MXPA00003656A - Cycloolefin polymer reduced in catalyst residue content, use thereof, and process for producing the same - Google Patents

Abstract

A cycloolefin polymer reduced in the content of catalyst residues;and use thereof as an optical material. The catalyst used in polymerization and/or hydrogenation for producing a cycloolefin polymer is efficiently decomposed by adding at least one compound selected from the group consisting of a-hydroxy acids and b-hydroxy acids each having one hydroxyl group and one carboxyl group in the molecule and their derivatives in each of which the hydroxyl group has been replaced with an alkoxyl group. The decomposition products are insolubilized in the reaction solvent used in the polymerization and/or hydrogenation and are thus efficiently precipitated and removed.

Description

CYCLOOLEFIN POLYMER WITH REDUCED CONTENT OF CATALYST RESIDUES, ITS USE, AND PROCESS FOR ITS PRODUCTION TECHNICAL FIELD The present invention relates to a cyclic olefin polymer and to applications and production method thereof. More particularly, it relates to a cyclic olefin polymer that substantially does not contain catalyst residue and to applications and production process thereof. BACKGROUND OF THE ART Cyclic olefin polymers having a bulky cyclic olefin as one of the constituent elements are a synthetic resin excellent in transparency, heat resistance, chemical resistance, solvent resistance, moisture resistance, dielectric characteristics and Various mechanical properties and are widely used in numerous fields. These cyclic olefin polymers can be classified mainly into addition copolymers, ring-opened copolymers as well as hydrogenated copolymers, depending on the structure. The addition copolymers are produced by the copolymerization by the addition of a cyclic olefin and an alpha-olefin in a hydrocarbon solvent in the presence of a catalyst selected from a Ziegler catalyst and a metallocene catalyst. The ring-opened polymers are produced by the ring-opening polymerization of a cyclic olefin in a hydrocarbon solvent in the presence of a metathesis catalyst. The hydrogenated polymers are produced by the reaction of the double bonds between carbons contained in an addition copolymer or an open ring copolymer produced from a cyclic olefin containing two or more double bonds between carbons with hydrogen in the presence of a selected catalyst between a Ziegler catalyst and a metallocene catalyst to saturate the double bonds. The thermal resistance, weather resistance and light resistance of a cyclic olefin polymer can be further improved by saturation of the double bonds. In the production process of a cyclic olefin polymer, the removal of a catalyst metal is an extremely important step to maintain properties such as transparent, weather resistance, moisture resistance, and thermal resistance of a resin. The following methods have been proposed to date to remove the catalyst metal: (1) a method comprising the steps of injecting a polymer solution into a large amount of a lean solvent to deposit a copolymer precipitate and wash the precipitate with the solvent poor; (2) a method comprising the steps of washing a polymer solution with water containing an acid to extract and remove the catalyst residue (see JP-A 2 24319 and JP-A 6-100668); (3) a method comprises the steps of washing a polymer solution with water containing an alcohol or the like to extract and remove the catalyst residue (see JP-A 4-45103 and JP-A 6-228235); (4) a method comprising the steps of adding an oxidizing agent or a basic compound to a polymer solution to extract and remove the catalyst residue with a lean solvent (see JP-A 7-109310); and (5) a method comprising the steps of adding an alcohol, water and the like to a polymer solution, also adding an adsorbent and a filter aid there, and removing the catalyst residue by filtration or centrifugation. (see JP-A 3-66725, JP-A 4-161421 and JP-A 4- 363312). As for method (1), the poor solvent must be used at least several times higher than the polymer solution, which is a significant load in terms of equipment and cost when carried out on an industrial scale, including the recovery of the poor solvent, and the purification efficiency is not so high. Regarding methods (2), (3) and (4), a residual solution containing a relatively large amount of a catalyst metal is generated., thus bleaching a large waste problem of the residual solution. Regarding method (5) even though no significant amount of residual solution is produced, the purification efficiency is not so high unless large amounts of adsorbent and filter aid are used, a smooth filtration is difficult to carry There are problems with the disposal of the filter aid and the recovery of the polymer. Generally speaking, the catalyst components used to produce a cyclic olefin polymer include an organic aluminum compound such as alkylaluminium or alkylaluminoxane, and the amount of organic aluminum compound is much greater than the amount of the other catalyst components. . The organic aluminum compound reacts extremely easily with water, alcohol or acid and becomes insoluble in a hydrocarbon solvent used in the polymerization reaction. However, its reaction product is generally separated in the form of a gel containing a large amount of solvent and, in most cases, it appears to be a homogeneous reaction solution with the naked eye. Accordingly, if the reaction solution is filtered directly, the filter is capped and it is almost impossible to obtain a smooth filtration. Therefore, an adsorbent and a filter aid should be used in most cases. PRESENTATION OF THE INVENTION It is an object of the present invention to provide a process for the production of a cyclic olefin polymer having a small content of a catalyst residue, which generates almost no residual solution containing a large amount of metal and can remove the catalyst residue efficiently through simple means. It is another object of the present invention to provide a process for producing a cyclic olefin polymer having a small content of a catalyst residue, which can remove the catalysts used for polymerization and / or hydrogenation reactions for the production of the cyclic olefin polymer. by decomposing the catalysts efficiently and to render the decomposition products insoluble in a reaction solvent used for the polymerization and / or hydrogenation reaction to efficiently precipitate them. It is another object of the present invention to provide a process for producing a cyclic olefin polymer having a small content of a catalyst residue, which substantially does not generate any by-product of colorful decomposition through the decomposition of the above catalysts or which can remove the colorful decomposition product by its adsorption to catalyze decomposition products or include it in the catalyst decomposition products as it is generated. It is a further object of the present invention to provide a process for producing a cyclic olefin polymer having a small content of a catalyst residue, which can produce the aforementioned catalyst decomposition products not in the form of a remarkably swollen gel but in form of a solid that can be easily filtered. It is a further object of the present invention to provide a product for producing a cyclic olefin polymer having a small content of a catalyst residue, which can almost completely remove even a stable compound such as tris (acetylacetonate) aluminum which inevitably occurs collaterally when an acetylacetonate complex and an organic aluminum compound are used. It is a further object of the present invention to provide a cyclic olefin polymer having a small content of catalyst residue. It is another object of the present invention to offer the use of the cyclic olefin polymer of the present invention as an optical material.

