triethoxysilyl) ethyl-2-norbornene, 5 -(1-
Chlorodiethoxysilyl) ethyl-2-norbornene,
5- (2-chlorodiethoxysilyl) ethyl-2-norbornene, 5- (2-trimethoxysilyl) propyl-
2-norbornene, 5- (3-trimethoxysilyl) propyl-2-norbornene, 5- (2-triethoxysilyl) propyl-2-norbornene, 5- (3-triethoxysilyl) propyl-2-norbornene, 5 -Norbornene-2-carboxylic acid trimethoxysilylpropyl, 5-norbornene-2-carboxylic acid triethoxysilylpropyl, 5-norbornene-2-carboxylic acid dimethoxymethylsilylpropyl, 2-methyl-5-norbornene-2-carboxylic acid tricarboxylic acid Methoxysilylpropyl,
2-Methyl-5-norbornene-2-carboxylic acid dimethoxymethylsilylpropyl, 2-methyl-5-norbornene-2-carboxylic acid triethoxysilylpropyl, 2
-Acetyl-5-norbornene, 5-norbornene-2
-Methyl carboxylate, ethyl 5-norbornene-2-carboxylate, t-butyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 2-methyl-5-norbornene- Ethyl 2-carboxylate, 2-methyl-5-norbornene-2-carboxylate-t-butyl, 2-methyl-5-norbornene-2
-Trifluoromethyl carboxylate, 5-norbornen-2-yl acetate, 2-methyl-5-norbornene-2-acetate
2-methyl-5-norbornene-2-yl acrylate
2-methyl-5-norbornene-2, methacrylate
-Yl, dimethyl 5-norbornene-2,3-dicarboxylate, diethyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylic anhydride,
8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and spiro ring compounds as shown below.

[0028]

[Chemical 4]

The above polar group-containing cyclic olefin is used in a molar ratio of 0.1 to 100%, preferably 0.1 to 30%, and more preferably 1 to 20%, based on all monomers. .

By introducing the above-mentioned structural unit derived from a cyclic olefin containing a polar group, the addition polymer is provided with good dispersibility, adhesiveness, adhesion, etc. with a multi-material, and a cross-linking point is introduced. You can For example, an addition polymer having an acid anhydride introduced therein can form a cross-linked product by a chemical bond with another material having an amide group or a hydroxyl group. Further, those containing a repeating unit composed of norbornene having an alkoxysilyl group in an appropriate ratio can be suitably used for a complex with a metal oxide such as silica, alumina or titania. Further, the introduced polar group may be converted into another substituent by a known method.

In the method for producing a cycloolefin addition polymer of the present invention, it is desirable to copolymerize a nonpolar cycloolefin represented by the following formula (3) in addition to the polar group-containing cycloolefin.

[0032]

[Chemical 5]

[In the formula (3), B¹, B², B³, B^FourIs the same
One or different, hydrogen atom, halogen atom, carbon number 1 to
10 alkyl groups, halogenated alkyl groups, aralkyl
Group, cycloalkyl group, aryl group, B¹And B²Formed by
Alkylidene group or B ¹And B³Al combined with
Xylene group, cycloalkylene group, cycloalkenylene
Group, an alkenylene group, an arylene group, r is 0 to
Represents an integer of 3. ]

Specifically, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,
5-isopropyl-2-norbornene, 5-butyl-2
-Norbornene, 5-t-butyl-2-norbornene,
5-hexyl-2-norbornene, 5-decyl-2-norbornene, tricyclo [4.3.0.1 ^2,5 ] -3-
Decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, tricyclo [4.4.0.1 ^2,5 ] -3-undecene, tricyclo [4.3.0.1 ^2,5 ] -3,7-decadiene (dicyclo Unsubstituted or alkyl-substituted cyclic olefins such as pentadiene), 5-phenyl-2-norbornene, 5-methyl-5-phenyl-2-norbornene, 5-benzylnorbornene, 5-naphthyl-2-norbornene, 5-biphenyl-2 -Norbornene, 1,
Aryl or aralkyl-substituted norbornene such as 4-methano-1,4-dihydronaphthalene (benzonorbornene) and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, and alkylidene substitution such as 5-ethylidene-2-norbornene Cyclic olefins,
You may use these in combination of 2 or more type. In particular,
2-norbornene, tricyclo [4.3.0.1 ^2,5 ]
-3-decene, tetracyclo [4.4.0.1 ^2,5 . 1
^It is preferable that one or more cyclic olefins having no chain substituent selected from ^7,10 ] -3-dodecene are used in combination, and most preferably, 2-norbornene is used in combination. These non-polar cyclic olefins are
It is used in a molar ratio of 0 to 99.9%, preferably 70 to 99.9%, particularly preferably 80 to 99%, based on the total cyclic olefin.

