JPH05132523A - Production of cycloolefin polymer - Google Patents

Abstract

PURPOSE:To markedly improve the activity of a polymerization catalyst, to develop a process which can dispense with any deashing step and to reduce equipment cost and energy cost by simply removing impurities such as a cyclic olefin oxide which cannot be removed by distillation from cycloolefin monomers in the production of a cycloolefin homopolymer or a cycloolefin/alpha-olefin copolymer. CONSTITUTION:A cycloolefin is purified by contact with an inorganic substance such as aluminum, activated aluminum, silica, active carbon, quick lime, aluminum silicate, diatomaceous earth, activated clay, kaolinite or zeolite to remove impurities such as a cyclic olefin oxide, a polymerization inhibitor and an antioxidant. The purified cycloolefin is homopolymerized or copolymerized with an alpha-olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cyclic olefin polymer such as a cyclic olefin homopolymer or a cyclic olefin / α-olefin copolymer, more specifically, a highly purified cyclic olefin as a raw material. The present invention relates to a method for producing a cyclic olefin polymer used.

[0002]

2. Description of the Related Art Conventionally, various techniques have been reported as a method for producing a cyclic olefin polymer (JP-A-61).
-271308, JP-A-61-221206, JP-A-64-106, JP-A-2-173112). However, in the production of a cyclic olefin polymer, unpurified cyclic olefin is conventionally used as a monomer, so that there is a problem that the polymerization activity of the catalyst is lowered. That is, in the unpurified cyclic olefin which is commercially available or supplied as an industrial raw material, water, an epoxy compound, a ketone compound, a peroxide, a t-butylcatechol as a polymerization inhibitor,
Contains impurities such as antioxidants. For example, norbornene contains epoxynorbornane, 2-oxonorbornane, 2-aminonorbornane and the like, and cyclohexene contains cyclohexanone peroxide, cyclohexylamine and the like. It is considered that these impurities hinder the polymerization activity of the catalyst. Therefore, in the production of cyclic olefin polymer,
It is desirable to use highly purified cyclic olefin monomers.

[0003]

Distillation is generally known as a method for purifying cyclic olefins, but the distillation has the following problems 1 to 4. 1. As a result of research, the present inventors have found that among the impurities contained in commercial or industrial cyclic olefins, cyclic olefin oxides particularly inhibit the polymerization activity of the catalyst. However, this cyclic olefin oxide is difficult to separate by distillation. For example, commercially available industrial norbornene contains impurities such as epoxy norbornane at 120%.
The content is about 300 ppm and the phenolic antioxidant is about 1000 ppm. Here, the phenolic antioxidant can be separated by distillation, but the epoxy norbornane is difficult to separate by distillation. 2. According to the study by the present inventors, norbornene from which the antioxidant is removed by distillation gradually undergoes an oxidation reaction to form epoxynorbornane, which further inhibits the polymerization activity of the catalyst. As described in 3.1, the purification of cyclic olefins by the distillation method involves a large amount of residual epoxynorbornane, which lowers the polymerization activity of the catalyst, and thus requires a large amount of catalyst during the production of the polymer. Therefore, a large amount of metal (IVB to VB group transition metal, aluminum, etc.) remains in the product after polymerization,
Since it causes deterioration and coloring, it is necessary to perform deashing after the polymerization, and it is difficult to use a deashless process. 4. The distillation method has high equipment cost and energy cost.

The present invention has been made in view of the above circumstances. It is possible to easily remove impurities such as cyclic olefin oxides, which cannot be removed by a distillation method, to significantly improve the polymerization activity of the catalyst. An object of the present invention is to provide a method for producing a cyclic olefin-based polymer, which can be made into an ash process and can reduce equipment costs and energy costs.

[Means for Solving the Problems]

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, in obtaining a cyclic olefin polymer by homopolymerizing a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin. It was found that the above object can be effectively achieved by using a cyclic olefin that has been subjected to a contact treatment with an inorganic substance such as alumina or silica gel, and has completed the present invention. Therefore, the present invention provides a method for producing a cyclic olefin-based polymer, which comprises homopolymerizing a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin by using the cyclic olefin that has been subjected to a contact treatment with an inorganic substance. ..

A method for purifying a cyclic olefin by treating the cyclic olefin with silica gel, alumina or the like is known (East German Patent No. 213667). However, this publication does not show anything about producing a cyclic olefin polymer using a purified cyclic olefin,
It is not a suggestion of the invention.