Other objects and advantages of the present invention will be apparent from the following description. In accordance with the present invention, first the aforementioned objects and advantages of the present invention are achieved through a process for the production of a cyclic olefin polymer in the presence of a transition metal catalyst component soluble in an organic solvent. and an organic aluminum compound as catalysts, the process comprises the steps of adding at least one compound selected from the group consisting of an alpha-oxyacid and beta-oxyacid having a hydroxyl group and a carboxyl group in the molecule, and derivatives obtained by substitution of the hydroxyl groups with alkoxyl groups, to a reaction product to precipitate a compound containing a transition metal and aluminum, and to separate the precipitate by filtration. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the absorption spectrum of infrared light of an achromatic solid obtained in reference example 1; Figure 2 shows the infrared light absorption spectrum of tris (acetylacetonate) aluminum; Figure 3 shows the infrared light absorption spectrum of 2-hydroxy-2-methylpropionic acid; Figure 4 shows the infrared light absorption spectrum of another achromatic solid obtained in reference example 1; Figure 5 shows the absorption spectrum of infrared light of an achromatic solid obtained in reference example 2; Figure 6 shows the absorption spectrum of infrared light of an achromatic solid obtained in reference example 2; Figure 7 shows the infrared light absorption spectrum of tris (acetylacetonate) cobalt; Figure 8 shows the filtration curves of pulp 3-2 and pulp 4-2 obtained in examples 3 and 4, where a curve A and a curve B correspond respectively to pulp 3-2 and pulp 4-2, respectively; Figure 9 shows the infrared light absorption spectrum of a precipitate (precipitate 3-5) obtained in Example 3; and Figure 10 shows the solid NMR spectrum of a precipitate (precipitate 3-5) obtained in Example 3. The process of the present invention will be described in detail below. (organic aluminum compound) The organic aluminum compound used in the present invention is a compound having at least one aluminum-carbon bond in the molecule. Illustrative examples of the organic aluminum compound include trialkylaluminum compounds such as for example triethylaluminum and triisobutylaluminum; organic compounds of aluminum alkoxide such as diethylaluminum ethoxide, diisobutylaluminum butoxide and ethylaluminum sesquiethoxide; organic oxyaluminium compounds such as for example methylaluminoxane and ethylaluminoxane; and organic aluminum halide compounds such as for example diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, and isobutylaluminum dichloride. (transition metal catalyst component) The transition metal catalyst component that is employed in the present invention is not particularly limited insofar as it has the catalytic function of producing a cyclic olefin polymer in the presence of an organic compound of aluminum and is soluble in an organic solvent. The transition metal catalyst component is preferably a metallocene catalyst component, metathesis catalyst component or Ziegler catalyst component. Both the metallocene catalyst component and the Ziegler catalyst component are the catalyst components of a catalyst for an addition copolymerization reaction between a cyclic olefin and an alpha-olefin and a hydrogenation reaction of a polymer, and the component of metathesis catalyst is the catalyst component of a catalyst for a ring opening polymerization reaction of a cyclic olefin. The metallocene catalyst component, metathesis catalyst component and Ziegler catalyst component will be described in details below. (metallocene catalyst component) The metallocene catalyst component used in the present invention can be classified among the components suitable for addition copolymerization and the components suitable for use as a hydrogenation catalyst according to the reaction system. The metallocene catalyst components suitable for addition copolymerization are preferably represented by the following general formula (III): where "M is a transition metal selected from group 4 of the periodic table, R29 and R30 are the same or different and are each a hydrogen atom, halogen atom, saturated or unsaturated hydrocarbon group having from 1 to 12 carbon atoms, alkoxide group having 1 to 12 carbon atoms or aryloxy group having 6 to 12 carbon atoms, R27 and R28 are the same or different and are each a monocyclic or polycyclic hydrocarbon group which can form a sandwich structure with the central metal M, and R26 is a bridge to connect the group R27 with the group R28 and is selected within the following structures: R3 R31 R33 R31 R33 R31 I -C - C - Si - - c - o- > 32 0 R "RJ i- R3 RJ! -C- • c- -Si- -Si-> 34 R31 R31 R33 RJ? 1 I i I -Si- Si - Si- -Yi O- R32 R32 R3 < 1" -s- -so2 - C- II II O 0 (R31 to R34 are the same or different and are each 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 group aryloxy having from 6 to 12 carbon atoms, provided that R31 and R32 or R33 and R34 can form a ring). In the metallocene catalyst component represented by the above formula (III), the central metal M is the transition metal of group 4 such as for example zirconium, titanium or hafnium, among which zirconium is especially preferred from the perspective of the catalytic activity. R29 and R30 may be the same or different and is preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom (especially chlorine atom). Preferred cyclic hydrocarbon groups such as R27 and R28 are a cyclopentadienyl group, indenyl group and fluorenyl group. They may be substituted by a hydrogen atom, an alkyl group such as, for example, a methyl group, an ethyl group, isopropyl group or tert-butyl group, or a substituent such as, for example, a phenyl group or a benzyl group. R31 to R34 are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 26 is preferably a lower alkylene group such as a methylene group, an ethylene group or a propylene group, an alkylidene group such as, for example, isopropylidene, a substituted alkylene group such as, for example, diphenylmethylene, a silylene group, or a substituted silene group, such as, for example, dimethylsilylene or diphenylsilylene. The following compounds can be mentioned as examples of the metallocene whose central metal M is zirconium: Di-ethylsilylene-bis (1-indenyl) zirconium dichloride, diphenylsilylene-bis (1-indenyl) zirconium dichloride, dibenzylsilylene-dichloride (1- indenyl) zirconium, diphenylsilylene-bis (1-indenyl) zirconium dichloride, dedibenzylsilylene-bis (1-indenyl) zirconium dichloride, methylene-bis (1-idenyl) 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, 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, diclo diphenylmethylene-bis [1- (2,4-, 7-trimethyl) idenyl] zirconium oxide, isopropylidene-bis [1- (2,4-, 7-trimethyl) indenyl] zirconium dichloride, phenyl ethyl silylene-bis dichloride [1] - (2, 4, 7-trimethyl) indenyl] zirconium, dimethylsilylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, diphenylsilylene-bis [1- (2,4-dimethyl) indenyl] dichloride] zirconium, 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 dichloride [1. (2, -dimethyl) indenyl] zirconium, isopropylidene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, phenylmethylsilylene-bis [1 (2,4-dimethyl) indenyl] zirconium dichloride, dimethylsilylene dichloride -bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium, diphenylsilylene-bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium dichloride, dibenzylsilylene-bis dichloride [1 - (4, 5, 6, 7-tetrahydro) indenyl] zirconium, methylene-bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium dichloride, ethylene-bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium, diphenylmethylene-bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium dichloride, isopropylidene-bis [1- (4, 5, 6, 7-tetrahydro) indenyl] zirconium, phenylmethylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, dimethylsilylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylsilylene dichloride (9) -fluorenyl) (cyclopentadienyl) zirconium, dibenzylsilylene- (9-fluorenyl) dichloride (cyclopentadienyl) zirconium, methylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, ethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene dichloride- (9) -fluorenyl) (cyclopentadienyl) zirconium, phenylmethylsilylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, di-ethylsilylene dichloride (9. fluorenyl) [1- (3-tert-butyl) cyclopentadienyl) zirconium, diphenylsilylene- (9-fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, dibenzylsilylene- (9-fluorenyl) dichloride [1 - (3-tert-butyl) cyclopentadienyl) zirconium, methylene- (9-fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, ethylene- (9-fluorenyl) dichloride [1- (3- tert-butyl) cyclopentadienyl] zirconium, diphenyl ethylene- (9-fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-tert-butyl ) cyclopentadienyl] zirconium, phenylmethylsilylene- (9-fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, dimethylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, dichloride diphenylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium, dibenzylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, methylene- (9-fluorenyl) dichloride [1- (3-methyl) cyclopentadienyl] zirconium, ethylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, diphenylmethylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene dichloride (9) -fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium, phenylmethylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, dimethylsilylene- [9- (2,7- tert-butyl) fluorenyl] (cyclopentadienyl) zirconium, diphenylsilylene- [9- (2,7-di-tert-butyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, dibenzylsilylene d- [9- (2,7- tert-butyl) fluorenyl] (cyclopentadienyl) zirconium, methylene- [9- (2,7-di-tert-butyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, ethylene- [9- (2,7- tert-butyl) fluorenyl] (cyclopentadienyl) zirconium, diphenylmethylene- [9- (2,7-di-tert-butyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, isopropylidene- [9- (2,7- di- tert-butyl) fluorenyl] (cyclopentadienyl) zirconium, dichloride of f enylmethylsilylene- [9- (2,7-di-tert-butyl) fluorenyl] (cyclopentadienyl) zirconium, dimethylsilylene- (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 dichloride- (1-) indenyl) (cyclopentadienyl) zirconium, isopropylidene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- (1-indenyl)) cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, diphenylsilylene-bis (cyclopentadienyl) zirconium dichloride, dibenzylsilylene-bis (cyclopentadienyl) zirconium dichloride, methylene-bis dichloride (cyclopentadienyl) zirconium, ethylene-bis (cyclopentadienyl) zirconium dichloride, diphenylmethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene dichloride- ( 1-indenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium, isopropylidene- (9-fluorenyl) [1- (3-isopropyl) cyclopentadienyl] zirconium dichloride, isopropylidene- [1- (2, 4-dichloride , 7-tri ethyl) indenyl] (cyclopentadienyl) zirconium, ethylene- (cyclopentadienyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, ethylene- (cyclopentadienyl) [1- (3-phenyl) cyclopentadienyl dichloride] ] zirconium, isopribromide opylidene- (9-fluorenyl) (cyclopentadienyl) zirconium, dimethylsilylene-bis (1-indenyl) zirconium dibromide, and ethylene-bis (1-indenyl) methylzirconium monochloride. In the present invention, is especially preferred as the metallocene isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene- (9-fluorenyl) dichloride [1-] (3-methyl) cyclopentadienyl] zirconium, isopropylidene- (9-fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, ethylene dichloride bis (1-indenyl) zirconium, and isopropylidene-bis (1-indenyl) zirconium dichloride. The amount of the metallocene catalyst component can be determined in accordance with its polymerization activity. It is used in an amount of 10"6 to 10 ~ 2 mol, preferably 10-5 to 10-3 mol, per mol of the cyclic olefin added to a polymerization reaction system.The organic aluminum compound is preferably a composed of organic oxyaluminium such as alkylaluminoxane or trialkylaluminum, of the compounds presented in the above list When an alkylaluminoxane is used as the organic aluminum compound, it is used in combination with a metallocene catalyst component When a trialkylaluminum is used is used in combination with a metallocene catalyst component and an ionic boron compound The alkylaluminoxane can be represented by the general formula (IV) for a linear structure or by the general formula (V) in the case of a cyclic structure: (IV) where R35 to R40 are the same or different and are each an alkyl group having from 1 to 6 carbon atoms such as for example a methyl group, ethyl group, propyl group, or butyl group, phenyl group or benzyl group, preferably a a methyl group or an ethyl group and especially a methyl group; and m is an integer of 2 or more, preferably from 5 to 100. However, the exact structure of the alkylaluminoxane is not known. The alkylaluminoxane can be produced by a method conventionally produced, for example, by the reaction of a compound containing adsorbed water or a salt (such as copper sulphate hydrate) containing water of crystallization with an organic aluminum compound as per trialkylaluminum example in an inert solvent (such as toluene). The alkylaluminoxane may contain a small amount of an organic aluminum compound derived from the production method. The alkylaluminoxane has the function of alkylating the metallocene catalyst component and of further returning the cationic metallocene catalyst component, thereby obtaining a polymerization activity. The activation of the metallocene catalyst component is carried out in a solution, preferably by dissolving the metallocene catalyst component in an alkylaluminoxane solution. A solvent used for the activation is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon, more preferably toluene. The metallocene catalyst component is generally activated by the alkylaluminoxane before use in a polymerization reaction. The activation time is from one minute to 10 hours, preferably from 3 minutes to one hour. The activation temperature is -40 to 110 ° C, preferably from Q to 80 ° C. As for the ratio between the alkylaluminoxane and the metallocene catalyst component, the alkylaluminoxane is employed in an amount of 30 to 20,000 moles, preferably 100 to 5,000 moles, per mole of the metallocene catalyst component. The use of the alkylaluminoxane in too small a quantity based on the metallocene catalyst component can not provide sufficiently high polymerization activity. On the other hand, the use of too large a quantity of alkylaluminoxane, even though the polymerization activity is high, is not economic since it is expensive and makes the purification difficult after the polymerization.

