JP2000119328A - Cyclic olefinic polymer with low content of catalyst residue, its use and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject polymer with a low content of catalyst residues scarcely producing a waste liquor containing a large amount of metals and capable of efficiently removing the catalyst residues by a simple means, by adding a specific compound and precipitating a compound containing a transition metal and aluminum. SOLUTION: At least one kind of compound selected from the group consisting of an α-hydroxy acid or a β-hydroxy acid respectively having one hydroxyl group and one carboxyl group in the molecule and a derivative in which the hydroxyl group thereof is substituted with an alkoxyl group is added to a solution of a reactional product using (A) an organic solvent-soluble transition metal catalyst component and (B) an organoaluminum compound as a catalyst to precipitate a compound containing the transition metal and aluminum. The resultant precipitate is then separated by filtration to produce the objective polymer. A metallocene catalyst component, a metathetic catalyst component, or the like, are preferably used as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a purified cyclic olefin polymer, its use, and its production method.
More specifically, the present invention relates to a cyclic olefin polymer substantially containing no catalyst residue, its use, and its production method.

[0002]

2. Description of the Related Art A cyclic olefin polymer having a bulky cyclic olefin as one of its constituents has high transparency, heat resistance,
Synthetic resin excellent in chemical resistance, solvent resistance, moisture resistance, dielectric properties, and various mechanical properties, and is widely used in various fields.

[0003] Cyclic olefin-based polymers can be mainly classified into addition copolymers, ring-opened polymers and hydrogenated products thereof, depending on the difference in structure. The addition copolymer is produced by subjecting a cyclic olefin and an α-olefin to addition copolymerization in a hydrocarbon solvent in the presence of a catalyst selected from a Ziegler catalyst and a metallocene catalyst. The ring-opened polymer is produced by subjecting a cyclic olefin to ring-opening polymerization in a hydrocarbon solvent in the presence of a metathesis catalyst. The hydrogenated product is an addition copolymer produced from a cyclic olefin containing two or more carbon-carbon double bonds, and a catalyst wherein the carbon-carbon double bond contained in the ring-opening polymer is selected from a Ziegler catalyst and a metallocene catalyst. And saturated with hydrogen in the presence of By saturating the double bond, the heat resistance, weather resistance and light resistance of the cyclic olefin polymer can be further improved.

[0004] In the production process of a cyclic olefin polymer, removal of the catalyst metal is a very important step in maintaining the properties of the resin such as transparency, weather resistance, moisture resistance and heat resistance. Heretofore, the following methods have been proposed for removing catalytic metals. (1) A method in which a polymer solution is charged into a large amount of a poor solvent to precipitate a copolymer precipitate, and the precipitate is washed with a poor solvent. (2) A method in which the polymer solution is washed with water containing an acid to extract and remove catalyst residues (see JP-A-2-24319 and JP-A-6-100668). (3) A method in which the polymer solution is washed with alcohol-containing water or the like, and the catalyst residue is extracted and removed (JP-A-4-4510).
3 and JP-A-6-228235). (4) A method in which an oxidizing agent or a basic compound is added to a polymer solution, and a catalyst residue is extracted and removed with a poor solvent (see JP-A-7-109310). (5) A method in which alcohol and water are added to the polymer solution, and thereafter, an adsorbent and a filter aid are added, and the catalyst residue is removed by filtration or centrifugation (JP-A-3-66725).
JP, JP-A-4-161421 and JP-A-4-161421
-36312).

In the case of (1), the poor solvent must be used at least several times the amount of the polymer solution, and this imposes a heavy burden on equipment and cost in industrial practice including recovery of the poor solvent. Also, the purification efficiency was not good. Further, regarding (2), (3) and (4), since a waste liquid containing a relatively large amount of catalyst metal is generated, there is a serious problem in the treatment of the waste liquid. The method (5) does not generate a large amount of waste liquid, but the purification efficiency is not good unless a large amount of an adsorbent and a filter aid is used, and it is difficult to perform a smooth filtration. Undesirably in the treatment of the polymer and the recovery rate of the polymer. Generally, the catalyst component used in producing the cyclic olefin polymer contains an organoaluminum compound such as alkylaluminum or alkylaluminoxane, and the amount of these used is much larger than other catalyst components. The organic aluminum compound is water, alcohol,
It reacts very easily with acids and the like and becomes insoluble in the hydrocarbon solvent used for the polymerization reaction. However, the reaction product generally separates as a gel containing a large amount of solvent,
In many cases, the reaction solution is sufficiently homogeneous to the naked eye. Therefore, even if the filtration is performed as it is, the filter agent is clogged,
Smooth filtration is almost impossible. Therefore, in many cases, an adsorbent and a filter aid must be used together.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyclic olefin system having a low catalyst residue content which hardly generates a waste liquid containing a large amount of metal and which can efficiently remove the catalyst residue by simple means. An object of the present invention is to provide a method for producing a polymer.

Another object of the present invention is to efficiently decompose a catalyst used in polymerization and / or hydrogenation reaction for producing a cyclic olefin polymer and to polymerize and / or decompose the decomposed product.
Another object of the present invention is to provide a method for producing a cyclic olefin polymer having a low catalyst residue content, which can be insolubilized in a reaction solvent used in a hydrogenation reaction and can be efficiently precipitated and removed.

It is a further object of the present invention to provide a method in which the above-mentioned catalyst is decomposed to produce substantially no colored decomposed product by-produced, or even if it is produced, it is adsorbed or included in the decomposed product of the catalyst. It is an object of the present invention to provide a method for producing a cyclic olefin-based polymer having a small content of a catalyst residue which can be removed together with a product.

Still another object of the present invention is to provide a cyclic olefin having a low catalyst residue content, which is capable of producing the above-mentioned catalytic decomposition product not as a remarkably swollen gel but as a solid which can be easily filtered off. An object of the present invention is to provide a method for producing a polymer.

Still another object of the present invention is to remove almost completely even a stable compound such as tris (acetylacetonato) aluminum which is inevitably produced as a by-product when an acetylacetonate complex and an organoaluminum compound are used. It is an object of the present invention to provide a process for producing a cyclic olefin polymer having a low catalyst residue content.

Still another object of the present invention is to provide a cyclic olefin polymer having a low content of catalyst residues. Still another object of the present invention is to provide use of the cyclic olefin polymer of the present invention for an optical material.
Still other objects and advantages of the present invention will become apparent from the following description.

[0012]

According to the present invention, the above objects and advantages of the present invention are as follows. First, a cyclic olefin polymer is prepared by using a transition metal catalyst component soluble in an organic solvent and an organic aluminum compound as a catalyst. In the production method, the reaction product is selected from the group consisting of α-oxy acids, β-oxy acids, each having one hydroxyl group and one carboxyl group in the molecule, and derivatives in which those hydroxyl groups are substituted with an alkoxyl group. This is achieved by a process for producing a cyclic olefin polymer, which comprises adding at least one compound to precipitate a compound containing a transition metal and aluminum, and then filtering the precipitate. Hereinafter, the method of the present invention will be described in detail.

(Organic aluminum compound) The organic aluminum compound used in the present invention is a compound having at least one aluminum-carbon bond in a molecule. Specifically, triethylaluminum, trialkylaluminum compounds such as triisobutylaluminum,
Organoaluminum alkoxide compounds such as diethylaluminum ethoxide, diisobutylaluminum butoxide and ethylaluminum sesquiethoxide; organic aluminum oxy compounds such as methylaluminoxane and ethylaluminoxane; diethylaluminum chloride; diisobutylaluminum chloride; ethylaluminum sesquichloride; butylaluminum sesquichloride ,
Organic aluminum halide compounds such as ethylaluminum dichloride and isobutylaluminum dichloride can be exemplified.

(Transition metal catalyst component) The transition metal catalyst component used in the present invention is prepared in the presence of an organoaluminum compound.
There is no particular limitation as long as it has a catalytic ability to produce a cyclic olefin polymer and is soluble in an organic solvent, but preferred examples thereof include a metallocene catalyst component, a metathesis catalyst component, and a Ziegler catalyst component. it can. Both the metallocene-based catalyst component and the Ziegler-based catalyst component are catalyst components for the addition copolymerization reaction of a cyclic olefin with an α-olefin and for the hydrogenation reaction of a polymer, and the metathesis-based catalyst component is a ring-opening polymerization reaction of a cyclic olefin. Catalyst component of the catalyst. Hereinafter, the metallocene catalyst, the metathesis catalyst component, and the Ziegler catalyst component will be described in detail.

(Metallocene-based catalyst component) The metallocene-based catalyst component used in the present invention depends on the reaction mode.
They can be classified into metallocene-based catalyst components suitable for addition copolymerization and metallocene-based catalyst components suitable for hydrogenation catalysts.
As the metallocene catalyst component suitable for addition copolymerization, those represented by the following general formula (III) are preferably used.

[0016]

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[In the formula (III), M is a transition metal selected from Group 4 of the periodic table, R ²⁹ and R ³⁰ are the same or different, and are a hydrogen atom, a halogen atom, a saturated or unsaturated compound having 1 to 12 carbon atoms. A saturated hydrocarbon group, an alkoxyl group having 1 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, wherein R ²⁷ and R ²⁸ are the same or different and form a sandwich structure with the central metal M a monocyclic or polycyclic hydrocarbon radical which can, R ²⁶ is a R ²⁷ group R
A bridge connecting ²⁸ units,

[0018]

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Wherein R ^{31 to} R ³⁴ are the same or different and are a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carbon atom having 1 to 12 carbon atoms. 6-12 Ali - aryloxy or a group, or the R ³¹ and R ³² or R ³³ and R ³⁴ may have to form a ring. ]

In the metallocene-based catalyst component represented by the formula (III), the central metal M is a transition metal of Group 4 such as zirconium, titanium and hafnium, and zirconium is most preferable in terms of catalytic activity. R ²⁹ and R ³⁰ may be the same or different, but have 1 to 6 carbon atoms.
Is preferably an alkyl group or a halogen atom (particularly a chlorine atom). Desirable cyclic hydrocarbon groups for R ²⁷ and R ²⁸ include a cyclopentadienyl group, an indenyl group and a fluorenyl group. These may be substituted by a hydrogen atom, or an alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, or a substituent such as a phenyl group or a benzyl group. R ³¹ to R ³⁴ is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms is preferable, as R ²⁶ is,
Preferable examples include a lower alkylene group such as a methylene group, an ethylene group and a propylene group, an alkylidene group such as isopropylidene, a substituted alkylene group such as diphenylmethylene, a silylene group or a substituted silylene group such as dimethylsilylene and diphenylsilylene.

As the metallocene whose central metal M is zirconium, the following compounds can be exemplified.