The present invention will be described in more detail below.
In the method for producing a cyclic olefin polymer of the present invention, a cyclic olefin monomer that has been subjected to a contact treatment with an inorganic substance is used as a raw material. Here, the inorganic substance is not particularly limited, but alumina, activated alumina, silica, activated carbon, quick lime, aluminum silicate, diatomaceous earth, activated clay,
Examples include kaolinite and zeolite. These inorganic substances may be used alone or in combination of two or more. Among these inorganic substances, alumina, activated alumina and the like are particularly preferable. The properties and the like of these inorganic substances are not particularly limited. The contact treatment conditions are usually a treatment temperature of about 0 to 70 ° C. and a treatment amount of 0.001 to 10
It is about 0 [liter / h · Kg · inorganic substance]. The contact treatment is performed, for example, by filling the column with the above-mentioned inorganic substance and passing a cyclic olefin through the column. In this case, it is preferable to adopt a continuous processing method.

Before the treatment with the above-mentioned inorganic substance, the cyclic olefin monomer is degassed under reduced pressure, or a dry inert gas is bubbled through the cyclic olefin monomer so that the water content in the cyclic olefin monomer is increased. Is effective. The standard of water removal in this case may be appropriately selected depending on the situation, but normally, the water content may be set to 5 ppm or less by vacuum deaeration or aeration bubbling. Further, before the treatment with the above-mentioned inorganic substance, the cyclic olefin monomer is subjected to a contact treatment with an organoaluminum compound, and thereafter, (a) is treated with the above-mentioned inorganic substance, or
(B) Hydrolysis may be carried out, followed by treatment with the above-mentioned inorganic substance.

Here, as the organoaluminum compound, various ones can be mentioned, but a typical one is represented by the following general formula: AlR ^a _i R ^b _j R ^c _{3- (i + j)} (wherein R ^a , R ^b And R ^c each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group or a halogen atom, i and j each represent an integer of 0 to 3, and i
+ J is an integer of 0-3. ). Specific examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trioctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum hydride, diisobutyl aluminum hydride, and diethyl aluminum ethoxide. Etc. Among these compounds, an organoaluminum compound containing no halogen atom is preferable, and an organoaluminum compound containing hydrogen, an ethyl group and / or an isobutyl group, for example, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum hydride and the like is particularly preferable. .. Further, it is also possible to use aluminoxane which is one component of the catalyst described later.

Prior to the contact treatment with the organoaluminum compound, it is preferable to quantify impurities such as a cyclic olefin containing a hetero atom in the cyclic olefin by gas chromatography or the like. Based on the result, the organoaluminum compound to be brought into contact with 1 mol of impurities can be appropriately added within the range of 1 to 1000 mol, but in many cases 1 to 10 mol is sufficient. However, even if an excessive amount of the organoaluminum compound is added to the reaction system, there is no particular problem. The treatment temperature is 0 to 100 ° C, preferably 20 to 40 ° C. The treatment time is 5 minutes to 10 hours, but 10 minutes to 1 hour is often sufficient. After the contact treatment with the organoaluminum compound,
(A) Treatment with the above inorganic substance, or (b) Treatment with the above inorganic substance after hydrolysis. The treatment conditions and the like with the inorganic substance are the same as those described above.

When the treatment with the above-mentioned inorganic substance is carried out after hydrolysis, the organoaluminum compound used is also hydrolyzed to produce aluminum hydroxide.
After separating the organic phase composed of the cyclic olefin-based monomer and the aqueous phase containing aluminum hydroxide or the like, it is preferable to perform the treatment with the above-mentioned inorganic substance. By performing the treatment with the inorganic substance after hydrolysis, the hydrolyzate of the reaction product of the organoaluminum compound and the impurities in the olefinic monomer can be adsorbed and removed by the inorganic substance. Impurities such as cyclic olefins containing a hetero atom can be effectively removed by using the contact treatment with the organoaluminum compound and the contact treatment with an inorganic substance. In this case, it is preferable that the amount of impurities such as a cycloolefin containing a hetero atom is 100 ppm or less.