Preferred organic aluminum compounds other than alkylaluminoxane include trialkylaluminum such as for example triethylaluminum or triisobutylaluminum. In this case, an ionic boron compound should be used in combination. The ionic boron compound is represented by any of the following general formulas (VI) a (IX): [R413C] + [BR424] "(VI) [R4? NH4-X]? BR424 G (VII) [R4? PH4-X]? BR424] (iix) 2 Li + [BR4?] (IX) where the R41 are the same or different and each of them is an aliphatic hydrocarbon group having from 1 to 8 carbon atoms or an aromatic hydrocarbon group having from 6 to 18 carbon atoms, the R42 are the same or different and are, each, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and x is 1, 2, 3, or 4. In the ionic boron compound represented by any of the above formulas (VI) to (IX), the R41 are preferably identical and each is an alkyl group such as, for example, methyl group, ethyl group, propyl group or butyl group, or an aryl group such as, for example, phenyl group. is a fluorinated or partially fluorinated aromatic hydrocarbon group, particularly a pentafluorophenyl group, x is 2 * 2 Preference 3. Illustrative examples of the compound include N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, trityl-tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) borate. The ionic boron compound has the function of returning the cationic metallocene catalyst component, and the organic aluminum compound has the function of alkylating the metallocene catalyst component. Accordingly, the polymerization activity can be obtained by the combination of these compounds. As for the ratio between the ionic boron compound and the metallocene catalyst component, the ion boron compound is employed in an amount of 0.5 to 10 moles, preferably 0.8 to 5 moles, more preferably 0.9 to 3. moles, per mole of the metallocene catalyst component. The organic aluminum compound is used in an amount of 2 to 500 moles per mol of metallocene. When the ionic boron compound is employed, there is a tendency in the sense that the required amount of the organic aluminum compound based on the metallocene catalyst component is much lower and the catalytic activity is much higher than when an alkylaluminoxane is employed as the organic aluminum compound. Accordingly, the use of the ionic boron compound is advantageous from an economic perspective because the amount of the metallocene catalyst component and the amount of the cocatalyst can be reduced and is also very profitable in terms of purification after polymerization. Meanwhile, a compound represented by the following general formula (X) is preferably used as the metallocene catalyst component suitable for a hydrogenation reaction, in addition to the compound represented by the above general formula (III).

R44 In the metallocene catalyst components represented by the above formulas (III) and (X), the central metal M is the transition metal of group 4 of the periodic table such as for example titanium, zirconium or hafnium, preferably titanium, from the perspective of catalytic activity. R 45 and R 46 may be the same or different and are preferably an alkyl group having from 1 to 8 carbon atoms, aryl group or halogen atom (particularly chlorine atom). Preferred examples of the cyclic hydrocarbon group represented by R43 and R44 include a cyclopentadienyl group, indenyl group and fluorenyl group. They may be substituted by a hydrogen atom, an alkyl group such as for example a methyl group, ethyl group, isopropyl group or tert-butyl group, or a substituent such as for example a phenyl group or a benzyl group. The following compounds can be mentioned as examples of the metallocene whose central metal M is titanium, ie titanócene: bis (cyclopentadienyl) t: tanium dichloride, bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) titanium, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dimethyl, bis (methylcyclopentadienyl) titanium diphenyl, bis (methylcyclopentadienyl) titanium ditolyl, bis (butylcyclopentadienyl) titanium dichloride, bis (dimethyl) butylcyclopentadienyl) titanium, bis (butylcyclopentadienyl) titanium diphenyl, bis (butylcyclopentadienyl) titanium ditolyl, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dimethyl, bis (pentamethylcyclopentadienyl) titanium diphenyl, bis (pentamethylcyclopentadienyl) ditolyl titanium, dichloride (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium, dimethyl of (cyclopentadienyl) (pentamethylcyclopentadinil) titanium, diphenyl of (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium and ditolyl of (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium. Among these, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium diphenyl and bis (cyclopentadienyl) titanium ditolyl are especially preferred because they are relatively easy to handle and have a high activity. The amount of the metallocene catalyst component can be determined in accordance with its polymerization activity. It is used in an amount of 10-6 to 10 ~ 2 mol, preferably 10-5 to 10"3 mol, per mol of the cyclic olefin added to the polymerization reaction system When used as a hydrogenation catalyst, the metallocene catalyst component is preferably used in combination with an organolithium compound to improve its catalytic activity The organolithium compound is a compound having a lithium atom attached to a hydrocarbon group Illustrative examples of the organolithium compound include compounds of monolithium such as methyllithium, ethyllithium, propylthio, isopropyllithium, butyllithium, suec-butyllithium, tert-butyllithium, pentillithium, phenyllithium and benzyl lithium, and dilithium compounds such as 1,4-dilithiobutane, 1,5-dilithiopentane and 1,2- Among these, methyllithium, butyllithium, sec-butyllithium and tert-butyllithium are especially preferred because they are easy to obtain. nolithium and