Dimethylsilylene-bis (1-indenyl) zirconium dichloride, diphenylsilylene-bis (1-indenyl) zirconium dichloride, dibenzylsilylene-bis (1-indenyl) zirconium dichloride, methylene-bis (1-indenyl) zirconium dichloride , Ethylene-bis (1-indenyl) zirconium dichloride, diphenylmethylene-bis (1
-Indenyl) zirconium dichloride, isopropylidene-bis (1-indenyl) zirconium dichloride, phenylmethylsilylene-bis (1-indenyl)
Zirconium dichloride, dimethylsilylene-bis [1
-(2,4,7-trimethyl) indenyl] zirconium dichloride, diphenylsilylene-bis [1- (2,4,
7-trimethyl) indenyl] zirconium dichloride, dibenzylsilylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, methylene-bis [1- (2,4,7-trimethyl) indenyl]
Zirconium dichloride, ethylene-bis [1- (2,
[4,7-trimethyl) indenyl] zirconium dichloride, diphenylmethylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, isopropylidene-bis [1- (2,4,7-trimethyl) indenyl] Zirconium dichloride, phenylmethylsilylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, dimethylsilylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, diphenylsilylene-bis [1 − (2,4
-Dimethyl) indenyl] zirconium dichloride, dibenzylsilylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, methylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, ethylene-bis [ 1- (2,4-dimethyl) indenyl] zirconium dichloride, diphenylmethylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, isopropylidene-bis [1- (2,4-dimethyl) indenyl] zirconium Dichloride, phenylmethylsilylene-bis [1-
(2,4-dimethyl) indenyl] zirconium dichloride, dimethylsilylene-bis [1- (4,5,6,7-
Tetrahydro) indenyl] zirconium dichloride,
Diphenylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, dibenzylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, methylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, ethylene-bis [1-
(4,5,6,7-tetrahydro) indenyl] zirconium dichloride, diphenylmethylene-bis [1-
(4,5,6,7-tetrahydro) indenyl] zirconium dichloride, isopropylidene-bis [1- (4,
5,6,7-tetrahydro) indenyl] zirconium dichloride, phenylmethylsilylene-bis [1- (4,
5,6,7-tetrahydro) indenyl] zirconium dichloride, dimethylsilylene- (9-fluorenyl)
(Cyclopentadienyl) zirconium dichloride, diphenylsilylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, dibenzylsilylene- (9-fluorenyl) (cyclopentadienyl)
Zirconium dichloride, methylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, ethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium Dichloride, isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- (9-fluorenyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene- (9-fluorenyl) [1- (3-t
tert-butyl) cyclopentadienyl] zirconium dichloride, diphenylsilylene- (9-fluorenyl)
[1- (3-tertbutyl) cyclopentadienyl]
Zirconium dichloride, dibenzylsilylene- (9-
Fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, methylene-
(9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, ethylene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,
Diphenylmethylene- (9-fluorenyl) [1- (3
-Tertbutyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, phenylmethylsilylene- (9-fluorenyl) [1- ( 3-tertbutyl)
Cyclopentadienyl] zirconium dichloride, dimethylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride,
Diphenylsilylene- (9-fluorenyl) [1- (3
-Methyl) cyclopentadienyl] zirconium dichloride, dibenzylsilylene- (9-fluorenyl) [1
-(3-methyl) cyclopentadienyl] zirconium dichloride, methylene- (9-fluorenyl) [1-
(3-methyl) cyclopentadienyl] zirconium dichloride, ethylene- (9-fluorenyl) [1- (3
-Methyl) cyclopentadienyl] zirconium dichloride, diphenylmethylene- (9-fluorenyl) [1
-(3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl)
[1- (3-methyl) cyclopentadienyl] zirconium dichloride, phenylmethylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, dimethylsilylene- [9
-(2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, diphenylsilylene- [9- (2,7-di-tertbutyl)
Fluorenyl] (cyclopentadienyl) zirconium dichloride, dibenzylsilylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, methylene- [9-
(2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, ethylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, diphenylmethylene- [9- (2,7-di-ter
t-butyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, isopropylidene- [9-
(2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, dimethyl Silylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, diphenylsilylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dibenzylsilylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride Methylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, ethylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene-
(1-indenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethyl Silylene-bis (cyclopentadienyl) zirconium dichloride, diphenylsilylene-bis (cyclopentadienyl) zirconium dichloride, dibenzylsilylene-bis (cyclopentadienyl) zirconium dichloride, methylene-bis (cyclopentadienyl) zirconium dichloride , Ethylene-bis (cyclopentadienyl) zirconium dichloride, diphenylmethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene Bis (cyclopentadienyl)
Zirconium dichloride, phenylmethylsilylene-bis (cyclopentadienyl) zirconium dichloride,
Isopropylidene- (1-indenyl) [1- (3-t
tert-butyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl)
[1- (3-isopropyl) cyclopentadienyl] zirconium dichloride, isopropylidene- [1-
(2,4,7-trimethyl) indenyl] (cyclopentadienyl) zirconium dichloride, ethylene- (cyclopentadienyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, ethylene- (cyclopentane Dienyl) [1- (3-phenyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dibromide, dimethylsilylene-bis (1-indenyl) zirconium dibromide, Ethylene-bis (1-indenyl) methyl zirconium monochloride.

In the present invention, particularly preferred metallocenes are isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene-
(9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,
Isopropylidene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1-indenyl) zirconium dichloride, ethylene-bis (1-indenyl) zirconium dichloride, isopropylidene-bis (1-indenyl) zirconium Dichloride can be mentioned.

The concentration of the metallocene-based catalyst component may be determined according to the polymerization activity, but based on the cyclic olefin added to the polymerization reaction system, 1 m of cyclic olefin is used.
10 ^-6 to 10 ^-2 mol, preferably 10 ^-5,
Used at a concentration of 〜１０10 ^-3 mol.

As the organoaluminum compound, alkylaluminoxane and trialkylaluminum, which are organoaluminum oxy compounds, are preferably used.

When an alkylaluminoxane is used as the organoaluminum compound, it is used in combination with a metallocene catalyst component, and when a trialkylaluminum is used, it is used in combination with an ionic boron compound in addition to the metallocene catalyst component.

The alkylaluminoxane can be exemplified by the general formula (IV) in a linear structure and by the general formula (V) in a cyclic structure.

[0028]

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[0029]

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[In the formulas (IV) and (V), R ^35-
R ⁴⁰ is the same or different and is a methyl group, an ethyl group,
It is an alkyl group having 1 to 6 carbon atoms such as a propyl group or a butyl group, a phenyl group or a benzyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group.
m is an integer of 2 or more, preferably an integer of 5 to 100. However, the exact structure of the alkylaluminoxane is unknown.

The alkylaluminoxane is obtained by reacting a compound containing adsorbed water or a salt containing water of crystallization (eg, copper sulfate hydrate) with an organic aluminum compound such as trialkylaluminum in an inert solvent (eg, toluene). For example, it can be manufactured by a conventionally known method. The alkylaluminoxane may contain a small amount of an organoaluminum compound derived from the production method.

The alkylaluminoxane has a function of alkylating the metallocene catalyst component and converting the metallocene catalyst component to cationic, thereby obtaining polymerization activity. The metallocene-based catalyst component is activated in a solution, but it is preferable to dissolve the metallocene-based catalyst component in an alkylaluminoxane solution. As a solvent used for such activation, an aliphatic hydrocarbon or an aromatic hydrocarbon is preferable, and among them, toluene is most preferable. The activation of the metallocene-based catalyst component by the alkylaluminoxane is usually carried out before use in the polymerization reaction, in which case the activation time is one hour.
Minutes to 10 hours, preferably 3 minutes to 1 hour. Activation is from -40 to 110 ° C, preferably from 0 to 8
It is performed in a temperature range of 0 ° C.

The ratio of the alkylaluminoxane to the metallocene catalyst component is 1 mol of the metallocene catalyst component.
Alkyl aluminoxane 30 to 20,000 m
ol, preferably 100 to 5,000 mol. If the amount of the alkylaluminoxane relative to the metallocene catalyst component is too small, sufficient polymerization activity cannot be obtained, which is not preferable. On the other hand, if the amount of the alkylaluminoxane is too large, it is not economical because a large amount of expensive alkylaluminoxane is used although the polymerization activity is high, and purification after polymerization becomes difficult, which is not preferable.

As an organoaluminum compound suitably used other than the alkylaluminoxane, trialkylaluminums such as triethylaluminum and triisobutylaluminum can be mentioned. In this case, it is necessary to additionally use an ionic boron compound.

The ionic boron compound specifically refers to a compound represented by the following general formulas (VI) to (IX).

[0036] _{^{[R 41 3 C] + [}} BR 42 4] - ··· (VI) [R 41 x NH 4-x] + [BR 42 4] - ··· (VII) [R 41 x PH 4 _{^{-x] + [BR 42 4]}} - ··· (IIX) Li + [BR 42 4] - ··· (IX)

[In the formulas (VI) to (IX), R ⁴¹ is the same or different and is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R ⁴² is the same or different and is an aromatic hydrocarbon group having 6 to 18 carbon atoms. x is 1, 2, 3 or 4. ]

In the ionic boron compounds represented by the above formulas (VI) to (IX), R ⁴¹ is preferably the same, and an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a phenyl group And the like. R ⁴² is preferably the same, is preferably a fluorinated or partially fluorinated aromatic hydrocarbon group, and particularly preferably is a pentafluorophenyl group. x is preferably 3. Specific compounds include N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate and trityl-
Examples include tetrakis (pentafluorophenyl) borate and lithium-tetrakis (pentafluorophenyl) borate.

The ionic boron compound functions to convert the metallocene catalyst component to a cation, and the organoaluminum compound functions to alkylate the metallocene catalyst component. Is obtained.

The ratio of the ionic boron compound to the metallocene catalyst component was 1 mol of the metallocene catalyst component.
0.5 to 10 mol, preferably 0.8 to 5 mol, more preferably 0.9 to 3 m
ol is used. The organoaluminum compound is used in an amount of 2 to 500 mol per 1 mol of the metallocene. When an ionic boron compound is used, the required amount of the organoaluminum compound with respect to the metallocene-based catalyst component is significantly smaller than in the case where an alkylaluminoxane is used as the organoaluminum compound, and the catalytic activity tends to be higher. Therefore, the amounts of the metallocene-based catalyst component and the cocatalyst can be reduced, and the advantage is large in terms of economy and purification after polymerization.

On the other hand, as the metallocene-based catalyst component suitable for the hydrogenation reaction, those represented by the following general formula (X) are preferably used in addition to those represented by the above general formula (III).

[0042]

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In the metallocene catalyst components represented by the above formulas (III) and (X), the central metal M is a transition metal belonging to Group 4 of the periodic table such as titanium, zirconium and hafnium, and titanium is a catalyst. Preferred from the aspect of activity. R ⁴⁵ and R ⁴⁶ may be the same or different, but are preferably an alkyl group having 1 to 8 carbon atoms, an aryl group, or a halogen atom (particularly a chlorine atom). Preferred examples of the cyclic hydrocarbon group for R ⁴³ and R ⁴⁴ include a cyclopentadienyl group, an indenyl group, and a fluorenyl group. These may be substituted by a hydrogen atom, or an alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, or a substituent such as a phenyl group or a benzyl group.