For example, 2-norbornene, tricyclo [4.3.0.1 ^2,5 ] -3-decene, tetracyclo [4.4.0.1 ^2,5 . By increasing the proportion of structural units derived from a cyclic olefin having no chain substituent such as 1 ^7,10 ] -3-dodecene, an addition polymer having a small linear expansion coefficient and a high glass transition temperature can be obtained. On the contrary, when the addition polymer contains a structural unit derived from an alkyl-substituted norbornene having 3 or more carbon atoms, it is possible to lower the glass transition temperature of the addition polymer and to obtain a molded article having flexibility. Can be given. By appropriately copolymerizing an aromatic-containing cyclic olefin such as 5-phenyl-2-norbornene or 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, the optical properties such as birefringence of the addition polymer can be improved. Can be improved. Further, by including a structural unit derived from a cyclic olefin having a double bond functional group such as an alkylidene group, a crosslinking point for giving a three-dimensional network structure to the addition polymer can be introduced, and a double bond functional group can be further introduced. It is also possible to convert the group into another functional group by a known method such as epoxidation, hydrosilylation, or hydroboration, and to impart a function corresponding thereto.

Furthermore, in the method for producing a cycloolefin addition polymer of the present invention, one or more monocyclic monoolefins may be optionally used. Specific examples include cyclopentene and cyclohexene.

The cyclic olefin addition polymer of the present invention is produced by the following method. As a method of addition polymerization, under a nitrogen or argon atmosphere, a monomer composed of a solvent and a cyclic olefin and the above-mentioned polymerization catalyst are added to a reaction vessel, and polymerization is carried out in a range of -20 ° C to 100 ° C. Is. These polymerization operations can be carried out batchwise or continuously.

The molecular weight of the cyclic olefin addition polymer can be controlled by adding a molecular weight regulator such as α-olefin, hydrogen, a cyclic non-conjugated diene or an aromatic vinyl compound, adjusting the amount of the polymerization catalyst, controlling the polymerization temperature, and controlling the polymerization weight. A technique such as adjustment of the conversion rate to coalescence may be appropriately performed. The molecular weight is such that the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using o-dichlorobenzene as a solvent is 5,000 to 1,500,000, preferably 10.0.
It is 00 to 1,000,000. If the weight average molecular weight is less than 5,000, the breaking strength when formed into a film, thin film, sheet or the like will be insufficient, or the solvent resistance and liquid crystal resistance will be poor. On the other hand, when the weight average molecular weight exceeds 1,500,000, the sheet and film molding processability deteriorates, or when a cast film is formed,
Solution viscosity becomes high and handling becomes difficult.

A hydrocarbon solvent can be used as the solvent. For example, cyclohexane, cyclopentane,
A solvent selected from alicyclic hydrocarbon solvents such as methylcyclopentane, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as toluene, benzene, and xylene is used. These may be used alone or in combination of two or more. The solvent / monomer weight ratio is from 1 to 20.
It is done in the range of.

As described above, the polymerization catalyst component and the addition polymerization system used in the production method of the present invention are conventional in the following points, for example, the above nickel bisacetylacetonate and methylaluminoxane. It is essentially different from the one using a catalyst containing (JP-A-4-63807) and the one using a palladium catalyst component. First, the addition polymerization of cyclic olefins having polar groups is possible. The catalyst component of the present invention does not require multi-step synthesis or expensive palladium components. Second, high activity can be obtained by using a very small amount of alkylaluminoxane with respect to nickel atom as compared with the conventional method. Even if the alkylaluminoxane is used in excess of 100 times in terms of aluminum atom per 1 g atom of nickel in terms of aluminum atom as in the conventional method, no effect is obtained. Furthermore, of the alkylaluminoxane used,
By adjusting the ratio to the nickel compound component, the molecular weight distribution of the addition polymer can be adjusted. Thirdly, high polymerization activity is expressed in a hydrocarbon solvent without using a halogenated hydrocarbon solvent or nitromethane. These features include (i) the specific nickel compound, (ii) the Lewis acid compound, and
(Iii) It was achieved for the first time by polymerizing using a polymerization catalyst component containing an alkylaluminoxane.