the metallocene catalyst component, the organolithium compound is employed in an amount of 1.0 to 20 moles, preferably 1.5 to 10 moles, per mole of the metallocene catalyst component. The use of the organolithium compound in too small a quantity based on the metallocene catalyst component can not provide a sufficiently high polymerization activity. On the other hand, the use of the organolithium compound in too much quantity also has a disadvantage because it does not improve the polymerization reactivity and makes the purification subsequent to the polymerization difficult to carry out. The metallocene catalyst component is converted to a neutral alkylated metallocene and acquires a catalytic hydrogenation function when used in combination with an organolithium compound. The form of a polymer to be subjected to a hydrogenation reaction is not particularly limited and can be either isolated or in the form of a solution after a polymerization reaction. Nevertheless, in the first case, the polymer must be dissolved in a solvent again. Therefore, the second case is preferable from an industrial perspective. (metathesis catalyst component) The metathesis catalyst component used in the present invention is the transition metal compound of groups 3 to 8 of the periodic table, as exemplified by halides, oxyhalides, alkoxyhalides, alkoxides , carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes of the transition metals and derivatives thereof. Among these, titanium, vanadium, molybdenum, tungsten and rhenium compounds are preferred from the perspective of their high activity. Specific examples of the metathesis catalyst component include titanium trichloride, titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, vanadium oxytrichloride, vanadium oxytribromide, tungsten hexachloride, tungsten tetrachloride, tungsten dichloride, tungsten hexabromide, diiodide. of tungsten, tungsten dioxide, tungsten trioxide, tridecylammonium tungstate, molybdenum pentachloride, molybdenum trichloride, molybdenum dibromide, molybdenum diiodide, molybdenum trioxide, molybdenum dioxide, (oxy) molybdenum tetrachloride, tridecylammonium molybdate, rhenium trichloride, (oxy) rhenium trichloride, rhenium tribromide and (oxy) tribium rhenium. Among these, titanium tetrachloride, molybdenum pentachloride as well as tungsten hexachloride are particularly preferred.

The metathesis catalyst comprises the aforementioned metathesis catalyst component and an organic aluminum compound. The organic aluminum compound used in the catalyst is preferably a trialkylaluminum compound such as, for example, triethylaluminum or triisobutylaluminum. In addition, an additive can be added to increase the polymerization activity of the metathesis catalyst. Illustrative examples of the additive include nitrogen-containing compounds, oxygen-containing compounds, sulfur-containing compounds, and halogen-containing compounds, as exemplified by aliphatic tertiary amines, aromatic tertiary amines, molecular oxygen, water, alcohols, ethers, peroxides , carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, aldehydes, pyridine derivatives, thiophene derivative as well as molecular iodine. Among these, the aliphatic and aromatic tertiary amines, and especially triethylamine, dimethylaniline, tributylamine, pyridine and methylpyridine are preferred because they greatly enhance the polymerization activity. The amount of the metathesis polymerization catalyst component is from 10 ~ 5 to 10"1 mol, preferably from 10" 4 to 10-2 mol, per mol of the cyclic olefin taking into account the polymerization activity.

As for the amounts of the other components, the amount of the organic aluminum compound is from 1 to 100 moles, preferably from 2 to 50 moles, per mole of the metathesis catalyst component, and the amount of the additive is 0.005 to 10 moles, preferably 0.05 to 3 moles. When the amount of the organic aluminum compound is too small, sufficient activity can not be obtained whereas if said amount of organic aluminum compound is too large, the activity does not improve greatly and this represents a burden for catalyst removal. and the costs rise in a disadvantageous manner. When the amount of additive is too small, the improvement of the polymerization activity is not observed, whereas when it is too large, the additive de-activates the catalyst negatively. (Ziegler catalyst component) The Ziegler catalyst component employed in the present invention can be classified into two groups in accordance with the reaction system. That is, one group comprises Ziegler catalyst components suitable for addition copolymerization and the other group comprises Ziegler catalyst components suitable for a hydrogenation reaction. Ziegler catalyst components suitable for addition copolymerization include vanadium compounds represented by the following general formulas (XI) and (XII): V (OR47)Xd (XII) where R47 is an aliphatic hydrocarbon group having from 1 to 8 carbon atoms or an aromatic hydrocarbon group having from 6 to 18 carbon atoms, a, bcyd are integers that meet the following ratios: 0 < a < 3, 0 < b < 3, 2 < a + b < 3, 0 < c < 4, 0 < d < 4 and 3 < c + d < 4 Specifically, the vanadium compounds include (oxy) vanadium trichloride, (oxy) (ethoxy) vanadium dichloride, (oxy) (propoxy) vanadium dichloride, (oxy) (isopropoxy) vanadium dichloride, (oxy) (butoxy) vanadium dichloride, (oxy) (isobutoxy) vanadium dichloride, (oxy) (diethoxy) vanadium chloride, (oxy) (diisopropoxy) vanadium chloride, (oxy) (dibutoxy) vanadium chloride, (oxy) (diisobutoxy) vanadium chloride, vanadium (oxy) triethoxide, vanadium (oxy) tripidoxide, vanadium (oxy) triisopropoxide, vanadium (oxy) tributhoxide, vanadium (oxy) triisobutoxide, vanadium trichloride, tribromide of vanadium and vanadium tetrachloride. The amount of the vanadium compound can be determined