Impurities can be removed by performing (c) direct distillation treatment or (d) hydrolysis and distillation treatment after the contact treatment with the organoaluminum compound. In this case, distillation equipment is used. Will be required and the energy cost will be high. For example, in the case of directly distilling after contacting with the organoaluminum compound, the distillation operation may be carried out under the condition that the reaction product of the organoaluminum compound and the impurities is separated from the cyclic olefin monomer. Although the distillation conditions can be arbitrarily selected, distillation at a low temperature is more preferable, and vacuum distillation is more preferable than atmospheric pressure. The distillation temperature is 0 to 100 ° C, preferably 0 to 50 ° C. On the other hand, in the case of distillation after hydrolysis, distillation may be performed so that the hydrolyzate of the reaction product of the organoaluminum compound and the impurities in the cyclic olefin monomer is separated from the cyclic olefin monomer. Since the used organic aluminum compound is also hydrolyzed to produce aluminum hydroxide, it is preferable to distill after separating the organic phase composed of the cyclic olefin monomer and the aqueous phase containing aluminum hydroxide and the like.

In the method of the present invention, the cyclic olefin homopolymerized or the cyclic olefin and α-olefin are copolymerized by using the cyclic olefin which has been subjected to the contact treatment with the above-mentioned inorganic substance or the like. In this case, the cyclic olefin that has been subjected to the contact treatment with the inorganic substance is preferably used in a state where the content of the epoxynornbornane is 100 ppm or less, but if the cyclic olefin after the contact treatment is left as it is, the epoxynornbornane is not used. Nan increases again. Therefore, it is particularly preferable that the contact treatment is carried out before the polymerization apparatus and the cyclic olefin after the contact treatment is continuously supplied to the polymerization step.

The cyclic olefin used in the present invention includes
For example, the following can be mentioned. Monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene; substituted monocyclic cyclic olefins such as 3-methylcyclopentene and 3-methylcyclohexene; norbornene, 1,2-dihydrodicyclopentadiene, 1,4,5 , 8-Dimethano-
Polycyclic olefins such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene;

1-methylnorbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 5-chloronorbornene, 5- Fluoronorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 7-methylnorbornene, 5,6
-Dimethylnorbornene, 5,5-dichloronorbornene, 5,5,6-trimethylnorbornene, 5,5,6
-Trifluoro-6-trifluoromethylnorbornene, 2-methyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-
Substituted polycyclic olefins such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene Among these, polycyclic olefins, especially norbornene or a derivative thereof, are particularly preferable.

As the α-olefin, those having 2 to 25 carbon atoms such as ethylene, propylene, butene-1, 4-methylpentene-1 can be preferably used. Of these, ethylene is particularly preferable.

Further, in the present invention, a copolymerizable unsaturated monomer component other than the above may be used if necessary. As such an unsaturated monomer which may be optionally copolymerized, specifically, an α-olefin which has not been used before, a cyclic olefin which has not been used before, and a dicycloolefin. Examples thereof include cyclic dienes such as pentadiene and norbornadiene, and chain dienes such as butadiene, isoprene, and 1,5-hexadiene.

The polymerization catalyst used in the method of the present invention is not particularly limited, but the following vanadium (V) catalyst, transition metal / aluminoxane catalyst, transition metal / cation
Anion / (organoaluminum compound) -based catalysts and other catalysts for ring-opening polymerization by combining molybdenum, tungsten and the like with an organoaluminum compound are preferable. Vanadium-based catalyst A catalyst composed of a vanadium compound and an organoaluminum compound. Here, as the vanadium compound, bis (cyclopentadienyl) vanadium dichloride, bis (cyclopentadienyl) vanadium monochloride, vanadyl trichloride, vanadyl diethoxide, vanadyl diethoxide, vanadyl isobutoxide dichloride , Triethoxyvanadyl, vanadyl tribromide, tri (n-butoxy) vanadyl and the like.

Further, as the organoaluminum compound,
A compound having at least one Al-carbon bond in the molecule can be used. Examples of such compounds include those shown in (I) to (II) below. (I) the general formula _{^{R d m Al (OR e)}} n H p X q ( wherein, R ^d and R ^e are each carbon atoms usually 1-1
5, preferably 1-4 hydrocarbon groups, which may be the same or different from each other. X is a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0.
A number of ≦ q <3, m + n + p + q = 3 a is) an organoaluminum compound represented by (II) the general formula M ^a AlR ^d ₄ (where M ^a is Li, Na, a K, R ^d is the Alkyl) and a complex alkyl compound of group I and aluminum