The following compounds can be exemplified as the metallocene in which the central metal M is titanium, ie, titanocene. Bis (cyclopentazinyl) titanium dichloride, bis (cyclopentazinyl) titanium dimethyl, bis (cyclopentazinyl) titanium diphenyl, bis (cyclopentazinyl) titanium ditolyl, bis (methylcyclopentazinyl) titanium dichloride, Bis (methylcyclopentazinyl) titanium dimethyl, bis (methylcyclopentazinyl) titanium diphenyl, bis (methylcyclopentazinyl) titanium ditolyl, bis (butylcyclopentazinyl) titanium dichloride, bis (butylcyclopentazinyl) ) Titanium dimethyl, bis (butylcyclopentazinyl) titanium diphenyl, bis (butylcyclopentazinyl) titanium ditolyl, bis (pentamethylcyclopentazinyl) titanium dichloride, bis (pentamethylcyclopentazinyl) titanium di Butyl, bis (pentamethylcyclopentazinyl) titanium diphenyl, bis (pentamethylcyclopentazinyl) titanium ditolyl, (cyclopentadienyl) (pentamethylcyclopentazinyl) titanium dichloride, (cyclopentadienyl) (penta Methylcyclopentazinyl) titanium dimethyl, (cyclopentadienyl) (pentamethylcyclopentazinyl) titanium diphenyl, (cyclopentadienyl) (pentamethylcyclopentazinyl) titanium ditolyl.

Among these, bis (cyclopentazinyl) titanium dichloride, bis (cyclopentazinyl) titanium diphenyl, bis (cyclopentazinyl) titanium dichloride, and bis (cyclopentazinyl) titanium dichloride are particularly preferred from the viewpoint of relatively easy handling and high activity. (Pentazinyl) titanium ditolyl.

The concentration of the metallocene catalyst component may be determined in accordance with the polymerization activity.
10 ^-6 to 10 ^-2 mol, preferably 10 ^-5,
Used at a concentration of 〜１０10 ^-3 mol.

When used as a hydrogenation catalyst, it is preferable to combine a metallocene-based catalyst component with an organolithium compound from the viewpoint of enhancing the catalytic activity. An organic lithium compound is a compound in which a lithium atom and a hydrocarbon group are bonded. Specifically, methyl lithium, ethyl lithium,
Monolithium compounds such as propyllithium, isopropyllithium, butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, phenyllithium, benzyllithium and the like, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,2-dilithium Examples thereof include dilithium compounds such as thiodiphenylethane. Of these, methyl lithium, butyl lithium, sec-butyl lithium,
Tert-butyllithium is particularly preferred.

The ratio of the organolithium compound to the metallocene-based catalyst component is 1.0 to 20 mol, preferably 1.5 to 10 mol, of the organolithium compound per 1 mol of the metallocene-based catalyst component. If the amount of the organolithium compound relative to the metallocene catalyst component is too small,
It is not preferable because sufficient polymerization activity cannot be obtained. Conversely, if the amount of the organolithium compound is too large, the activity is not increased, and purification after polymerization becomes difficult, which is not preferable.

The metallocene-based catalyst component is converted into a neutral alkylated metallocene by combining with an organolithium compound to obtain a hydrogenation catalytic activity.

The form of the polymer subjected to the hydrogenation reaction is not particularly limited, and may be in an isolated state or a solution state after the polymerization reaction. However, in the former case, it is necessary to make the polymer into a solution again, and the latter is preferable in industrial practice.

(Metathesis-based catalyst component) The metathesis-based catalyst component used in the present invention is a compound of a transition metal belonging to Groups 3 to 8 of the periodic table, and a halide, oxyhalide, or alkoxyhalide of these transition metals. Alkoxide, carboxylate, (oxy) acetylacetonate, carbonyl complex, acetonitrile complex, hydride complex, derivatives thereof and the like. Of these, titanium, vanadium,
Molybdenum, tungsten and rhenium compounds are preferred. Specifically, titanium trichloride, titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, vanadium oxytrichloride, vanadium oxytribromide, tungsten hexachloride, tungsten tetrachloride, tungsten dichloride, tungsten hexabromide, Tungsten iodide, tungsten dioxide, tungsten trioxide, tridecylammonium tungstate, molybdenum pentachloride, molybdenum trichloride, molybdenum dibromide, molybdenum diiodide, molybdenum trioxide, molybdenum dioxide, (oxy) molybdenum tetrachloride, Tridecyl ammonium molybdate, rhenium trichloride,
(Oxy) rhenium trichloride, rhenium tribromide and (oxy) rhenium tribromide can be mentioned. Of these, particularly preferred compounds include titanium tetrachloride, molybdenum pentachloride, and tungsten hexachloride.

The metathesis catalyst is a catalyst obtained by combining the above-mentioned metathesis catalyst component with an organoaluminum compound. Particularly preferred as the organoaluminum compound used here are trialkylaluminum compounds such as triethylaluminum and triisobutylaluminum. Further, an additive may be added to increase the polymerization activity of the metathesis catalyst.

The additives include aliphatic tertiary amines, aromatic tertiary amines, molecular oxygen, water, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones and aldehydes. , Pyridine derivatives, thiophene derivatives, nitrogen-containing compounds such as molecular iodine, oxygen-containing compounds, sulfur-containing compounds, and halogen-containing compounds. Of these, aliphatic and aromatic tertiary amines are preferred, triethylamine, dimethylaniline,
Tributylamine, pyridine and methylpyridine are particularly preferred in that they significantly improve the polymerization activity.

In consideration of polymerization activity, the amount of the metathesis-based polymerization catalyst component is 10 to 1 mol of the cyclic olefin.
^-5 mol or more and 10 ^-1 mol or less, preferably 10 ^-4 mol
It is preferable to add in the range of 1 to 10 ^-2 mol.

The quantitative relationship of the other components is such that the amount of the organoaluminum compound is 1 mol or more and 100 mol or less, preferably 2 mol or more and 50 mol or less, and the additive is 0.005 mol or more with respect to 1 mol of the metathesis catalyst component. 10 mol or less,
Preferably, it is used in an amount of 0.05 mol or more and 3 mol or less.
If the amount of the organoaluminum compound is too small, sufficient activity cannot be obtained, and if the amount is too large, the activity does not increase, and it is not preferable because the catalyst removal is burdensome and the cost is increased. On the other hand, if the amount of the additive is too small, no improvement in polymerization activity is observed, and if the amount is too large, the catalyst is deactivated, which is not preferable.

(Ziegler-based catalyst component) The Ziegler-based catalyst component used in the present invention depends on the reaction mode.
They can be classified into types. That is, a Ziegler catalyst component suitable for addition copolymerization and a Ziegler catalyst component suitable for hydrogenation reaction. Suitable Ziegler catalyst components for addition copolymerization include vanadium compounds represented by the following general formulas (XI) to (XII). ^{_{VO (OR 47) a X b}} ··· (XI) V (OR 47) c X d ··· (XII)

[In the formulas (X) to (XI), R ⁴⁷ is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. a, b, c and d are 0 ≦ a
≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦
It is an integer satisfying d ≦ 4, 3 ≦ c + d ≦ 4. ]

More specifically, vanadium (oxy) trichloride, vanadium (oxy) (ethoxy) dichloride, vanadium (oxy) (propoxy) dichloride,
Vanadium (oxy) (isopropoxy) dichloride,
Vanadium (oxy) (butoxy) dichloride, vanadium (oxy) (isobutoxy) dichloride, vanadium (oxy) (diethoxy) chloride, vanadium (oxy) (diisopropoxy) chloride, vanadium (oxy) (dibutoxy) chloride, vanadium (oxy) )
(Diisobutoxy) chloride, vanadium (oxy) triethoxide, vanadium (oxy) tripropoxide, vanadium (oxy) triisopropoxide, vanadium (oxy) tributoxide, vanadium (oxy) triisobutoxide, vanadium trichloride, vanadium tribromide And vanadium tetrachloride.

The concentration of the vanadium compound may be determined in accordance with the polymerization activity, but based on the cyclic olefin added to the polymerization reaction system, 1 mol of the cyclic olefin is used.
10 ^-6 to 10 ^-2 mol, preferably 10 ^-5 to 1
Used at a concentration of 0 ^-3 mol.

The Ziegler catalyst suitable for the addition copolymerization is a catalyst produced by combining the vanadium compound and the organoaluminum compound. As the organoaluminum compound, an organoaluminum halide compound is particularly preferred, and specific examples thereof include diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

In order to improve the polymerization activity, an electron donor can be further added to the Ziegler catalyst. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, acid esters, acid amides, acid anhydrides, ethers, oxygen-containing electron donors such as alkoxysilanes, amines, nitriles, and isocyanates. it can.

The ratio of the organoaluminum compound to the vanadium compound is 2 to 500 mol, preferably 2 to 50 mol, more preferably 3 to 30 mol, based on 1 mol of the vanadium compound. If the amount of the organoaluminum compound is too small, high activity cannot be obtained, and if it is too large, the polymer may gel, which is not preferable. Similarly, the ratio of the electron donor to the vanadium compound is as follows:
The electron donor is used in an amount of from 0.005 mol to 10 mol, preferably from 0.05 mol to 3 mol, per mol. If the amount of the additive is too small, no improvement in the polymerization activity is observed, and if the amount is too large, the catalyst is deactivated, which is not preferable.

On the other hand, Ziegler catalyst components suitable as hydrogenation catalysts include vanadium, chromium, manganese,
Halides of transition metals such as iron, ruthenium, cobalt, rhodium, nickel and palladium, acetylacetonate complexes, carboxylate complexes, naphthate complexes, trifluoroacetate complexes, stearate complexes, etc. No. Specifically, triethyl vanadate, tris (acetylacetonate) chromium, tris (acetylacetonate) manganese, cobalt acetate, tris (acetylacetonate) cobalt, cobalt octenoate, bis (acetyl) (Acetonate) nickel and the like. Of these, cobalt and nickel compounds are preferred from the viewpoint of catalytic activity, and tris (acetylacetonate) is preferred.
Cobalt or bis (acetylacetonate) nickel is particularly preferred.

A Ziegler catalyst suitable for the hydrogenation reaction is produced by combining the transition metal compound with an organoaluminum compound. The organoaluminum compound used here is as described above, and particularly preferred are trialkylaluminum compounds such as triethylaluminum and triisobutylaluminum.

The quantitative relationship between the transition metal compound and the organoaluminum compound is as follows.
The metal component of the alkyl metal compound is 1 mol or more and 50 mol or less, preferably 10 mol or less.