according to its polymerization activity. It is employed in an amount of 10 ~ 6 to 10"2 mol, preferably 10" 5 to 10 ~ 3 mol, per mol of the cyclic olefin added to the polymerization reaction system. The Ziegler catalyst suitable for addition copolymerization is a catalyst produced from a combination of the vanadium compound and an organic aluminum compound. The organic aluminum compound is especially preferably an organic aluminum halide compound exemplified by diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride, and the like. An electron donor can be additionally added to the Ziegler catalyst to improve its polymerization activity. Illustrative examples of the electron donor include oxygen donors containing oxygen such as alcohols, phenols, ketones, aldehydes, carboxylic acids, acid esters, acid amides, acid anhydrides, ethers, and alkoxysilanes, amines, nitriles, isocyanates and Similar. As for the ratio between the organic aluminum compound and the vanadium compound, the organic aluminum compound is used in an amount of 2 to 500 moles, preferably 2 to 50 moles, more preferably 3 to 30 moles, per mole of the vanadium compound. When the amount of the organic aluminum compound is too small, high activity can not be obtained while when the amount is too large, the polymer can form gels in a disadvantageous manner. As for the ratio between the electron donor and the vanadium compound, the electron donor is employed in an amount of 0.005 mol to 10 mol, preferably 0.05 mol to 3 mol, per mol of the vanadium compound. When the amount of the additive is too small, the improvement of the polymerization activity is not observed whereas when the amount is too important, the catalyst is deactivated which is negative. The Ziegler catalyst component suitable for use as a hydrogenation catalyst is preferably a halide, acetyl acetonate complex, carboxylate complex, naphthenate complex, trifluoroacetate complex or transition metal stearate complex such as for example vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel or palladium. Specific examples of the Ziegler catalyst component include triethyl vanadate, tris (acetylacetonate) chromium, tris (acetylacetonate) manganese, cobalt acetate, cobalt tris (acetylacetonate), cobalt octoate, bis (acetylacetonate) nickel and the like. Among these, cobalt and nickel compounds, and especially tris (acetylacetonate) cobalt and bis (acetylacetonate) nickel are preferred from the perspective of catalytic activity. The Ziegler catalyst suitable for a hydrogenation reaction is produced from a combination of the above transition metal compound and an organic aluminum compound. The organic aluminum compound used in the catalyst is the same as the compound described above and is especially preferably a trialkylaluminum compound such as for example triethylaluminum or triisobutylaluminum. As for the quantitative reaction between the transition metal compound and the organic aluminum compound, the amount of the metal component of the alkyl-metal compound should be from 1 to 50 moles, preferably from 1 to 10 moles, per mole of the metal of the transition metal compound. The form of the polymer to be subjected to a hydrogenation reaction is not particularly limited. It can be isolated or in the form of a solution after a polymerization reaction. However, in the first case, the polymer must be dissolved in a solvent again. Accordingly, the second case is preferable from an industrial perspective, (cyclic olefin) The cyclic olefin used in the present invention is presented by the following general formula (I): where n is 0 or 1, m is 0 or a positive integer, p is 0 or 1, R1 to R20 are the same or different and are each a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having from 6 to 10 carbon atoms or aliphatic hydrocarbon group saturated or unsaturated having 1 to 12 carbon atoms, and R17 and R18, or R 19 R, can form an alkylidene group, R 17 or R, 18, and R > 1193 or Rv20 can form a ring, and the ring can have a double bond or can be an aromatic ring. The following compounds can be mentioned as examples of the cyclic olefin represented by the above formula (I): Bicycles derivatives [2.2. l] hept-2-ene such as, for example, bicyclo [2.2.1] hept-2-ene (norbornene), 1-methylbicyclo [2.2.1] ept-2-ene, 6-methylbicyclo [2.2.1] hept-2 -eno, 6-ethylbicyclo [2.2. l] hept-2-ene, 6-n-propylbicyclo [2.2.1] hept-2-ene, 6-isopropylbicyclo [2.2. l] hept-2-ene, 6-n-butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 6-ethylidenbicyclo [2.2.1] hept-2 eno, 6-propylidenbicyclo [2.2.1] hept-2-ene, ß-isopropylidene bicyclo [2.2.1] hept-2-ene, and 7-methylbicyclo [2.2. 1] hept-2-ene; tricycle [4 .3. O l2-5] -3-decene; tricycle derivatives [4.3.0. 12'5] -3-decene such as 2-methyltricyclo [4.3. 0.12-5] -3-decene, 5-methyltricyclo [4.3.0.12'5] -3-decene and 10-methyltricyclo [4.3. 0.1] -3-decene; dicyclopentadiene; tricyclic [4.4.0.12 - 5] -3-undecene derivatives such as, for example, tricyclo [4 .4.0.12-5] -3-undecene, 2-methyltricyclo [4.4 .0.12-5] -3-undecene, 5-methyl-tricyclo [4.4.0.1] -3-undecene-11-methyltricyclo [4.4.0.1 2.5] - -3-undecene; tetracyclo derivatives [4.4.0.1 2.5 n 7 .10] -3-dodecene such as tetracycle [4.4. 0. 12-5.17-10] -3-dodecene, 8-methyltetracyclo [4.4. 0. 1 2.5? 7 .10] -3-dodecene, 8-ethyltetracyclo [4.4.0.12 * 5.17-10] -3-dodecene, 8-n-propyltetracyclo [4.4.0.12-5.17-10] -3-dodecene, 8-isopropyltetracyclo [4.4 .0.1 2.5 -, 7.10] -3-dodecene, 8-n-butyltetracyclo [4.4.0.12-5.17-10] -3-dodecene, 8-isobutyl tetracyclo [4.4.0.12'5.17-10] -3-dodecene, 8- ethylidetraciclo [4.4.0.1 2.5 t7.10] -3-dodecene, 8-n-propylidentetracycle [4.4.0. l 'ü .1 -1U] -3-dodecene-isopropylidenetracyclo [4.4.0.12'5.17-10] -3-dodecene; pentaciclo [6.5.1.13-6.02-7.09-13] -4-pentadecene; pentacycle [6.5.1.13-6. O2-7.09"13] -4, 10-pentadecadiene.