The polymerization catalyst components may be introduced independently into a reaction vessel in which addition polymerization is carried out, or two or more components may be mixed in advance, and the order of introduction is not particularly limited.

The termination of the polymerization is stopped by water, alcohol, organic acid,
It is performed with a compound selected from carbon dioxide gas and the like. If necessary, the polymerization catalyst residue may be separated and removed from the cyclic olefin addition polymer solution, and a known method may be appropriately used. For example, the cyclic olefin addition polymer solution is hydrochloric acid,
Examples thereof include a method of adding an inorganic acid such as nitric acid and sulfuric acid and an organic acid such as maleic acid and fumaric acid, followed by washing with a solution of water or alcohol, and an adsorption method.

The cyclic olefin addition polymer can be obtained, for example, by putting a cyclic olefin addition polymer solution in an alcohol such as methanol, ethanol or isopropanol, solidifying and drying under reduced pressure. In this process,
Unreacted monomers remaining in the cyclic olefin addition polymer solution are also removed.

When the cyclic olefin addition polymer produced by the method of the present invention is used as a complex with a metal oxide such as silica, alumina or titania, a method of mixing in a solid state using a kneader, Method of removing solvent by mixing cycloolefin addition polymer solution and solvent dispersion of metal oxide, or solution of cycloolefin addition polymer and silicon, aluminum, titanium, tetraalkoxide such as zirconium, and / or alkyltrialkoxide, "Sol-gel method" in which a trialkoxide of a metal selected from aryltrialkoxides or hydrolysis / polycondensation before or after mixing these solutions is performed.
And so on. The ratio of the metal oxide in the composite is used in the range of 5 to 70% by weight, and the particle size of the metal oxide cannot be uniquely determined. When the diameter is less than 100 nm, a transparent composite body is obtained. The transparency of the composite decreases as the ratio of the particle size of the metal oxide in the cycloolefin addition polymer to 100 nm or more increases.

The cyclic olefin addition polymer produced by the method of the present invention contains a crosslinking agent containing a peroxide, sulfur, disulfide, polysulfide compound, dioxime compound, tetrasulfide, silane coupling agent, etc. It is possible to add 0.05 to 5 parts by weight to 100 parts by weight of the olefin addition polymer and convert it into a crosslinked product by heat or the like, or directly convert it into a crosslinked product by light or an electron beam.

The cyclic olefin addition polymer produced by the method of the present invention can be formed into a molded product by a method such as injection molding, blow molding, press molding, extrusion molding, a hydrocarbon solvent or a halogenated hydrocarbon. The cyclic olefin addition polymer can be dissolved in a solvent selected from polar solvents such as a solvent, a ketone, an ether, an ester, an amine, an amide, and a urea, and then subjected to casting and evaporation steps to form a thin film, a film and a sheet. Further, after swelling the cyclic olefin addition polymer with these solvents,
It is also possible to form and process into a film or sheet while evaporating the solvent with an extruder.

The cycloolefin addition polymer produced by the process of the present invention also contains other thermoplastic resins such as
Ring-opening (co) polymer and / or hydride of the (co) polymer, cyclic olefin and ethylene and / or α-
Addition copolymer with olefin, polymethylmethacrylate, polyarylate, polyether sulfone, polyarylene sulfide, polyethylene, polypropylene,
It can also be used as a thermoplastic polymer composition blended with polyester, polyamide, petroleum resin and the like.

The cycloolefin addition polymer produced by the method of the present invention includes 2,6-di-t-butyl-4-methylphenol and 4,4'-thiobis- (6-t-butyl-3-). Methylphenol), 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-t-butylphenol),
2,5-di-t-butylhydroquinone, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-
Addition of a phenolic antioxidant such as hydroxyphenyl) propionate or a hydroquinone antioxidant, and a phosphorus antioxidant such as tris (4-methoxy-3,5-diphenyl) phosphite or tris (nonylphenyl) phosphite, Oxidation stability can be improved.