The form of the polymer to be subjected to the hydrogenation reaction is not particularly limited, and may be in an isolated state or in a solution state after the polymerization reaction. However, in the former case, it is necessary to make the polymer into a solution again, and the latter is preferable in industrial practice.

(Cyclic Olefin) The cyclic olefin used in the present invention is represented by the following general formula (I).

[0068]

Embedded image

[In the formula (I), n is 0 or 1, m
Is 0 or a positive integer, p is 0 or 1, R
¹ to R ²⁰ are the same or different, a hydrogen atom, a halogen atom, an aromatic hydrocarbon group or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, 6 to 10 carbon atoms, also, R ¹⁷ And R ¹⁸ or R ¹⁹ and R ²⁰ may form an alkylidene group, or R ¹⁷ or R ¹⁸ and R ¹⁹ or R ²⁰ may form a ring,
Further, the ring may have a double bond or an aromatic ring. The following compounds can be exemplified as the cyclic olefin represented by the above formula (I).

Bicyclo [2.2.1] hept-2-ene (norbornene), 1-methylbicyclo [2.2.1] hept-2-ene, 6-methylbicyclo [2.2.1] hept- 2-ene, 6-ethylbicyclo [2.2.1] hept-2-ene, 6-n-propylbicyclo [2.2.1] hept-2-ene, 6-isopropylbicyclo [2.2.
1] Hept-2-ene, 6-n-butylbicyclo [2.
2.1] Hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 6-ethylidenebicyclo [2.2.1] hept-2-ene, 6-propylidenebicyclo [ Bicyclo [2.2.1] hept-2-ene, 6-isopropylidenebicyclo [2.2.1] hept-2-ene and 7-methylbicyclo [2.2.1] hept-2-ene 2.2.1] hept-2-ene derivatives, tricyclo [4.3.0.1 ^{2.5]-3-decene,} 2-methyl-tricyclo [4.3.0.1 ^{2.5]-3-decene,} 5 - methyltricyclo [4.3.0.1 ^2.5] -3- decene, 10-methyl tricyclo [4.3.0.1 ^2.5] -3- tricyclo such decene [4.3.0.1 ^2.5 ] -3-decene derivatives, dicyclopentadiene, tricyclo [4.4.0.1 ^2.5] -3-undecene, 2-Mechirutorishiku Russia [4.4.0.1 ^2.5] -
3- undecene, 5-methyl-tricyclo [4.4.0.1 ^2
.5 ] -3-undecene, 11-methyltricyclo [4.
4.0.1 ^2.5] -3-undecene tricyclo [4.4.0.1 ^2.5] -3-undecene derivatives such as tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-
Methyl tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-
Dodecene, 8-ethyl tetracyclo [4.4.0.1 ^2.5.
1 ^7.10] -3-dodecene, 8-n-propyl-tetracyclo [4.4.0.1 ^{2 .5} .1 ^7.10] -3-dodecene, 8-isopropyl-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10 ]-
3-dodecene, 8-n-butyltetracyclo [4.4.
0.1 ^2.5 .1 ^{7.1 0]} -3-dodecene, 8-isobutyl-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2.5.1 .
^7.10] -3-dodecene, 8-n-propylidene-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-
Isopropylidene tetracyclo [4.4.0.1 ^2.5 .1
^7.10 ] Tetracyclo [4.4.0.
1 ^2.5 .1 ^7.10] -3-dodecene derivatives, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} -4- pentadecene, pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ]-
4,10-pentadecadiene. Of these, bicyclo [2.2.1] hept-2-ene (norbornene) derivative, dicyclopentadiene, and tetracyclo [4.4.0.
1 ^2.5 .1 ^7.10] -3-dodecene derivatives are preferable, norbornene, dicyclopentadiene is particularly preferable. These may be used alone or in combination of two or more.

(Cyclic Olefin Polymer) The cyclic olefin polymer produced in the present invention is not particularly limited as long as it is a polymer containing a cyclic olefin as a polymer unit, but the cyclic olefin polymer mainly depends on the structure of the polymer. And α-olefins, ring-opened polymers of cyclic olefins, and hydrogenated products thereof.

(Addition Copolymer) In the present invention, an α-olefin having 2 or more carbon atoms and a cyclic olefin are used in the presence of a hydrocarbon catalyst in the presence of a polymerization catalyst selected from the group consisting of metallocene catalysts and Ziegler catalysts. An α-olefin-cyclic olefin copolymer is produced by addition copolymerization in a solvent.

The addition copolymer has a repeating structure represented by the following general formula (XIII).

[0074]

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In the formula (XIII), n, m, p, R ^{1 to} R ²⁰
Has the same meaning as in formula (I). R ⁴⁸ is a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms. The cyclic olefin component / α-olefin component (molar ratio) is not particularly limited, but is preferably 90/10 to 10 /.
90, more preferably 80/20 to 20 /.
The range is 80.

As the α-olefin having 2 or more carbon atoms used in the present invention, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include α-olefins having 2 to 20 carbon atoms, such as -methyl-1-pentene, 1-heptene, 1-octene, and 1-decene. Among them, ethylene and propylene are preferred from the viewpoint of polymerization activity and molecular weight of the polymer, and ethylene is particularly preferred. These may be used alone or in combination of two or more.
The cyclic olefin, metallocene catalyst and Ziegler catalyst are as described above.

The hydrocarbon solvents used herein include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and cyclooctane, benzene And aromatic hydrocarbons such as toluene, xylene, mesitylene and diethylbenzene.
These may be used alone or in combination of two or more. Among these, aromatic hydrocarbons and alicyclic hydrocarbons are preferable because of high solubility of the catalyst and the polymer, and benzene, toluene, cyclohexane and methylcyclohexane are particularly preferable.

The molar ratio between the α-olefin unit and the cyclic olefin unit in the copolymer can be easily controlled by controlling the ratio of the monomer concentrations of both.
In particular, when the α-olefin is a gas at normal temperature such as ethylene, the rate of introduction into the polymer can be controlled by the pressure of the α-olefin.

The temperature and time of the polymerization reaction may be determined according to the type of the monomer and the catalyst used for the addition copolymerization. Usually, the temperature is between 0 ° C and 100 ° C, preferably 1 ° C.
The reaction time is from 0 ° C to 80 ° C, and the reaction time is from 0.1 hour to 10 hours.

(Hydrogenation product of addition copolymer) When a cyclic olefin having two or more carbon-carbon double bonds is used in the production of the above-mentioned addition copolymer, the addition polymer has a carbon-carbon double bond. Bonds remain. In that case, a hydrogenation catalyst can be produced by adding a hydrogenation catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst to the reaction solution after polymerization, and performing hydrogenation. The structure of the hydrogenated product has a repeating structure represented by the following general formula (XIV).

[0081]

Embedded image [In the formula (XIV), n, m, and p have the same meanings as in the formula (I). R ⁴⁹ to R ⁶⁸ are the same or different, a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and, R ⁶⁵ or R ⁶⁶ and R ⁶⁷ or R ⁶⁸ may form a ring, and the ring may have an aromatic ring. ]

Examples of the cyclic olefin having two or more carbon-carbon double bonds include the following compounds. 6
-Ethylidenebicyclo [2.2.1] hept-2-ene,
Bicyclo [2.2.1] hept-2-ene such as 6-propylidenebicyclo [2.2.1] hept-2-ene and 6-isopropylidenebicyclo [2.2.1] hept-2-ene derivatives, dicyclopentadiene, 8-ethylidene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3- dodecene,
8-n-propylidene-tetracyclo [4.4.0.1 ^2.5.
1 ^7.10] -3-dodecene, 8-isopropylidene-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10, such as] -3- dodecene derivatives, pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0
^9.13 ] -4,10-pentadecadiene. Of these,
Dicyclopentadiene is preferred from the viewpoint that it is inexpensive and easily available. The metallocene catalyst and Ziegler catalyst used as the hydrogenation catalyst are as described above.

In the present invention, the solution after the polymerization reaction is used for the hydrogenation reaction. However, even if the solvent is an aromatic hydrocarbon, only the polymer can be selectively hydrogenated. The temperature, hydrogen pressure, and reaction time of the hydrogenation reaction of the addition copolymer may be determined according to the type of the monomer used for the addition copolymerization and the type of the hydrogenation catalyst. Usually, the temperature is above 0 ° C, 2
00 ° C or less, preferably 20 ° C or more and 180 ° C or less, hydrogen pressure is 0.1 kgf / cm ² or more, 200 kgf / cm
² or less, preferably 1 kgf / cm ² or more, 100 kgf
/ Cm ² or less, and the reaction time is 0.1 to 10 hours.

The hydrogenation ratio (hydrogenation ratio of carbon-carbon double bond) of such a copolymer is 98% or more, preferably 99% or more, and more preferably 99.5% or more. If the degree of hydrogenation is lower than 98%, thermal stability is insufficient, and coloring and the like are likely to occur during melt molding, which is not preferable. (Ring-opening polymer)

In the present invention, a cyclic olefin ring-opened polymer is produced by subjecting a cyclic olefin to ring-opening polymerization in a hydrocarbon solvent in the presence of a metathesis catalyst.

The cyclic olefin ring-opening polymer produced in the present invention is a polymer in which the carbon-carbon double bond of the norbornene skeleton portion of the cyclic olefin is ring-opened, and has a repeating structure represented by the following general formula (XV). Have.

[0087]

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[In the formula (XV), n, m, p and R ^{1 to} R ²⁰ have the same meanings as in the formula (I). ]

The cyclic olefin, metathesis catalyst and ring-opening polymer are as described above. The hydrocarbon solvent used here is the same as the hydrocarbon solvent used in the addition copolymerization reaction.

The temperature and time of the polymerization reaction may be determined according to the type of the monomer and the catalyst used for the ring-opening polymerization.
Usually, the temperature is 0 ° C or higher and 150 ° C or lower, preferably 10 ° C
The reaction time is from 0.1 hour to 10 hours. (Hydrogenated ring-opened polymer)

Since the ring-opening polymer produced by the ring-opening polymerization reaction inevitably contains a carbon-carbon double bond, in the present invention, the solution after the ring-opening polymerization contains a metallocene catalyst and a Ziegler catalyst. Hydrogenation can be carried out by adding a hydrogenation catalyst selected from the group consisting of:

The structure of the hydrogenated product is represented by the following general formula (XVI)
Having a repeating structure of

[0093]

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[In the formula (XVI), n, m and p have the same meanings as in the formula (I). R ⁴⁹ to R ⁶⁸ are the same or different, a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and, R ⁶⁵ or R ⁶⁶ and R ⁶⁷ or R ⁶⁸ may form a ring, and the ring may have an aromatic ring. ]

Suitable metallocene catalysts and Ziegler catalysts as the hydrogenation catalyst are as described above. The conditions for the hydrogenation reaction are exactly the same as the conditions for the hydrogenation reaction following the addition copolymerization reaction.