[0020] As the organoaluminum compounds belonging to the (I) are, for example, the general formula _{^{R d m Al (OR e)}} 3-m ( wherein R ^d and R ^e are as defined above, m is preferably 1.5 ≦ m ≦ 3.) General formula R ^d _m AlX _3-m (where R ^d and X are the same as above, and m is preferably 0 <m <3.) General The formula R ^d _m AlH _3-m (where R ^d is as defined above, and m is preferably 2 ≦
m <3. ) The general formula R ^d _m Al (OR ^e ) _n X _q (where R ^d , R ^e and X are the same as above, and 0 <m ≦
3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the aluminum compound belonging to (I) include trialkyl aluminum such as triethyl aluminum, tributyl aluminum and triisopropyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; ethyl aluminum sesqui Alkyl aluminum sesquialkoxides such as ethoxide and butyl aluminum sesquibutoxide; R ^d _2.5 A
Partially alkoxylated alkylaluminum having an average composition represented by l (OR ^e ) _0.5, etc .; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride Alkyl aluminum sesquihalide such as ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride etc. Dialkyl aluminum hydride, ethyl aluminum dihydride, propyl Partially hydrogenated alkylaluminums such as alkylaluminium dihydrides such as aluminum dihydride; partially aluminumized and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide are exemplified. can do.

The compound similar to the compound (I) may be an organoaluminum compound in which two or more aluminum atoms are bound to each other through an oxygen atom or a nitrogen atom. Such compounds include, for _{example, (C 2 H 5) 2} AlOAl (C 2 H 5) 2 (C 4 H 9) 2 AlOAl (C 4 H 9) can be exemplified _2. Examples of the compound belonging to (II) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₆ H ₁₃ ) _{4 and the} like. Among the above compounds, it is particularly preferable to use alkyl aluminum halide, alkyl aluminum dihalide or a mixture thereof.

Transition metal / aluminoxane catalyst A catalyst comprising (a) a transition metal compound and (b) an aluminoxane. The transition metal compound (a) which is a catalyst constituent component is a compound of a transition metal selected from the group consisting of IVB group, VB group, VIB group, VIIB group and VIII group of the periodic table, and examples thereof include titanium and zirconium. , Hafnium, vanadium, chromium, manganese, nickel, palladium,
A compound such as platinum can be exemplified. Among these transition metal compounds, titanium, zirconium, nickel,
Palladium compounds are preferable, and zirconium and nickel compounds are particularly preferable because they have high activity. The transition metal compound (a) is preferably a compound having a hydrocarbon group or a compound having a hydrocarbon group and a halogen atom. Among them, a transition metal compound having at least one, especially two hydrocarbon groups and having at least one, especially two halogen atoms is preferable. As the hydrocarbon group, specifically, a methyl group, an ethyl group, an n-butyl group,
Cycloalkyl groups such as sec-butyl group, tert-butyl group, isobutyl group, neopentyl group and other alkyl groups, isopropenyl group, 1-butynyl group and other alkenyl groups, cyclopentadienyl group, methylcyclopentadienyl group, etc. Examples thereof include an aralkyl group such as an enyl group, a penzyl group, a neophyl group and the like, and a cycloalkadienyl group is particularly preferable, and a cyclopentadienyl group is particularly preferable. Further, as the halogen atom, specifically, fluorine,
Examples are chlorine, bromine and iodine atoms.

Specific examples of the transition metal compound (a) include bis (cyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) diisopropyl titanium, and bis (methylcyclo). Pentadienyl) dimethyl titanium, bis (cyclopentadienyl) methyl titanium monochloride, bis (cyclopentadienyl) ethyl titanium monochloride,
Bis (cyclopentadienyl) isopropyl titanium monochloride, bis (cyclopentadienyl) methyl titanium monobromide, bis (cyclopentadienyl) methyl titanium monoiodide, bis (cyclopentadienyl) titanium difluoride, bis ( Titanium compounds such as cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (methylcyclopentadienyl) titanium diiodide,

Bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (methylcyclopentadienyl) diisopropylzirconium, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentapenta Dienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) methyl zirconium monobromide, bis (cyclopentadienyl) methyl zirconium monoiodide, bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) )
Zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium diiodeide, etc. Zirconium compound,

Hafnium compounds such as bis (cyclopentadienyl) dimethylhafnium, bis (cyclopentadienyl) methylhafnium monochloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) vanadium dichloride, bis Vanadium compounds such as (cyclopentadienyl) vanadium monochloride,

Tetramethylchromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium , Tricarbonyltris (triphenylphosphonate) chromium, tris (allyl)
Chromium compounds such as chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate),