The cyclic olefin addition polymer produced by the method of the present invention has excellent heat resistance, optical properties, solvent resistance, chemical resistance, liquid crystal resistance and homogeneity, and therefore, liquid crystal display element substrates, electro Chromic display element substrate, various window materials, polarizing film, retardation film, liquid crystal film,
Optical films such as antireflection films, OHP films, substrates for printed circuit boards, etc., optical materials such as optical disks, optical fibers, lenses, prisms, optical filters, light guide plates, optical waveguides, etc., and electronic component materials such as semiconductor encapsulants. It is preferably used for medical devices, various containers, coating agents, adhesives, binders and the like.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The monomer composition ratio (mol%) in the cycloolefin addition polymer is ¹ H-NMR, ¹³ C-NMR, F
It was determined using the T-IR method as appropriate. The polystyrene-equivalent weight average molecular weight (Mw) and the polystyrene-equivalent number average molecular weight (Mn) were measured in o-dichlorobenzene by Waters 150CV gel permeation chromatography, manufactured by Waters, Inc., USA.

Reference Example 1 (Preparation of catalyst component A) 8.2 ml of cyclohexane and n-heptane were placed in a well-dried and nitrogen-substituted polytetrafluoroethylene (Teflon, manufactured by DuPont, USA) container. 10 mmol of nickel 2-ethylhexanoate dissolved in the mixed solvent (mixing ratio 9: 1) was added, and the mixture was cooled in an ice bath. While stirring with a magnetic stirring rod made of polytetrafluoroethylene, 3.0 g (12.7 mmol) of hexafluoroantimonic acid was added dropwise, and the temperature was gradually raised to room temperature. Toluene was added to 20 ml and the insoluble component was filtered off with a glass filter to obtain a solution of catalyst component A. Measure atomic concentration of nickel and antimony in solution by atomic absorption spectrophotometry.
The ratio to 1 was confirmed to be present in solution and provided for polymerization.

On the other hand, the insoluble component separated by filtration was washed with toluene, dried under vacuum, dissolved in methanol, and analyzed by the atomic absorption spectrophotometry. As a result, since the ratio of nickel atom to antimony atom was 1: 2, it was a compound in which 2-ethylhexanoate anion, which is a counter anion of nickel atom, was completely eliminated and replaced with SbF ₆ ^−. Became clear.

Reference Example 2 (Preparation of catalyst component B) 8.2 ml of cyclohexane and n-heptane were placed in a well-dried and nitrogen-substituted polytetrafluoroethylene (Teflon, manufactured by DuPont, USA) container. 10 mmol of nickel 2-ethylhexanoate dissolved in the mixed solvent (mixing ratio 9: 1) was added, and the mixture was cooled in an ice bath. 1.8 g of a diethyl ether solution of tetrafluoroboric acid (54% by weight) was added dropwise while stirring with a polytetrafluoroethylene magnetic stirring bar, and the temperature was gradually raised to room temperature. After adding 10 ml of toluene, the solvent was removed under vacuum, and the residue was dissolved in toluene again and dissolved in toluene.
It was milliliters. The insoluble component was filtered off with a glass filter, and the atomic concentration of nickel in the solution was measured by analysis by an atomic absorption spectrophotometric method and provided for polymerization.

Example 1 170 ml (0.85 mol) of 2-norbornene dissolved in dry toluene to a concentration of 5.0 mol / l was placed in a stainless steel 1 liter reaction vessel that had been thoroughly dried and purged with nitrogen. , 5-triethoxysilyl-2-norbornene (38.5 g, 0.15 mol) and dry toluene (400 ml) were charged, and further, 10 mmol of 1-hexene dissolved in 10 ml of toluene was added and the system was stirred. Was adjusted to 20 ° C. 1.6 ml of methylaluminoxane (manufactured by Toso Akzo Co., Ltd., hereinafter referred to as “MAO”) adjusted to 1.57 mol / liter with aluminum atoms in dry toluene,
1.25 ml of boron trifluoride diethyl ether complex prepared at 1.0 mol / l in dry toluene was added, and 0.25 mmol of the catalyst component A prepared in Reference Example 1 was added in terms of nickel atom. For 100 minutes. It was diluted with 0.5 liter of toluene, 2 g of lactic acid dissolved in 20 ml of isopropyl alcohol was added, and the mixture was washed twice with about 0.5 liter of purified water. Subsequently, it is solidified in about 4 liters of isopropyl alcohol, dried under vacuum at 90 ° C. for 40 hours, and then dried.
5 grams (89%) of cycloolefin addition polymer was obtained. Weight average molecular weight (Mw) is 377,000, number average molecular weight (Mn) is 124,000, Mw / Mn is 3.0.
Met. As a result of ¹ H-NMR analysis, the content of structural units derived from norbornene was 86 mol%, and 5-
The content of structural units derived from triethoxysilyl-2-norbornene was 14 mol%.