(Removal of Catalyst) In the present invention, an α-oxy acid, β-oxy acid having one hydroxyl group and one carboxyl group in the molecule, respectively, and a solution of the reaction product after the production of the cyclic olefin polymer, and a mixture thereof. At least one compound selected from the group consisting of derivatives in which a hydroxyl group is substituted with an alkoxyl group is added to decompose and deactivate the catalyst, and at the same time, to precipitate a catalytic metal component. At least one compound selected from the group consisting of α-oxy acids, β-oxy acids and derivatives in which a hydroxyl group is substituted with an alkoxyl group is represented by the following general formula (II).

[0097]

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[In the formula (II), q is 0 or 1, and R
²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² , R ²³ , R ²⁴ and R ²⁵ are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. It is. Preferred examples of the compound represented by the above formula (II) include the following.

Glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxy-2-methylpropionic acid, 2-hydroxy-2-methylbutyric acid, 2-
Hydroxy-3-methylbutyric acid, 3-hydroxy-2,2
-Dimethyl lactic acid, mandelic acid, diphenyl glycolic acid, tropic acid, 3-hydroxy-3-phenylpropionic acid, methoxyacetic acid, 2-methoxypropionic acid, 3-
Methoxypropionic acid, α-methoxyphenylacetic acid.

Of these, glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxy-butyric acid are preferred because they have a boiling point of about 200 ° C. or less at 10 mmHg and can be easily removed in the subsequent solvent distillation step.
2-Methylpropionic acid, methoxyacetic acid, 2-methoxypropionic acid and 3-methoxypropionic acid are preferred.
Further, α-oxy acids are preferred from the viewpoint that the chelating effect is large and the metal component is easily insolubilized, and glycolic acid, lactic acid, 2-hydroxybutyric acid, and 2-hydroxy-2-acid are used.
Methylpropionic acid is particularly preferred.

The amount of the compound represented by the above formula (II) is preferably determined by the amount of the catalyst metal contained in the reaction system. That is, the product of the mole number of the transition metal catalyst component and the oxidation number of the transition metal, the product of the mole number of the organoaluminum compound and the oxidation number of aluminum (3), and if necessary, the mole number of the organolithium compound and the oxidation of lithium. It is preferable to add 0.1 to 5 mol per 1 equivalent of the sum of the products of the number (1).

It is also preferable to add a compound selected from the group consisting of water and alcohol, in addition to the compound represented by the formula (II). The amount of water to be added is 0 to 9.9 mol, preferably 0 to 8 mol, based on the above criteria.
In addition, the amount of alcohol to be added is 0 to 5 with respect to the above standard.
Mole, preferably from 0 to 4 mole. However, the addition is preferably performed so that the total of the compound represented by the formula (II), water and alcohol is in the range of 0.1 to 10 mol.

If the amount of the compound represented by the above formula (II), water and alcohol is too small, the catalyst component is incompletely precipitated, which is not preferable. On the other hand, if the amount is too large, the polarity of the polymer solution increases, and a part or all of the catalyst component is supplemented by the dissolved compound represented by the formula (II), water and alcohol, and the polymer solution is added to the polymer solution. It is not preferable because it has been melted. Of course, if the amount of the compound represented by the above formula (II), water and alcohol is unnecessarily large, the compound far deviates in solubility in the polymer solution. Therefore, they must be separated before filtering. Such a state is not preferable because a waste liquid containing a large amount of metal is generated.

The water used in the present invention not only reacts with the catalyst and the catalytically active species by itself to insolubilize the catalyst and the catalytically active species, but also has the effect of significantly increasing the reactivity by assisting the ionization of the oxycarboxylic acid. .

The alcohol used in the present invention includes an aliphatic alcohol having 1 to 5 carbon atoms.
Such alcohols include methanol, ethanol,
Examples include propanol, isopropanol, n-butanol, and isobutanol. Polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin are also preferably used. Among them, ethylene glycol is not only inexpensive, but also reacts with a catalytic metal to form an alcoholate, and at least a part of another hydroxyl group remains. It is particularly preferred for insolubilizing the catalytic metal due to its polar effect. Also, in consideration of the solvent recovery step, it is preferable to select an active hydrogen-containing compound which has a significantly different boiling point from the solvent used and is easily separated and purified. The compound represented by the above formula (II), water and alcohol can be added alone or in combination of two or more.

The addition of the compound represented by the formula (II), water and alcohol to the polymer solution is carried out at 0 to 200 ° C., preferably 10 to 180 ° C., more preferably from room temperature to the boiling point of the solvent used. If the reaction temperature is too low, the reaction does not proceed sufficiently, and if it is too high, the precipitates are easily dissolved in the polymer solution, which is not preferable.

The reaction time is 1 minute to 10 hours, preferably 5 minutes to 5 hours, more preferably 10 minutes to 3 hours.
Less than an hour. If the reaction time is shorter than this, the reaction does not proceed completely, which is not preferable, and if it is longer than this, there is no effect and only time is wasted.

When an active hydrogen-containing compound is added to the polymer solution, the metallocene-based catalyst and the hydrogenation catalyst are converted to the above formula (II)
And a bond with water and alcohol. Hereinafter, α-olefin-cyclic is obtained by using isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride as a metallocene, trityltetra (pentafluorophenyl) borate as a cocatalyst, and triisobutylaluminum as an alkylating agent. The case where the catalyst is removed using lactic acid / water system as an active hydrogen compound after polymerizing olefin will be described in detail as an example. Further, the case where tris (acetylacetonate) cobalt is hydrogenated using triisobutylaluminum as an alkylating agent and then the catalyst is removed using lactic acid / water as an active hydrogen compound will be described in detail as an example.

(Removal of polymerization catalyst) Regarding the polymerization catalyst,
From the metallocene, a lactic acid / water reactant of zirconium metal [Zr (OLc) _m (OH) _4-m : OLc represents a lactic acid residue, m is an integer of 0 to 4], a isopropylidene ligand ( It is believed that derivatives from the 9-fluorenyl) (cyclopentadienyl) group and hydrogen halides, as well as partial reactants of the metallocene with lactic acid and / or water, are formed. Further, a triphenylmethyl compound containing triphenylmethane is generated from a cation component of trityltetra (pentafluorophenyl) borate as a cocatalyst, and boric acid [HB (C ₆ F ₅ ) ₄ ] is generated from an anion component. From triisobutylaluminum, alkanes and Al (OLc) _n (OH) _3-n [OLc is n
Is an integer of 0 to 3] and / or a condensate thereof. Generally, in the case of a condensate, the higher the degree of condensation, the more likely it is to form a gel.

Of these, decomposition products containing zirconium, decomposition products containing aluminum, hydrogen halide, boric acid, etc. are precipitated from a hydrocarbon-based polymer solution having high inorganicity and low polarity. At this time, the decomposition products of metallocene, boric acid, and the like are very small in amount, so that it is difficult to precipitate almost completely by themselves, but because they are included in the decomposition products derived from triisobutylaluminum that exists in large amounts. In addition, it becomes possible to separate the polymer solution very efficiently. In particular, a triisobutylaluminum compound is preferable because it easily becomes a decomposition product having a high degree of condensation, and thus a decomposition product of metallocene and boric acid are easily included.

(Removal of Hydrogenation Catalyst) Representative Ziegle
Tris (acetylacetonato) cobalt, one of the r-type hydrogenation catalysts, has no hydrogenation catalytic activity itself, and becomes catalytically active as an active species only after being reduced by triisobutylaluminum to a compound containing an isobutyl group. Demonstrate. Since the compound is alkylated, it reacts very easily with the active hydrogen-containing compound used in the present invention to form a decomposition product insoluble in the hydrocarbon polymer solvent. And
As described above, it precipitates together with or included in the decomposition product derived from triisobutylaluminum.
However, since the hydrogenation reaction is performed at a high temperature, acetylacetonate groups are exchanged between tris (acetylacetonato) cobalt and triisobutylaluminum, and tris (acetylacetonato) aluminum is by-produced. The compound itself is extremely stable and cannot be decomposed with water, alcohols, or ordinary carboxylic acids. In addition, the acetylacetonate group covers aluminum, which is the central metal, and the methyl group is oriented outward, so it has low polarity, so it is soluble in non-polar hydrocarbon solvents, and it is a decomposition product derived from highly polar triisobutylaluminum. Is difficult to be absorbed and included. However, because lactic acid is a stronger chelating agent than acetylacetone, even tris (acetylacetonato) aluminum can be chelated to a more polar compound [eg,
Al (OLc) ₃ : Lc is as described above]. Therefore, the by-product can be efficiently precipitated and separated.

Further, organic substances which are components other than metal components and inorganic substances (derivatives from the above-mentioned isopropylidene (9-fluorenyl) (cyclopentadienyl) group, organic substances derived from ligands such as acetylacetone, etc., alkanes and trityl groups) At least partially remains in the polymer solution, but can be removed when removing the solvent and the residual cyclic olefin or its hydrogenated product. The precipitated catalyst metal residue can be removed from the polymer solution by a conventional method such as filtration or centrifugal separation.

In the present invention, in order to remove the catalytic metal residue and the coloring component more highly and efficiently, the active hydrogen compound is added, and after the decomposition reaction, the reaction solution is treated with an adsorbent. You can do it. The adsorbent is not particularly limited, but acid clay, activated clay, activated carbon,
Diatomaceous earth, silica gel, alumina, silica alumina gel,
Zeolite and the like are preferably used. Examples of the treatment method include a method of adding an adsorbent to a polymer solution, mixing and stirring, and then removing the mixture by filtration or the like, and a method of flowing the polymer solution through a packed phase (packed column) of the adsorbent. At this time, since the metal component derived from the polymer solution has been substantially removed in the previous stage, the amount of the adsorbent used is very small in the case of mixing and stirring, and when the packed phase is used, the amount of the packed phase is reduced. The number of exchanges and regeneration is small. Industrially, a method of flowing a polymer solution through a packed phase of an adsorbent is advantageous.

When washing with an aqueous solution, acid,
A neutral or basic aqueous solution can be used, and one or more of these can be used stepwise. In this case, washing waste liquid is generated, but since the metal component derived from the polymer solution has been almost completely removed in the previous stage, the treatment of the waste liquid does not pose any problem.

The total amount of the transition metal element, aluminum element and lithium element contained in the cyclic olefin polymer thus obtained is preferably 5 ppm or less,
It is more preferably at most 3 ppm, particularly preferably at most 2 ppm. The transition metal element is 2p
pm or less, and particularly preferably 1 ppm or less. Aluminum element is 3ppm
Or less, and particularly preferably 1 ppm or less.

(Recovery of Polymer) The polymer solution from which the catalytic metal residue has been removed by the above steps is further recovered as a polymer through a solvent removing step. The solvent is removed by a device such as a heating vacuum concentrator or a vented extruder. Alternatively, the polymer can be recovered by putting the polymer solution into a usual poor solvent and separating the polymer by precipitation.