Tricarbonyl (cyclopentadienyl)
Manganese compounds such as manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate),

Dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), chlorohydridobis (tricyclohexylphosphine) nickel, chloro (phenyl) bis ( Triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,2′-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, Bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) nickel, (cyclopentadienyl) (cyclooctadiene) nickel tetrafluoroborate, bis (cycloocta Diene) nickel, nickel bisacetylacetonate, allyl nickel chloride, tetrakis (triphenylphosphine) nickel, nickel chloride, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) CH = P (C ₆ H ₅ ). ₂ } {P
(C ₆ H ₅ ) ₃ }, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) C (SO ₃ Na) = P (C ₆ H ₅ ) ₂ } {P (C ₆
H ₅ ) ₃ } and other nickel compounds,

Dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, bis (t-butylisocyanide) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) ) Palladium, dichloro (1,5-cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl)
Palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonato) (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, etc. Palladium compounds and the like can be mentioned.

Specific examples of the aluminoxane (b) as a catalyst constituent include the following general formula:

[Chemical 1] Or the following general formula

[Chemical 2] (In both formulas, R ^f represents a hydrocarbon group, and r represents an integer of 2 or more). In the aluminoxane, R ^f is a hydrocarbon group such as methyl group, ethyl group, propyl group and butyl group. A methyl group and an ethyl group are preferable, and a methyl group is particularly preferable. m is an integer of 2 or more, preferably an integer of 5 or more, particularly preferably an integer of 10 to 100.

Transition metal / cation / anion / (organoaluminum compound) -based catalyst A catalyst containing the following compounds (A) and (B) as main components or the following compounds (A), (B) and (C) as main components It is a catalyst that does. (A) Transition metal compound (B) Compound which reacts with transition metal compound to form an ionic complex (C) Organoaluminum compound

Here, as the transition metal compound (A),
A transition metal compound containing a transition metal belonging to the IVB group, VB group, VIB group, VIIB group, and VIII group of the periodic table can be used. Specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable as the above transition metal, and among them, zirconium, hafnium, titanium, nickel and palladium are preferable.

Examples of such a transition metal compound include various compounds. In particular, compounds containing a transition metal of IVB group or VIII group, especially a transition metal selected from IVB group of the periodic table, that is, titanium (Ti ), Zirconium (Zr) or hafnium (Hf) is preferably used, and in particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or a compound thereof A derivative, a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 d R 2 e ... (II) (Cp-A f -Cp) M 1 R 1 d R 2 e ... (III) M ¹ R ¹ _g R ² _h R ³ _i R ⁴ _j (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr.
Or Hf atom, Cp is a cyclopentadienyl group,
A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom,
Oxygen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, acyloxy group having 1 to 20 carbon atoms, Allyl group,
Shows a σ-bonding ligand such as a substituted allyl group and a substituent containing a silicon atom, a chelating ligand such as an acetylacetonate group and a substituted acetylacetonate group, or a ligand such as a Lewis base, A indicates crosslinking by covalent bond. a, b, and c are each an integer of 0 to 3, and d and e are each 0.
2 is an integer, f is an integer of 0 to 6, and g, h, i and j are integers of 0 to 4, respectively. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. Formula (II) and (II
In the formula (I), two Cp's may be the same or different from each other. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. Specific examples of R ^{1 to} R ⁴ include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group, and iso as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, A phenyl group as an alkylaryl group or an arylalkyl group,
Tolyl group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: dimethyl ether, diethyl ether, tetrahydrofuran as Lewis base , Ethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N,
Amines such as N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline, phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene, 1-pentene, isoprene, pentadiene as chain unsaturated hydrocarbons, 1-Hexene and derivatives thereof; examples of cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslinks by the covalent bond of A include methylene crosslinks, dimethylmethylene crosslinks, ethylene crosslinks, 1,1′-cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compound of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydride zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethyl zirconium, dimethylsilylene bis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclopenta) Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,3)
5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (indenyl) dichlorozirconium

Other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III), the effect is not impaired. Examples of such compounds include compounds of the formula (IV), for example, tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium,
Tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,
5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), or these zirconiums with hafnium,
Examples thereof include a zirconium compound, a hafnium compound, and a titanium compound having one or more kinds of an alkyl group, an alkoxy group and a halogen atom, such as a compound substituted with titanium.

The transition metal compound containing a Group VIII transition metal is not particularly limited, and specific examples of the chromium compound include, for example, tetramethyl chromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl). ) Chromium, hydridotricarbonyl (cyclopentadienyl)
Chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl)
Examples thereof include chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like.