Among these, bicyclo derivatives [2.2. l] hept-2-ene (norbornene), dicyclopentadiene and tetracyclo derivatives [4.4.0.12'5.17'10] -3-dodecene because they are inexpensive and can be synthesized and isolated easily, and norbornene and dicyclopentadiene are especially preferred. They can be used alone or in combination of two or more. (cyclic olefin polymer) The cyclic olefin polymer produced in the present invention has no particular limitations insofar as it contains a cyclic olefin as a polymerized unit. Basically, the cyclic olefin polymer can be classified in the group of copolymers of addition of cyclic olefins and alpha-olefins, in the group of open ring polymers of cyclic olefins or in the group of the hydrogenated polymers thereof according to the structure of the polymer, (addition copolymer) In the present invention, a cyclic alpha-olefin-olefin copolymer is produced by the copolymerization by addition of an alpha-olefin having two or more carbon atoms and a cyclic olefin in a solvent of hydrocarbon in the presence of a polymerization catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst. The addition copolymer has a recurring structure represented by the following general formula (XIII) where n, m, p and R1 to R20 are the same as defined in formula (I) and R48 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. The molar ratio between the cyclic olefin component and the alpha-olefin component has no particular limitation but is preferably within the range of 90/10 to 10/90, more preferably 80/20 to 20/80. Illustrative examples of alpha-olefins having 2 or more carbon atoms that are employed in the present invention include alpha-olefins having from 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. Among these, ethylene and propylene are preferred from the perspective of the polymerization activity and the molecular weight of the polymer, with ethylene being particularly preferred. They can be used alone or in combination of two or more. The cyclic olefin, the metallocene catalyst and the Ziegler catalyst are in accordance with what has already been described above. Specific examples of the hydrocarbon solvent used herein include aliphatic hydrocarbons such as, for example, pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and cyclooctane; and aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and diethylbenzene. They can be used alone or in combination of two or more. Among these, aromatic hydrocarbons and alicyclic hydrocarbons are preferred because they have a high solubility for catalysts and polymers, and benzene, toluene, cyclohexane and methylcyclohexane are especially preferred. The molar ratio between the alpha-olefin unit and the cyclic olefin unit in the copolymer can be easily controlled by controlling the ratio between the concentrations of both monomers. Particularly when the alpha-olefin is gaseous at normal temperature such as ethylene, the rate of introduction into the polymer can be controlled by the pressure of the alpha-olefin. The temperature and time of a polymerization reaction can be determined in accordance with the types of monomers and the catalyst that are employed in addition copolymerization. Generally, the temperature is from 0 to 100 ° C, preferably from 10 to 80 ° C, and the reaction time is from 0.1 to 10 hours. (hydrogenated polymer of addition copolymer) When a cyclic olefin having two or more double bonds between carbon atoms is used to produce the above-mentioned addition copolymer, the double bonds between the carbon atoms remain in the addition copolymer. In this case, a hydrogenated copolymer can be produced by the addition of a hydrogenation catalyst selected from the group consisting of a metallocene catalyst and a Ziegler catalyst to a reaction solution obtained after the polymerization to carry out the hydrogenation. The hydrogenated polymer has a recurrent structure represented by the following general formula (XIV): (XIV) where n, m and p are the same as defined in formula (I), and R49 to R68 are the same or different and each represents 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, provided that R or R 66 and R or R, 68 can form a ring and the ring can have an aromatic ring. Illustrative examples of the cyclic olefin having two or more double bonds between carbon atoms include bicyclo derivatives [2.2. l] hept-2-ene such as 6-propylidenbicyclo [2.2. l] hept-2-ene and 6-isopropylidenbicyclo [2.2. l] hept-2-ene; dicyclopentadiene; tetracyclo derivatives [4.4.0.1.2'5.17-10] -3-dodecene, such as 8-ethylidentetracycle [4.4. O.l.2.55.17-10] -3-dodecene, 8-n-propylidermicyclo [4.4.0.1 2.5-, 7.10] -3-dodecene and isopropylidenetracyclo [4.4.0.1. .1] -3-dodecene; pentacycle [6.5.1.1? .0 > ' O5 * - "] -4, 10-pentadecadiene Among these, dicyclopentadiene is preferred because it is inexpensive and easy to obtain.The metallocene catalyst and the Ziegler catalyst used as the hydrogenation catalyst are in accordance with what has already been described above. In the present invention, the solution obtained after a polymerization reaction is used in the hydrogenation reaction.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 can be determined in accordance with the types of monomers and hydrogenation catalyst used in the addition copolymerization Generally speaking, the temperature is from 0 to 290 ° C, preferably from 20 to 180 ° C. C, the hydrogen pressure is from 0.1 to 200 kgf / cm2 'preferably from 1 to 100 kgf / cm2, and the reaction time is from 0.1 to 10. The degree of hydrogenation of the copolymer (rate of hydrogenation of the double bonds between carbon atoms) is 98% or more, preferably 99% or more, more preferably 99.5% or more. When the degree of hydrogenation is less than 98%, the thermal stability becomes insufficient and discoloration easily occurs at the time of the melt molding, which is disadvantageous, (ring-opened polymer). In the present invention, an open polymer in Cyclic olefin ring is produced by the ring opening polymerization of a cyclic olefin in a hydrocarbon solvent in the presence of a metathesis catalyst. The cyclic olefin ring-opened polymer produced in the present invention is a polymer having the double bonds between open carbon atoms in the norbornene skeleton of a cyclic olefin having a recurring structure represented by the following general formula (XV): where n, m, p and R1 to R20 are in accordance with that defined in formula (I). The cyclic olefin, the metathesis catalyst and the ring-opened polymer are in accordance with what has already been described above. The hydrocarbon solvent used herein is the same as the hydrocarbon solvent used in the addition copolymerization reaction. The temperature and time of the polymerization reaction can be determined in accordance with the types of monomers and catalyst employed in the ring-opening polymerization. Generally speaking, the temperature is 0 to 150 ° C, preferably 10 to 100 ° C, and the reaction time is 0.1 to 10 hours. (hydrogenated polymer of a ring-opened polymer) In the present invention, since the ring-opened polymer produced by a ring-opening polymerization reaction will inevitably contain double bonds between carbon atoms, a hydrogenation catalyst selected within the group that consists of a metallocene catalyst and a Ziegler catalyst is added to the solution obtained after the ring-opening polymerization when carrying out the hydrogenation. The hydrogenated polymer has a recurring structure represented by the following general formula (XVI): where n, m and p are in accordance with that defined in the formula above (I), and R49 to R68 are the same or different and each is a hydrogen atom, halogen atom, aromatic hydrocarbon group having from 6 to 10 carbon atoms. carbon