Various additives such as an antioxidant may be added to the cyclic olefin-based polymer obtained according to the present invention, if necessary. Examples of antioxidants include 2,6-di-
t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [2- (3,5-di-t-butyl) -4-Hydroxyphenyl) ethyl propione
G] methane, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], tris (2,4, -di-t-butylphenyl) phosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite and the like. Can be mentioned.

The cyclic olefin polymer obtained according to the present invention has a very high purity without substantially containing a polymerization catalyst residue, and therefore has various properties such as transparency, heat resistance, light resistance, dielectric properties and opportunity properties. It has excellent characteristics and can be suitably used as an optical material such as an optical disk substrate and a camera lens.

That is, according to the present invention, a cyclic olefin polymer having a total content of a transition metal element, an aluminum element and a lithium element of 5 ppm or less, a cyclic olefin polymer having an aluminum element content of 3 ppm or less, Also provided are the use of these polymers for optical materials.

According to the present invention, a catalyst residue is obtained from a cyclic olefin polymer solution obtained using a metallocene catalyst or a hydrogenated cyclic olefin copolymer solution obtained using a homogeneous hydrogenated solvent. It can be efficiently removed by a simple method that does not generate metal-containing waste liquid,
An extremely high purity copolymer can be obtained.

[0121]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.

Examples were carried out under an inert atmosphere such as argon or nitrogen, unless otherwise specified.

Toluene (solvent), dicyclopentadiene, norbornene, 8-ethylidenetetracyclo [4.
4.0.1 ^2.5 .1 ^7.10] -3-dodecene and triethylamine used was sufficiently dried perform distillation purification by a conventional method. As the metallocene, isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was purchased from Boulder Scientific and used as it was. As the ionic boron compound, trityl-tetrakis (pentafluorophenyl) borate was purchased from Tosoh Akzo Co., Ltd. and used as it was. Triisobutylaluminum was purchased from Tosoh Akzo Co., Ltd. at a concentration of 2 M in toluene and used as it was. Tris (acetylacetonate) cobalt, titanium tetrachloride, lactic acid aqueous solution and 2-hydroxy-2-methylpropionic acid were purchased from Wako Pure Chemical Industries, Ltd. and used as they were.

The items measured in the examples were measured by the following methods. Glass transition temperature (Tg (° C.)): TA Instrument
ents 2920 type DSC, temperature rise rate is 2
It was measured at 0 ° C./min. Molecular weight: 30 ° C. of a toluene solution having a concentration of 0.5 g / dL
Was measured for the reduced viscosity η _sp / c (dL / g). Hydrogenation rate: Quantified by ¹ H-NMR. JEOL JN
An MA-400 type nuclear magnetic resonance absorption apparatus was used. Residual metal concentration in the polymer: quantified by ICP emission spectrometry. Infrared absorption spectrum: Spectrometer 176 manufactured by PerkinElmer
It was measured by KBr method using OX. Ultraviolet-visible absorption spectrum: spectrometer U-32 manufactured by Hitachi, Ltd.
Measured using 0. A 1 cm cell was used for the measurement. The compensation cell contained toluene. Solid ¹³ C-NMR spectrum: DSX30 manufactured by Brooker
It measured using 0WB.

In the following Examples and Comparative Examples, the product of the mole number of the transition metal component and the oxidation number of the transition metal, the product of the organic aluminum compound and the oxidation number of aluminum (3) and, if necessary, the organic lithium The mole number of the compound represented by the formula (II), the mole number of water, and the mole number of the alcohol added to one equivalent of the sum of the product of the mole number of the compound and the oxidation number (1) of lithium are f ₁ and f, respectively. ₂ and f ₃ .

Reference Example 1 Tris (acetylacetonato) aluminum 0.97
g was dissolved in 300 g of toluene. The solution was heated to 100 ° C. and 0.62 g (f ₁ = 2.0) of 2-hydroxy-2-methylpropionic acid was added with stirring. afterwards,
The mixture was heated and stirred at the same temperature for 2 hours. The generated precipitate was separated by filtration to obtain 1.0 g of a colorless solid powder. The infrared absorption spectrum of this powder (FIG. 1) and the starting materials tris (acetylacetonato) aluminum (FIG. 2) and 2-hydroxy-2
-Methylpropionic acid (FIG. 3). From apparent produced powder from FIG have strong peak at 1730 cm ^-1 vicinity from strong peaks and 2-hydroxy-2-methylpropionic acid of 1540 cm ^-1 vicinity from tris (acetylacetonato) aluminum disappeared ,
The strong peak attributable to the carbonyl group of aluminum bonded with 2-hydroxy-2-methylpropionic acid is 162.
It was observed near 0 cm ^-1 . As is clear from the above, it was found that tris (acetylacetonato) aluminum was changed to aluminum 2-hydroxy-2-methylpropionate.

A similar experiment was conducted by adding 0.3 g of water in addition to the 2-hydroxy-2-methylpropionic acid used above, and a precipitate was obtained in the same manner as described above. The infrared absorption spectrum of the precipitate (FIG. 4) was the same as the infrared absorption spectrum of the precipitate (FIG. 1).

Instead of the 2-hydroxy-2-methylpropionic acid used above, ethylene glycol was used in 1.3.
A similar experiment was performed with the addition of g. However, no precipitation was observed.

A similar experiment was conducted by adding 0.4 g of acetic acid instead of the 2-hydroxy-2-methylpropionic acid used above. However, no precipitation was observed.

Reference Example 2 1.3 g of tris (acetylacetonato) aluminum
Was dissolved in 300 g of toluene. The solution was heated to 100 ° C., and 8.4 g of a 90% by weight lactic acid aqueous solution was added dropwise with stirring. Thereafter, the mixture was heated and stirred at the same temperature for 2 hours. The formed precipitate was separated by filtration to obtain 0.8 g of a colorless solid powder. The infrared absorption spectrum of this powder (FIG. 5) and the spectrum of the raw material tris (acetylacetonato) aluminum (FIG. 2) were compared. As is clear from the figure, a strong peak around 1540 cm ^-1 originating from the raw material disappeared from the resulting powder, and a strong peak based on the carbonyl group of aluminum lactate was observed around 1620 cm ^-1 instead. The infrared absorption spectrum of the obtained powder almost coincided with the infrared absorption spectrum of aluminum lactate. The solid ¹³ C-NMR of the powder shows CH of aluminum lactate.
Peaks based on _three groups,> CH- group and -COO- group were observed at around 23 ppm, around 63 ppm and around 180 ppm, respectively. As is clear from the above, it was found that tris (acetylacetonato) aluminum was changed to aluminum lactate. Ethylene glycol was used instead of the lactic acid aqueous solution used above.
A similar experiment was performed with the addition of 3 g. However, no precipitation was observed.

A similar experiment was conducted by adding 0.4 g of acetic acid instead of the lactic acid aqueous solution used above. However, no precipitation was observed.

Reference Example 3 0.8 g of triisobutylaluminum was added to 300 parts of toluene.
g. Subsequently, 0.30 g of cobalt tris (acetylacetylacetonate) was added to prepare a hydrogenation catalyst. The solution was heated to 100 ° C., and 8.4 g of 90% by weight lactic acid was added dropwise with stirring. Thereafter, the mixture was heated and stirred at the same temperature for 2 hours. The resulting precipitate was filtered off to obtain 1.9 g of a light pink solid powder. The infrared absorption spectrum of this powder (FIG. 6) was compared with the spectrum of raw material tris (acetylacetonato) aluminum (FIG. 2) and the spectrum of tris (acetylacetylacetonato) cobalt (FIG. 7). As can be seen, from the product powder has a peak of tris (acetylacetonato) aluminum peak of 1540 cm ^-1 vicinity from even tris (acetyl acetylacetonate) cobalt from the 1520 cm ^-1 also disappeared, instead A peak based on aluminum lactate was observed at 1620 cm ^-1 .

REFERENCE EXAMPLE 4 186 g of dicyclopentadiene, 1320 g of toluene and 3.6 g of triisobutylaluminum were added to a 3 L stainless steel reaction vessel. The atmosphere in the vessel was replaced with ethylene at normal pressure, 119 mg of isopropylene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride and 252 mg of trityl-tetrakis (pentafluoroborate) were added, and polymerization was carried out at 30 ° C. During the polymerization, ethylene at normal pressure was constantly supplied, and the ratio of the addition rate of dicyclopentadiene to the consumption rate of ethylene was 4%.
Dicyclopentadiene 16 at a rate such that it becomes 2:58
3 g were added. At a time (150 minutes) when the consumption of ethylene reached the molar amount corresponding to the total amount of added dicyclopentadiene of 350 g (150 minutes), the supply of ethylene was stopped to terminate the reaction.

The reduced viscosity (η _sp / c) measured at 30 ° C. using a 0.5% toluene solution of the polymer obtained by fractionating a small amount of the obtained solution and purifying it by a conventional method was 0.58 dL.
/ G, and the Tg measured using DSC was 155 ° C.

The resulting reaction solution (reaction solution a) was fed under pressure to a 10 L autoclave, and 3.0 g of tris (acetylacetylacetonato) cobalt and 4.8 g of triisobutylaluminum were added to the reaction solution. Thereafter, a hydrogenation reaction was performed at a hydrogen pressure of 45 atm for 120 minutes to obtain a reaction solution b. A small amount of the reaction solution was collected and precipitated in a large amount of methanol to obtain a measurement sample. ^{From the 1} H-NMR spectrum, the degree of hydrogenation of this polymer was 99.9% or more. The reduced viscosity (η _sp / c) measured at 30 ° C. using a 0.5% toluene solution was 0.45 dL / g. Also, D
Tg measured using SC was 151 ° C.

Example 1 At 100 ° C., 32.0 g of 2-hydroxy-2-methylpropionic acid (f ₁ = 2) was added to the reaction solution b obtained in Reference Example 4 (defined as reaction solution 1-1 for distinction). .0) was added with stirring and reacted at the same temperature for 2 hours. The reaction solution changed from black-brown to a cloudy pink slurry. The slurry was subsequently filtered. The apparatus used was a cylindrical filter having a diameter of 11 cm. The filter is Naslon NF-0
5 was filled with 5 cm of celite and covered with a flannel fabric. The filtration pressure was 4 kg / cm ² (gauge pressure). Filtration proceeded very smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, Zr: 0.
1 ppm or less, B: 0.2 ppm or less, Co: 0.4 pp
m and Al: 0.8 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. The UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer is 500 nm of the solution.
Was 99% or more.

Example 2 Reaction solution b obtained by the method of Reference Example 4 (reaction solution 2-
Defined as 1. ) In at 100 ° C. 2-hydroxy-2-methylpropionic acid 32.0g and water 2.8g (f ₁ = 2.
0, f ₂ = 1.0) with stirring, and reacted at the same temperature for 2 hours. The reaction solution changed from black-brown to a cloudy pink slurry. The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, based on the polymer, Zr: 0.1 ppm or less, B: 0.3 p
pm or less, Co: 0.5 ppm or less and Al: 1.2p
pm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, the transmittance at 500 nm of the solution was 99% or more.