Specific examples of the manganese compound include tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like.

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), and chlorohydridobis (tricyclohexyl). Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allyl nickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel chloride, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) CH = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ }, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) C (SO ₃ Na) = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ } and the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanide) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
Examples include (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, and the like.

Any compound can be used as the compound (B) as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound composed of a bound anion, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element can be preferably used. The compound consisting of such a cation and an anion in which a plurality of groups are bound to an element is represented by the following formula (V) or (VI)
The compound represented by can be preferably used. ([L ¹ −R ⁷ ] ^{k +} ) _p ([M ³ Z ¹ Z ² … Z ⁿ ] ^(nm)- ) _q … (V) ([L ² ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² …. Z ⁿ ] ^(nm)- ) _q (VI) (where L ² is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R ¹¹ M ⁶ )

In the formulas ((V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Elements selected from the VA group, M ⁵ and M ^6, are IIIB group, IVB group, VB group, VIB group, VIIB group, VIII of the periodic table, respectively.
Element selected from group, IA group, IB group, IIA group, IIB group and VIIA group, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 respectively.
To C20 aryloxy group, C1 to C20 alkyl group, C6 to C20 aryl group, alkylaryl group, arylalkyl group, C1 to C20 halogen-substituted hydrocarbon group, C1 to C20 2 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms
20 represents an aryl group, an alkylaryl group or an arylalkyl group, R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is a C 1-20 group. An alkyl group, an aryl group, an alkylaryl group or an arylalkyl group is shown. R ¹¹ is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M ³ , M
An integer of 1 to 7 with a valence of ⁴ , n is an integer of 2 to 8, k is an integer of 1 to 7 with an ionic valence of [L ¹ -R ⁷ ], [L ² ],
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As and Sb.
As specific examples of M ⁵ , Li, Na, Ag, Cu, B
Specific examples of M ⁶ , such as r, I, and I ₃ , include Mn, Fe, and C.
o, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; and a carbon number of 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group having an alkyl group having 1 to 20 carbon atoms,
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; aryl group having 6 to 20 carbon atoms,
As an alkylaryl group or an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br as halogen atoms
I: Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
Examples are the same as those listed above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 5. (V), (V
Among the compounds of formula I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following can be used particularly preferably. Compound of formula (V) triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenylphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ，

Triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) borate (tetraethylammonium), tetra (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetra (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetra (pentafluoro) Phenyl) methyl diphenylammonium borate, tetra (pentafluorophenyl) methyl triphenylammonium borate Dimethyl diphenyl (pentafluorophenyl) borate Phenylammonium, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) ) Dimethyl borate (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium),

Pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N- Benzylpyridinium), tetra (pentafluorophenyl) boric acid (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, tetra (3,5)
-Ditrifluoromethylphenyl) dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of Formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (1,1'-Dimethylferrocenium, tetra (pentafluorophenyl)
Decamethylferrocenium borate, Acetylferrocenium tetra (pentafluorophenyl) borate, Formylferrocenium tetra (pentafluorophenyl) borate,
Cyanoferrocenium tetra (pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, sodium tetra (pentafluorophenyl) borate, tetra ( Pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenic acid Silver, silver hexafluoroantimonate,

Compounds other than those represented by formulas (V) and (VI), such as tri (pentafluorophenyl) boron, tri (3,3)
5-di (trifluoromethyl) phenyl) boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include those represented by the following general formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms, Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) Specific examples of the compound of formula (VII) include trimethylaluminum, triethylaluminum, and triisobutyl. Examples thereof include aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum sesquichloride.

[0055]

[Chemical 3] (R ¹² represents the same as in formula (VII). S represents the degree of polymerization, and is usually 3 to 50.) A chain aluminoxane.