Example 2 The same operation as in Example 1 was conducted except that the amount of MAO added was 3.2 ml and the amount of 1-hexene was 8 mmol, and 107 g (90%) of cyclic olefin addition weight was added. Got united. Weight average molecular weight (Mw) is 317,0
00, number average molecular weight (Mn) is 118,000, Mw /
Mn was 2.7, and the molecular weight distribution was narrower than that of Example 1. As a result of ¹ H-NMR analysis, the content of structural units derived from norbornene was 84 mol%, and 5
The content of structural units derived from -triethoxysilyl-2-norbornene was 16 mol%.

Example 3 The same operation as in Example 1 was conducted except that the amount of MAO added was 6.4 ml and the amount of 1-hexene was 5 mmol, and 104 g (98%) of cyclic olefin addition weight was added. Got united. Weight average molecular weight (Mw) is 239,0
00, number average molecular weight (Mn) is 112,000, Mw /
Mn was 2.1, and the molecular weight distribution was narrower as compared with Examples 1 and 2. As a result of ¹ H-NMR analysis, the content of the structural unit derived from norbornene was 85 mol%, and the content of the structural unit derived from 5-triethoxysilyl-2-norbornene was 15 mol%.

Example 4 The same operation as in Example 1 was carried out except that 2.5 mmol of modified-methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd., hereinafter referred to as "MMAO") was added as an aluminum atom instead of MAO. , 98 grams (83%) of addition polymer was obtained. Weight average molecular weight (Mw) is 368,00
0, number average molecular weight (Mn) 132,000, Mw / M
n was 2.8. As a result of ¹ H-NMR analysis,
The content of the structural unit derived from norbornene was 85 mol%, and the content of the structural unit derived from 5-triethoxysilyl-2-norbornene was 15 mol%.

Example 5 In a glass flask thoroughly dried and purged with nitrogen,
Toluene solutions of both MAO and triethylaluminum were mixed so as to have an aluminum atom ratio of 75/25, and stirred for 2 hours while maintaining at 50 ° C. to modify. The same operation as in Example 1 was carried out except that this modified aluminoxane (hereinafter referred to as "modified MAO") was used in place of MAO to obtain 100 g (84%) of an addition polymer. The weight average molecular weight (Mw) is 265,000, the number average molecular weight (Mn) is 109,000, and Mw / Mn is 2.
It was 4. As a result of ¹ H-NMR analysis, the content of structural units derived from norbornene was 85 mol%, and 5
The content of structural units derived from -triethoxysilyl-2-norbornene was 15 mol%.

Comparative Example 1 The same operation as in Example 1 was performed except that nickel 2-ethylhexanoate (catalyst component C) was added in place of the catalyst component A in an amount of 0.25 mmol of nickel atom. as a result,
The addition polymer obtained was 9.0 g (7.6%), which was very small compared with Examples 1 and 2. Weight average molecular weight (Mw) is 206,000, number average molecular weight (Mn) is 95,000, Mw / Mn is 2.2.
Met. As a result of analysis by ¹ H-NMR, the content derived from the structural unit of norbornene was 86 mol%, and 5-
The content of structural units derived from triethoxysilyl-2-norbornene was 14 mol%.

Comparative Examples 2 to 3 Example 1 was repeated except that 0.25 mmol of nickel bisacetylacetonate (catalyst component D) was added in place of the catalyst component A and no boron trifluoride diethyl ether complex was added. The same operation was performed. As shown in Table 1, the amount of added MAO was changed, but neither addition polymer was obtained.