Example 3 Reaction solution b obtained by the method of Reference Example 4 (reaction solution 3 for distinction)
Defined as 1. ) At 100 ° C was added with stirring with an aqueous lactic acid solution containing 28.9 g of lactic acid and 2.9 g of water (f ₁ = 2.0, f ₂ = 1.0), and reacted at the same temperature for 2 hours. The reaction solution changed from black-brown to pink turbid slurry (slurry-3-2). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. The filtration pressure was 4 kg / cm ² (gauge pressure). As shown by the curve A in FIG. 8, the filtration proceeded very smoothly, and about 1.6 kg of the slurry could be processed in 90 minutes. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless and transparent treatment liquid (treatment liquid 3-3). The residual metal in the liquid was measured by ICP emission spectrometry. As a result, with respect to the polymer, Zr: 0.1 ppm or less, B: 0.1 ppm or less, C
o: 0.3 ppm and Al: 0.7 ppm. As a result, it was found that the purity was extremely high. Especially Al
Was also found to be extremely low. Unreacted substances and the solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless and transparent polymer (purified polymer 3-4). No sublimation of aluminum tris (acetylacetonate) was observed during the treatment. 20w of the obtained polymer
In the ultraviolet-visible absorption spectrum of the t-% toluene solution, no strong absorption based on tris (acetylacetonato) aluminum was observed.

On the other hand, the precipitate (precipitate 3-5) was analyzed. The infrared absorption spectrum of the precipitate (FIG. 9)
Tris absorption (acetylacetonate) cobalt and tris (acetylacetonate), respectively 1520 cm ^-1 and near 1540 cm ^-1 vicinity based on aluminum was not observed at all, a strong absorption based on lactate was observed instead. In addition, in the solid ¹³ C-NMR spectrum of the precipitate (FIG. 10), a peak based on lactate was 23 pp.
m (CH ₃ ), 63 ppm (> CH-) and 180 ppm (-COO-). These results indicate that the catalytic components used in large quantities, tris (acetylacetonato) cobalt and triisobutylaluminum, are effectively precipitated as lactate.

Example 4 Reaction solution b obtained by the method of Reference Example 4 (reaction solution 4-
Defined as 1. ) Was added at 100 ° C. with stirring while a solution containing 21.7 g of lactic acid and 2.9 g of water (f ₁ = 1.5, f ₂ = 1.0) was reacted at the same temperature for 2 hours. The reaction solution was a black-brown to pink turbid slurry (Slurry-4).
-2). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. As shown by the curve B in FIG. 8, the filtration proceeded very smoothly.
The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 4-3). The residual metal in the solution was measured by ICP published analysis. As a result, based on the polymer, Zr: 0.1 ppm or less, B: 0.1 ppm
Hereinafter, Co was 0.6 ppm and Al was 0.9 ppm. As a result, it was found that the purity was extremely high.
Unreacted substances and the solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer (purified polymer 4-4). During the treatment, tris (acetylacetonate)
No sublimation of aluminum was observed. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. The transmittance of the solution at 500 nm was 99% or more.

On the other hand, the precipitate (precipitate 4-5) was analyzed. The infrared absorption spectrum of the precipitate showed that each of the precipitates was based on tris (acetylacetonato) cobalt and tris (acetylacetonato) aluminum.
Peak peak and 1640 cm ^-1 vicinity of 20 cm ^-1 vicinity was not observed at all, a strong absorption based on lactate was observed in the vicinity of 1620 cm ^-1 instead. These results indicate that the highly used catalyst components tris (acetylacetonato) cobalt and triisobutylaluminum are effectively precipitated as lactate.

Example 5 Reaction solution b obtained by the method of Reference Example 4 (reaction solution 5-
Defined as 1. ) At 100 ° C. was added with stirring while a solution containing 28.9 g of lactic acid and 2.9 g of water (f ₁ = 2.0, f ₂ = 1.0) was reacted at the same temperature for 2 hours. The reaction solution changed from black-brown to a pink turbid slurry.
The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1, and a filtrate was obtained. ICP for residual metal in the liquid
It was measured by emission spectroscopy. As a result, Zr: 0.3 ppm or less, B: 0.4 ppm or less, C
o: 0.8 ppm and Al: 2.7 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. No sublimation of aluminum tris (acetylacetonate) was observed during the treatment. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed.

On the other hand, the precipitate was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed. These results indicate that the highly used catalyst components tris (acetylacetonato) cobalt and triisobutylaluminum are effectively precipitated as lactate.

Example 6 Reaction solution a obtained by the method of Reference example 4 (reaction solution 6-
Defined as 1. ) At 100 ° C. with 5.0 g of lactic acid and 1.0 g of water
And 3.5 g of ethylene glycol (f ₁ =
1.0, f ₂ = 1.0, f ₃ = 1.0) were added with stirring, and reacted at the same temperature for 2 hours. The reaction solution changed from a pale yellow solution to a pale yellow cloudy slurry. The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, based on the polymer, Zr: 0.1 ppm or less, B: 0.1 ppm or less, and Al: 0.5 ppm. As a result, it was found that the purity was extremely high. The treated liquid was precipitated in a large amount of methanol, and the deposited precipitate was separated by filtration and dried to obtain a colorless flaky polymer. 20 wt-% of the obtained polymer
No strong absorption was observed in the ultraviolet-visible absorption spectrum of the toluene solution, and the transmittance of the solution at 500 nm was 9%.
9% or more.

On the other hand, the precipitate was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed.

Reference Example 5 The flake polymer obtained in Example 6 was dissolved in 1320 g of toluene introduced into an autoclave. The air in the autoclave containing the solution was sufficiently replaced with nitrogen gas. 3.0 g of tris (acetylacetylacetonato) cobalt and 4.8 g of triisobutylaluminum were added to the solution. Then, at a hydrogen pressure of 45 atm, 12
A hydrogenation reaction was performed for 0 minutes to obtain a reaction solution. A small amount of the reaction solution was collected and precipitated in a large amount of methanol to obtain a measurement sample. ^{From the 1} H-NMR spectrum, the degree of hydrogenation of this polymer was 99.9 or more. The reduced viscosity (η _sp / c) measured at 30 ° C. using a 0.5% toluene solution is 0.47.
dL / g. The Tg measured by DSC is 14
9 ° C.

Example 7 A solution containing 17.6 g of lactic acid and 1.8 g of water (f ₁ = 2, f ₂ = 1) was added to the reaction solution obtained in Reference Example 5 at 100 ° C. while stirring. For 2 hours. The reaction solution is
The solution turned from a dark brown solution to a pink cloudy slurry.
The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, Co: 0.4 ppm or less and Al:
0.7 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. No sublimation of aluminum tris (acetylacetonate) was observed during the treatment. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. In addition, 50 of the solution
The transmittance at 0 nm was 99% or more.

On the other hand, the precipitate was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed. These results indicate that the highly used catalyst components tris (acetylacetonato) cobalt and triisobutylaluminum are effectively precipitated as lactate.

Reference Example 6 To a 2 L autoclave, 320 g of norbornene, 1280 of toluene, and 44 ml of a toluene solution of 2M aluminoxane were added. The air in the autoclave was pressurized with 4 atm of ethylene which was replaced with ethylene at normal pressure, and 150 mg of isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was added.
44 ml of M aluminoxane solution was added, and polymerization was carried out at 30 ° C. During the polymerization, 3 atm of ethylene was constantly supplied to obtain a reaction solution. The ethylene-norbornene copolymer obtained here has a Tg of 182 ° C. and a reduced viscosity of 1.23 dL / g.
And the molar fraction of norbornene units in the copolymer was 57%.

Example 8 An aqueous solution of lactic acid containing 31.8 g of lactic acid and 3.2 g of water at 100 ° C. (f ₁ = 2.0, f ₂ = 1.10) was added to the reaction solution obtained in Reference Example 6 at 100 ° C.
0) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution changed from a pale yellow solution to a pale yellow cloudy slurry. The slurry was subsequently filtered.
Filtration was performed in the same manner as in Example 1. Filtration is Example 1
It proceeded very smoothly as well. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid.
The residual metal in the solution was measured by ICP published analysis. As a result, based on the polymer, Zr: 0.1 ppm or less,
And Al: 2.1 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, the transmittance of the solution at 500 nm was 99% or more. On the other hand, the precipitate was analyzed. In the infrared absorption spectrum of the precipitate, a peak based on lactate was observed.

Comparative Example 1 The reaction solution b obtained by the method of Reference Example 4 (reaction solution 7-
Defined as 1. ) Was added at 100 ° C with stirring while a solution containing 115.4 g of lactic acid and 11.6 g of water (f ₁ = 8, f ₂ = 4) was reacted at the same temperature for 2 hours. The reaction solution is
The color changed from blackish brown to pink, and turned into a noticeably cloudy slurry. In addition, a supersaturated lactic acid aqueous solution phase-separated. From the slurry, the lactic acid aqueous solution was looked into, and the toluene phase was subjected to a filtration treatment. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the solution was measured by ICP published analysis. As a result, based on the polymer, Zr: 5 ppm, B: 8 ppm
Hereinafter, Co was 15 ppm or less and Al was 32 ppm. The purity of the polymer obtained from this result was not always high. Unreacted substances and the solvent were distilled off (flushing treatment) from the treatment liquid to obtain a light brown polymer.

Comparative Example 2 Reaction solution b obtained by the method of Reference Example 3 (reaction solution 8-
Defined as 1. ) At 100 ° C contains 0.75 g of lactic acid and 0.2 g of water (f ₁ = 0.05, f ₂ = 0.00).
5) was added with stirring, and reacted at the same temperature for 2 hours. However, the resulting reaction solution remained brown. The slurry was subsequently filtered. But,
Filtration was extremely difficult and the filtrate still remained brown.

[0153] stainless steel reactor vessel Reference Example 7 3L 8- ethylidene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3- dodecene 285 g, toluene 1100 g, 1-hexene 4.2
g, 7.5 g of triethylamine and 15 g of triisobutylaluminum, and 2.8 g of titanium tetrachloride were further added, followed by polymerization at -10 ° C for 2 hours to obtain a solution of a ring-opened polymer. A small amount of the obtained solution was fractionated and purified using a 0.5% toluene solution of a polymer obtained by a conventional method.
The reduced viscosity (η _sp / C) measured at 0.6 ° C. is 0.65 dL / g.
And the Tg measured using DSC was 186 ° C.