[0056]

[Chemical 4] (R ¹² has the same meaning as in formula (VII), s represents the degree of polymerization, and the preferred number of repeating units is 3 to 50.) A cyclic alkylaluminoxane having a repeating unit. Among the compounds of formulas (VII) to (IX),
The compound of the formula (VII) is preferable, and the compound of the formula (VII) having r = 3 is preferable, and trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum is particularly preferable.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

The use conditions of each of the above components are not limited,
The ratio (molar ratio) of component (A): component (B) is 1: 0.01.
˜1: 100, especially 1: 0.5 to 1:10, especially 1:
It is preferably 1 to 1: 5. The operating temperature is −
The temperature is preferably in the range of 100 to 250 ° C., and the pressure,
The time can be set arbitrarily. The amount of the component (C) used is usually 0 to 2,000 with respect to 1 mol of the component (A).
It is 0 mol, preferably 5 to 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the polymer, which is not preferable. There is no limitation on the use mode of the catalyst. For example, the components (A) and (B) may be contacted in advance, or the contact product may be separated and washed before use. May be used. Further, the component (C) may be used by being brought into contact with the contact product of the component (A), the component (B) or the component (A) and the component (B) in advance. Contact
It may be contacted in advance or in the polymerization system. Further, the catalyst component can be added to the monomer or the polymerization solvent in advance, or can be added to the polymerization system.

Polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250 ° C, particularly preferably -50 to 200 ° C. The ratio of the catalyst to the reaction raw material is 1 to 1 of raw material monomer / component (A) (molar ratio) or raw material monomer / component (B) (molar ratio).
It is preferably 0 ⁹ , and particularly preferably 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to
100 Kg / cm ² G, preferably normal pressure to 50 Kg / c
m ² G. The method for controlling the molecular weight of the polymer can be based on the amount of each catalyst component used, the selection of the polymerization temperature, and further the polymerization reaction in the presence of hydrogen.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, pentane and hexane,
Aliphatic hydrocarbons such as heptane and octane, halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent.

According to the production method of the present invention, a cyclic olefin
When the α-olefin copolymer is produced, the ratio of the structural unit derived from the α-olefin to the structural unit derived from the cyclic olefin is 0.1: 99.9 to 99.9: 0.
In 1, it is possible to obtain a copolymer in which each structural unit is randomly arranged and which is substantially linear. It can be confirmed that the copolymer is substantially linear by completely dissolving the copolymer in decalin at 135 ° C. In this case, it is usually possible to obtain a copolymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in decalin at 135 ° C. Further, the cyclic olefin-based copolymer obtained by the production method of the present invention is used in all fields, and is particularly useful as an optical material, a packaging material, and a thermoplastic elastomer. Although the production method of the present invention has been specifically described above, the method of the present invention is not limited thereto and can be applied to all polymerizations using a cyclic olefin. Therefore, as the cyclic olefin homopolymer, it is possible to obtain a ring-opening polymer, a vinylene type polymer or a copolymer composed of these two structural units.

[0062]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, physical properties were measured as follows. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Norbornene content From the ratio of the sum of the peaks due to ¹³ C-NMR around 30 ppm due to ethylene and the peaks due to methylene at the 5 and 6 positions of norbornene and the peak due to methylene groups at 7 position of norbornene near 32.5 ppm. I asked.

Example 1 (1) Purification of norbornene 70 g of crude norbornene containing 145 ppm of epoxynorbornane as an impurity and 1000 ppm of 2,6-di (t-butyl) -4-oleylphenol as an antioxidant was mixed with 30 g of dry toluene. In addition, a 70 wt% toluene solution of norbornene was prepared. This norbornene solution was passed under reduced pressure at 300 ° C. for 8 hours through a column filled with 300 g of calcined alumina at 20 ml / min. As a result, the content of epoxy norbornane in norbornene was 0 p by gas chromatography analysis.
It became pm and it was confirmed that the epoxy norbornane was completely removed.

(2) Copolymerization of ethylene-norbornene Dry toluene 400 m in a 1 liter autoclave.
1, triisobutylaluminum 0.6 mmol, bis (cyclopentadienyl) dichlorozirconium 0.0
01 mmol and 0.002 mmol of dimethylanilinium tetra (pentafluorophenyl) borate were charged, and 400 mmol of the purified norbornene obtained in the above (1) was charged therein, and the temperature was adjusted to 90 ° C. and ethylene pressure of 6 kg / cm ² . After polymerization for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate a copolymer. When this was filtered and dried, 46 g of a copolymer was obtained. Polymerization activity is 50
4 Kg / g · Zr, 2.8 Kg / g Al, norbornene content of the obtained copolymer is 10 mol%, intrinsic viscosity [η]
Was 0.81 dl / g.

Example 2 In Example 1 (2), except that the amount of triisobutylaluminum compounded was 0.2 mmol and 0.001 mmol of zirconium tetrachloride was used instead of bis (cyclopentadienyl) dichlorozirconium. Example 1
Copolymerization of ethylene and norbornene was carried out in the same manner as in. As a result, 42 g of a copolymer was obtained. The polymerization activity was 460 Kg / g · Zr and 7.8 Kg / gAl, the norbornene content of the obtained copolymer was 10 mol%, and the intrinsic viscosity was 0.82 dl / g.