[0061]

[Table 1]

C = nickel 2-ethylhexanoate D = nickel bisacetylacetonate

Example 6 19.8 ml of 2-norbornene dissolved in dry toluene to a concentration of 4.9 mol / liter in a glass-made 200 ml pressure-resistant container which had been sufficiently dried and purged with nitrogen was added in 19.8 ml of dry toluene. 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodeca-3-ene (hereinafter referred to as "cyclic olefin (I)") was charged in an amount of 1.0 ml, dry toluene was added in an amount of 50 ml, and a 0.1 mol / liter dry toluene solution was prepared. 0.25 ml of 5-cyclooctadiene was added, and the system temperature was adjusted to 30 ° C while stirring. In dry toluene, 0.16 ml of MAO adjusted to 1.57 mol / liter with aluminum atoms and 0.2 ml of boron trifluoride diethyl ether complex adjusted to 1.0 mol / l in dry toluene were added, and The catalyst component A prepared in Reference Example 1 was added in an amount of 0.025 mmol in terms of nickel atom to initiate polymerization. 10
After reacting for 0 minutes, dilute with about 30 ml of toluene, add 0.4 g of lactic acid dissolved in 1 ml of isopropyl alcohol, and add 2 ml with 30 ml of purified water.
Washed once. Subsequently, it is solidified in about 1 liter of isopropyl alcohol and dried under vacuum at 90 ° C. for 40 hours,
7.5 grams (76%) of addition polymer was obtained. Weight average molecular weight (Mw) is 824,000 and Mw / Mn is 2.6.
Met. In the FT-IR spectrum of the addition polymer, strong absorption due to stretching vibration of the carbonyl group was 1,732.
It was observed at cm ^-1 . ^{By 1} H-NMR and FT-IR analysis, the content of the structural unit derived from the cyclic olefin (I) in the copolymer was determined to be 1.7 mol%.

Example 7 7.0 g (71%) was obtained in the same manner as in Example 6 except that the catalyst component B was replaced by 0.025 mmol of the catalyst component B in terms of nickel atom. An addition polymer of Weight average molecular weight (Mw) is 769,000, Mw /
Mn was 2.5. ¹ H-NMR and FT-IR
Analysis revealed that the cyclic olefin (I) in the copolymer
The content of the structural unit derived from was determined to be 1.6 mol%.

Comparative Examples 4 to 7 Using the catalyst components shown in Table 2, the same operation as in Example 6 was performed. As a result, in Comparative Examples 4 and 5 in which the Lewis acid was not used, the polymerization did not proceed at all. When nickel 2-ethylhexanoate is used in place of the catalyst component A, an addition polymer cannot be obtained even if MAO is used in an amount of 10 times the amount of aluminum atom with respect to nickel atom.
Polymerization finally proceeded using 100 times amount.

Examples 8-9 Instead of the cyclic olefin (I), itaconic anhydride / cyclopentadiene adduct (hereinafter referred to as "cyclic olefin (I
I) ”) was added, and the same operation as in Examples 6 and 7 was performed to obtain an addition polymer (Table 2). In the FT-IR spectrum of the addition polymer, strong absorption due to stretching vibration of the carbonyl group was 1,732 cm.
^It was observed at ^-1 .

Comparative Examples 8 to 11 Using the catalyst components shown in Table 2, the same operation as in Example 8 was performed. As a result, in Comparative Example 8 in which the catalyst component A was used and no Lewis acid was used, although a small amount of addition polymer was obtained, absorption based on stretching vibration of the carbonyl group was observed in the FT-IR spectrum. There wasn't. When nickel bisacetylacetonate was used instead of catalyst component A and no Lewis acid was used, only traces of addition polymer were obtained. When nickel 2-ethylhexanoate is used and a Lewis acid is used, MAO is converted into aluminum atoms by 1 with respect to nickel atoms.
Although the polymerization proceeded with the use of 00 times, no absorption based on the stretching vibration of the carbonyl group was observed in the FT-IR spectrum of the obtained addition polymer.

[0068]

[Table 2]

*: Cyclic olefin (I) or (I
I) Molar content C = nickel 2-ethylhexanoate D = nickel bisacetylacetonate

[0070]

According to the method for producing a cycloolefin addition polymer of the present invention, an easily available catalyst component is used, and
An addition polymer of a cyclic olefin having a polar group can be obtained without using a large amount of aluminoxane.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Noboru Oshima             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4J028 AA01A AB00A AC48A BA00A                       BA02B BB00A BB01B BC13B                       BC25B CA14B CA17B EB26                       EC01 EC02 GA01 GA06                 4J100 AR11P AR11Q BA20P BA71P                       BA77P BB01P BB18P BC43Q                       BC44Q BC53P BC55P CA04                       FA09