Example 9 7.8 g of lactic acid and 1.0 g of water (f ₁ = 0.30, f ₂ = 0.20) were added to the reaction solution obtained in Reference Example 7 at 100 ° C. with stirring, and The reaction was performed at a temperature for 2 hours. The reaction solution changed from black-brown to black turbid slurry. The slurry was subsequently filtered. Filtration was performed in the same manner as in the example. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, for the polymer,
Ti: 0.4 ppm or less and Al: 2.6 ppm. As a result, it was found that the purity was extremely high. The treated liquid was added to a large amount of ethanol, and the deposited precipitate was separated by filtration and dried to obtain a colorless flaky polymer. The UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer shows that the transmittance at 500 nm of the solution is 99%.
% Or more.

Reference Example 8 The flaky polymer obtained in Example 9 was dissolved in 1100 g of toluene introduced into an autoclave. The air in the autoclave containing the solution was sufficiently replaced with nitrogen gas. 3.0 g of tris (acetylacetonate) cobalt and 4.8 g of triisobutylaluminum were added to the solution, and a hydrogenation reaction was performed at 45 atm of hydrogen pressure for 120 minutes.
A reaction solution was obtained. The hydrogenation ratio of the polymer obtained by fractionating a small amount of the reaction solution and purifying it by a conventional method was 99.9% or more from the ¹ H-NMR spectrum. The reduced viscosity (η _sp / C) measured at 30 ° C. using a 0.5% toluene solution is 0.5.
3 dL / g, and the Tg measured by DSC was 14 dL / g.
It was 0 ° C.

Example 10 An aqueous solution of lactic acid containing 17.6 g of lactic acid and 1.8 g of water at 100 ° C. (f ₁ = 2.0, f ₂ = 1.10) was added to the reaction solution obtained in Reference Example 8 at 100 ° C.
0) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution changed from black-brown to a cloudy pink slurry. The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid. The residual metal in the liquid was measured by ICP emission spectrometry. As a result, Ti: 0.2 ppm or less and Co:
The content was 0.5 ppm or less and Al: 0.8 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer. The UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer is 50% of the solution.
The transmittance at 0 nm was 99% or more.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a colorless solid obtained in Reference Example 1.

FIG. 2 is an infrared absorption spectrum of aluminum tris (acetylacetonate).

FIG. 3 is an infrared absorption spectrum of 2-hydroxy-2-methylpropionic acid.

FIG. 4 is an infrared absorption spectrum of another colorless solid obtained in Reference Example 1.

FIG. 5 is an infrared absorption spectrum of the colorless solid obtained in Reference Example 2.

FIG. 6 is an infrared absorption spectrum of the colorless solid obtained in Reference Example 2.

FIG. 7 is an infrared absorption spectrum of tris (acetylacetonato) cobalt.

FIG. 8 shows a slurry 3 obtained in each of Examples 3 and 4.
2 is a filtration curve of Slurry 4-2. Curves A and B in the figure are filtration curves of the slurry 3-2 and the slurry 4-2, respectively.

FIG. 9 is an infrared absorption spectrum of a precipitate (precipitate 3-5) obtained in Example 3.

FIG. 10: Precipitate obtained in Example 3 (Precipitate 3-5)
3 is a solid-state NMR spectrum of the sample.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 232/00 C08F 232/00 C08G 61/08 C08G 61/08 (72) Inventor Michio Yamaura Hino-shi, Tokyo 4-3-2 Asahigaoka Teijin Tokyo Research Center Co., Ltd. (72) Inventor Kiyonari Hashizume 4-3-2 Asahigaoka, Hino City, Tokyo Teijin Co., Ltd. Tokyo Research Center (72) Inventor Hideaki Nitta Tokyo 4-3-2 Asahigaoka, Hino-shi Teijin Co., Ltd. Tokyo Research Center (72) Inventor Masaki Takeuchi 4-3-2 Asahigaoka, Hino-shi Tokyo Metropolitan Tokyo Research Center Co., Ltd. (72) Inventor Kaoru Iwata Tokyo Metropolitan Government 4-3-2 Asahigaoka, Hino City Teijin Tokyo Research Center F-term (reference) 4J028 AA01A AB01A AC08A AC 09A AC10A AC26A AC27A AC28A AC36A BA01B BA02B BB01B BC13B BC15B BC25B EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB18 EC02 FA02 GA04 GA19 4J032 CA34 CA35 CA36 CA38 CA43 CA45 CA46 A03 CD03 A03 CD03 ACO3 AA16P AA17P AA19P AR11Q AR22Q FA09 FA10 FA19 GA02 GA05 GA06 GA08 GA22 JA32 JA33 JA36

Claims (29)

[Claims] 1. A method for producing a cyclic olefin polymer using a transition metal catalyst component soluble in an organic solvent and an organoaluminum compound as a catalyst, wherein the reaction product solution contains one hydroxyl group and one carboxyl group in the molecule. Having at least one compound selected from the group consisting of α-oxy acids, β-oxy acids and derivatives having a hydroxyl group substituted with an alkoxyl group, thereby precipitating a compound containing a transition metal and aluminum. A method for producing a cyclic olefin-based polymer, wherein the precipitate is separated by filtration. 2. The method of claim 1, wherein the transition metal catalyst component soluble in an organic solvent is selected from the group consisting of a metallocene catalyst component, a metathesis catalyst component and a Ziegler catalyst component. 3. The method of claim 2 wherein the transition metal of the metallocene catalyst component is selected from the group consisting of zirconium, titanium and hafnium. 4. The method of claim 2, wherein the transition metal of the metathesis catalyst component is selected from the group consisting of titanium, molybdenum, tungsten and rhenium. 5. The method of claim 2, wherein the transition metal of the Ziegler catalyst component is selected from the group consisting of vanadium, cobalt and nickel. 6. The method according to claim 1, wherein the organoaluminum compound is selected from the group consisting of an alkylaluminum compound and an alkylaluminoxane compound. 7. The cyclic olefin polymer is represented by the following formula (I): [In the formula (I), n is 0 or 1, m is 0 or a positive integer, p is 0 or 1, R ^{1 to} R ²⁰ are the same or different, and represent a hydrogen atom, a halogen atom, a carbon atom, Number 6 ~
An aromatic hydrocarbon group of 10 or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and an alkylidene group formed by R ¹⁷ and R ¹⁸ or by R ¹⁹ and R ²⁰ ; And R ¹⁷ or R ¹⁸ and R ¹⁹ or R ²⁰ may form a ring, and the ring may have a double bond or an aromatic ring. The process according to claim 1, which contains polymerized units of the cyclic olefin to be produced. 8. An α-hydroxy acid or β-oxy acid having one hydroxyl group and one carboxyl group in the molecule, respectively, and derivatives obtained by substituting the hydroxyl group with an alkoxyl group are represented by the following formula (II): [Where q is 0 or 1, R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² , R ²³ , R
²⁴ and R ²⁵ are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group]. 9. The method according to claim 1, wherein the compound represented by the formula (II) has a boiling point of about 200 ° C. or less at 10 mmHg. 10. The compound represented by the above formula (II) is converted into the number of moles of the transition metal catalyst component and the oxidation number of the transition metal determined for the transition metal catalyst component and the organoaluminum compound contained in the reaction system. 2. The method according to claim 1, wherein 0.1 to 5 moles are added to 1 equivalent of the sum of the product of the number of moles of the organoaluminum compound and the number of oxidation of the aluminum metal (3). 11. The method according to claim 1, wherein a compound selected from the group consisting of water and alcohol is added in addition to the compound represented by the formula (II). 12. The process according to claim 11, wherein water is added in an amount of 0 to 9.9 mol based on the same standard as described in claim 10. 13. The method according to claim 11, wherein the alcohol is added in an amount of 0 to 5 mol based on the same standard as described in claim 10. 14. A reaction for producing a cyclic olefin-based polymer is performed by reacting an α-olefin having 2 or more carbon atoms with a cyclic olefin in the presence of a polymerization catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst. The method according to claim 1, wherein the reaction is a reaction for addition copolymerization in a hydrocarbon solvent. 15. After the addition copolymerization reaction is carried out, a hydrogenation catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst is added to the obtained homogeneous polymerization reaction solution, and hydrogenation is carried out. Claim 14
The method described in. 16. The method according to claim 14, wherein the metallocene-based catalyst is a combination of a metallocene catalyst component, an ionic boron compound and an alkylaluminum compound, or a combination of a metallocene catalyst component and an alkylaluminoxane. 17. The method according to claim 15, wherein the metallocene-based catalyst comprises a metallocene-based catalyst component and organolithium. 18. The number of moles of the transition metal catalyst component and transition metal required for the transition metal catalyst component, the organoaluminum compound and the alkyl lithium contained in the reaction system, and the compound represented by the formula (II) and water. And the product of the number of moles of the organoaluminum compound and the number of oxidations of the aluminum metal (3) and the product of the number of moles of the alkyl lithium and the number of oxidations of the lithium metal (1) are equivalent to 1 equivalent. 18. The method according to claim 17, wherein 0.2 to 10 moles are added. 19. The Ziegler catalyst is a combination of a Ziegler catalyst component selected from the group consisting of tris (acetylacetonato) cobalt and bis (acetylacetonato) nickel and alkylaluminum.
The method described in. 20. A reaction for producing a cyclic olefin-based polymer is carried out by converting a cyclic olefin into a polymer in the presence of a metathesis-based catalyst.
2. A reaction for ring-opening polymerization in a hydrocarbon solvent.
The method described in. 21. After the ring-opening polymerization is carried out, a hydrogenation catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst is added to the obtained homogeneous polymerization reaction solution, and hydrogenation is carried out. 20. The method according to 20. 22. The method of claim 20, wherein the metathesis-based catalyst comprises a combination of a metathesis catalyst component and an aluminum alkyl. 23. The method according to claim 21, wherein the metallocene-based catalyst comprises a metallocene-based catalyst component and organolithium. 24. The transition metal catalyst component, the number of moles of the transition metal catalyst component required for the transition metal catalyst component, the organoaluminum compound and the alkyl lithium contained in the reaction system and the transition metal And the product of the number of moles of the organoaluminum compound and the number of oxidations of the aluminum metal (3) and the product of the number of moles of the alkyl lithium and the number of oxidations of the lithium metal (1) are equivalent to 1 equivalent. 22. The method of claim 21 wherein from 0.2 to 10 moles are added. 25. The Ziegler-based catalyst is a combination of a Ziegler catalyst component selected from the group consisting of tris (acetylacetonato) cobalt and bis (acetylacetonato) nickel with alkylaluminum.
The method described in. 26. After filtering the precipitate, the obtained reaction solution is subjected to either (1) contact with an adsorbent or (2) washing with an aqueous solution, and then the reaction solvent is removed. 2. The method of claim 1, wherein said removing is performed. 27. A cyclic olefin polymer having a total content of a transition metal element, an aluminum element and a lithium element of 5 ppm or less. 28. A cyclic olefin polymer having a content of aluminum element of 3 ppm or less. 29. Use of the cyclic olefin polymer according to claim 27 or 28 for an optical material.