Comparative Example 1 Copolymerization of ethylene and norbornene was carried out in the same manner as in Example 1 except that the crude norbornene used in Example 1 was directly subjected to the polymerization reaction without any purification. As a result, no polymer was obtained.

Comparative Example 2 (1) Distillation of Norbornene The crude norbornene used in Example 1 was distilled to obtain distilled norbornene from which the antioxidant was removed. 30 g of dry toluene was added to 70 g of this distilled norbornene to prepare a 70 wt% toluene solution of norbornene. The content of epoxy norbornane in this norbornene solution is 136 pp
It was m. (2) Copolymerization of ethylene-norbornene Copolymerization of ethylene and norbornene was performed in the same manner as in Example 1 except that the above distilled norbornene was used. As a result, 11 g of a copolymer was obtained. The polymerization activity was 121 Kg / g · Zr and 0.68 Kg / gAl, the norbornene content of the obtained copolymer was 10 mol%, and the intrinsic viscosity was 0.78 dl / g.

Comparative Example 3 In Comparative Example 2, an epoxy norbornane content of 180 was obtained by distilling while changing the crude norbornene.
Copolymerization of ethylene and norbornene was performed in the same manner except that a ppm norbornene solution was used. As a result, 4.4 g of a copolymer was obtained. Polymerization activity is 4
8 Kg / g · Zr, 0.27 Kg / g Al, the norbornene content of the obtained copolymer was 10 mol%, and the intrinsic viscosity was 0.80 dl / g.

Comparative Example 4 Copolymerization of ethylene and norbornene was carried out in the same manner as in Comparative Example 3, except that a norbornene solution having an epoxy norbornane content of 210 ppm obtained by using a different crude norbornene was used. As a result, 1 g of a copolymer was obtained. Polymerization activity is 11Kg / gZr,
0.06 Kg / gAl, the obtained copolymer has a norbornene content of 12.4 mol% and an intrinsic viscosity [η] of 0.83 d.
It was 1 / g.

Example 3 30 ml of dry toluene, 5 mmol of triisobutylaluminum, 25 micromoles of nickel bis (acetylacetonate), 25 micromoles of dimethylanilinium tetra (pentafluorophenyl) borate were placed in a 500 ml glass container. When 500 mmol of the purified norbornene obtained in (1) of Example 1 was added and a polymerization reaction was carried out at 50 ° C. for 1 hour, 9.58 g of a polymer was obtained. The polymerization activity was 6.53 Kg / gNi. 1,
Mw measured at 135 ° C. in 2,4-trichlorobenzene
Was 1,210,000 and Mw / Mn was 2.37.

Comparative Example 5 Example 3 was repeated except that the norbornene obtained in Comparative Example 2 (1) was used.
Polymerization reaction was carried out in the same manner as above to obtain 2.11 g of a polymer. The polymerization activity was 1.44 Kg / gNi. Mw measured in the same manner as in Example 3 was 1,140,000, M
w / Mn was 2.10.

[0072]

As described above, the contact treatment with the inorganic substance used in the present invention poisons the oxide of the cyclic olefin in the cyclic olefin and the polymerization catalyst such as the polymerization inhibitor and the antioxidant to effect the polymerization. The inhibiting substance can be completely removed at room temperature without performing operations such as distillation. Therefore, according to the production method of the present invention, the polymerization activity of the catalyst can be significantly improved and a deashing-free process is possible. Further, it is possible to reduce equipment costs and energy costs.

Claims (3)

[Claims] 1. A process for producing a cyclic olefin polymer, characterized by carrying out homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an α-olefin using a cyclic olefin which has been subjected to a contact treatment with an inorganic substance. Method. 2. The inorganic substance is alumina, activated alumina,
Silica, activated carbon, quicklime, aluminum silicate, diatomaceous earth,
The method for producing a cyclic olefin polymer according to claim 1, wherein the method is at least one selected from activated clay, kaolinite, and zeolite. 3. The method according to claim 1, wherein after the cyclic olefin is subjected to a contact treatment with an inorganic substance, the cyclic olefin is supplied substantially directly from the contact treatment step with the inorganic substance to the polymerization step. A method for producing a cyclic olefin polymer.