Claims (7)

[Claims] 1. A cyclic olefin containing at least one polar group-containing cyclic olefin represented by the following formula (1):
(I) a nickel compound represented by the following formula (2), (i
A method for producing a cyclic olefin addition polymer, which comprises performing addition polymerization in a hydrocarbon solvent using a polymerization catalyst component containing i) a Lewis acid compound and (iii) an alkylaluminoxane. [Chemical 1] [In the formula (1), at least one of A ¹ , A ² , A ³ , and A ⁴ represents a polar group represented by — (CR ¹ R ² ) _q X; It is a group selected from an atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group, a cycloalkyl group and an aryl group. Here, X is ^{-C (O) R 3, -OC} (O)
R ⁴ , C (O) OR ⁵ or —SiY ¹ Y ² Y ³ is represented by R ¹
To R ⁵ are the same or different and each is a hydrogen atom or a carbon number of 1 to 10.
Represents a hydrocarbon group or a halogenated hydrocarbon group of Y,
^{1 to} Y ³ are the same or different and each is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group,
It represents an alkoxy group or an aryloxy group, which may be bonded to each other to form a 5- to 8-membered ring. A ¹ and A ² or A
¹ and A ³ may be ring-closed to form a cyclic ketone, lactone or acid anhydride. p and q represent the integer of 0-3. _{] [L n NiX] [A} ] ...... (2) [ in the formula (2), L is a ligand or solvent neutral molecules, n is 0 to 3, X is β- diketonate It is an anion or a carboxylic acid anion having a linear or branched alkyl group having 1 to 12 carbon atoms, and A is a non-coordinating or weakly coordinating anion. ] 2. In addition to the polar group-containing cyclic olefin,
Further, a non-polar cyclic olefin represented by the following formula (3)
The cyclic olefin according to claim 1, which copolymerizes with one or more kinds.
Method for producing addition polymer. [Chemical 2] [In the formula (3), B¹, B², B³, B^FourAre the same or different
A hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms
Group, halogenated alkyl group, aralkyl group, cycloalkyl group
Rualkyl group, aryl group, B¹And B²Archide formed by
Group or B ¹And B³An alkylene group combining
Chloroalkylene group, alkenylene group, cycloalkenylene
Is an aryl group or an arylene group, and r represents an integer of 0 to 3.
You ] 3. The non-coordinating or weakly coordinating anion constituting the component (i) is SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ ,
CF ₃ SO ₃ ⁻ and CF ₃ COO ⁻ , wherein the (ii) Lewis acid compound is boron trifluoride,
Aluminum trifluoride, titanium tetrachloride, antimony pentafluoride, tris (pentafluorophenyl) boron, and tris (3,5-bistrifluoromethylphenyl)
The method for producing a cycloolefin addition polymer according to claim 1 or 2, which is selected from boron. 4. A cyclic olefin containing at least one polar group-containing cyclic olefin represented by the above formula (1),
(I) a strong Bronsted acid-modified compound of a β-diketonate of nickel, or a compound of a carboxylate having a linear or branched alkyl group having 1 to 12 carbon atoms of nickel, (ii) a Lewis acid compound, and,
(Iii) A method for producing a cyclic olefin addition polymer, which comprises subjecting a polymerization catalyst component containing an alkylaluminoxane to addition polymerization in a hydrocarbon solvent. 5. In addition to the polar group-containing cyclic olefin,
Furthermore, the manufacturing method of the cycloolefin addition polymer of Claim 4 which copolymerizes 1 or more types of nonpolar cyclic olefins represented by said Formula (3). 6. The strong Bronsted acid compound (i) is hexafluoroantimonic acid, hexafluorophosphoric acid,
Selected from tetrafluoroboric acid, trifluoromethanesulfonic acid, and trifluoroacetic acid,
The (ii) Lewis acid compound is boron trifluoride, aluminum trifluoride, titanium tetrachloride, antimony pentafluoride,
The method for producing a cycloolefin addition polymer according to claim 4 or 5, which is selected from tris (pentafluorophenyl) boron and tris (3,5-bistrifluoromethylphenyl) boron. 7. The cyclic according to claim 1, wherein the (iii) alkylaluminoxane is used in a range of 1 to 50 times in terms of aluminum atom per nickel atom constituting the component (ii). Process for producing olefin addition polymer.