or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, provided that R65 or R6d and R66 or R68 can form a ring and the ring can have an aromatic ring. The metallocene catalyst and the Ziegler catalyst suitable for use as a hydrogenation catalyst are in accordance with what has already been described above. The conditions of the hydrogenation reaction are exactly the same as the conditions of a hydrogenation reaction after an addition copolymerization reaction, (catalyst removal) In the present invention, at least one compound selected from the group consisting of an alpha - oxyacid and beta-oxyacid having a hydroxyl group and a carboxyl group in the molecule and derivatives obtained by substitution of the hydroxyl group by an alkoxyl group is added to the solution of a reaction product after the production of a cyclic olefin polymer for decoating and deactivating the catalyst and for precipitating a catalyst metal component. The compound selected from the group consisting of the alpha-oxyacid, beta-oxyacid and derivatives thereof wherein the OH group is substituted by an alkoxy group is represented by the following general formula (II): (ID where q is 0 or 1, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R22, R23, R24 and R25 are the same or different and each is a carbon atom. hydrogen, alkyl group having 1 to 6 carbon atoms, phenyl group or benzyl group Preferred examples of the compound represented by the formula (II) include 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-hydroxybutyric acid, hydroxy-2, 2-dimethylactic, mandelic acid, diphenyl glycolic acid, tropic acid, 3-hydroxy-3-phenylpropionic acid, methoxyacetic acid, 2-methoxypropionic acid, 3-methoxypropionic acid and alpha-methoxyphenylacetic acid. Among these, glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxy-2-methylpropionic acid, methoxyacetic acid, 2-methoxypropionic acid and 3-methoxypropionic acid are preferred since the boiling point is from about 200 ° C or less to 10 mmHg and can be easily removed in the removal step by distillation of the solvent. In addition, alpha-oxyacids are especially preferred because they have a high chelating effect and easily turn an insoluble metal component, and glycolic acid, lactic acid, 2-hydroxybutyric acid and 2-hydroxy-2-methylpropionic acid are especially preferred. The amount of the compound represented by the above formula (III) is preferably determined by the total amount of metals in catalysts contained in the reaction system. That is, the compound is preferably added in an amount of 0.1 to 5 moles based on 1 equivalent of the total product of the number of moles of the transition metal catalyst component and the oxidation number of the transition metal and the product of the number of moles of the organic aluminum compound and the oxidation number of aluminum (3), and the product of the number of moles of the organolithium compound and the oxidation number of lithium (1) as required. It is also preferable to add a compound selected from the group consisting of water and alcohols in addition to the compound represented by the above formula (II). The amount of water is from 0 to 9.9 moles, preferably from 0 to 8 moles, based on the aforementioned standard while the amount of an alcohol is from 0 to 5 moles, preferably from 0 to 4 moles., based on the same standard. The compound represented by the above formula (II), water and alcohol are preferably added in a total amount of 0.1 to 10 moles. When the total amount of the compound represented by the above formula (II), water and alcohol is below the aforementioned range, the precipitation of the catalyst components becomes incomplete which presents a disadvantage. When the total amount is above the range, on the other hand, the polarity of the polymer solution rises and some or all of the catalyst components remain dissolved in the polymer solution because they are trapped by the compound represented by the formula above (II), water and alcohol dissolved there, which presents a disadvantage. Obviously, when the total amount of the compound represented by the formula above (II), water and alcohol is greater than required, the compound deviates greatly from its solubility in the polymer solution. Accordingly, the compound must be separated beforehand by filtration. In this case, a residual solution containing metals in large quantities is generated, which presents a disadvantage. The water employed in the present invention does not only react with a catalyst or a species of catalytic activation to cause the catalyst and the species of catalytic activation to become insoluble but also promotes the ionization of oxycarboxylic acid to greatly improve its reactivity. The alcohol employed in the present invention is an aliphatic alcohol having from 1 to 5 carbon atoms. Illustrative examples of the aliphatic alcohol include methanol, ethanol, propanol, isopropanol, n-butanol and isobutanol. Polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin are preferably used. Among these, ethylene glycol is particularly preferred because it is economical and renders the metals in insoluble catalysts because of their polar effect that at least part of another hydroxyl group remains even when reacted with a catalyst metal to form an alcoholate. The active hydrogen-containing compound is preferably a compound having a boiling point that differs greatly from the boiling point of the solvent employed and can be easily prepared by doping with the recovery step of the solvent taken into account. The compound represented by the above formula (II), water and alcohol can be added independently, or two or more of them can be added simultaneously. The addition of the compound represented by the above formula (II), water and alcohol to the polymer solution is carried out at a temperature of 0 to 200 ° C, preferably 10 to 180 ° C, more preferably of normal temperature to the boiling point of the solvent. When the reaction temperature is below the aforementioned range, the reaction is not fully realized whereas when the temperature is above the range, a precipitate can dissolve in the polymer solution, which presents a disadvantage. The reaction time is from 1 minute to 10 hours, preferably from 5 minutes to 5 hours, and especially from 10 minutes to 3 hours, when the reaction time is less than the aforementioned range, the reaction is not carried out totally, which presents a disadvantage. When the reaction time is greater than the aforementioned range, there is no effect and it is only a waste of time. When a compound containing active hydrogen is added to the polymer solution, the metallocene catalyst and the hydrogenation catalyst form bonds with the compound represented by formula (II) above, water and alcohol. What will be described with details as an example is a case in which a cyclic alpha-olefin-olefin is then polymerized using isopropylene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, as metallocene, tritiltetra (pentafluorophenyl) borate as cocatalyst and triisobutylaluminum as alkylating agent, the catalysts being removed using a lactic acid / water system as an active hydrogen compound. What will also be described with details as example is a case where after tris (acetylacetonate) cobalt is hydrogenated using triisobutylaluminum as an alkylating agent, the catalyst is removed using a lactic acid / water system as an active hydrogen compound, (removal of polymerization catalyst) The reaction product of a reaction between the metallocene zirconium and lactic acid / water [Zr) OLc) m (OH) -m: OLc is considered to be the residual lactic acid group and m is an integer of 0 to 4], a derivative of an isopropylidene (9-fluorenyl) (cyclopentadienyl) group which is a ligand, a hydrogen halide and the partial reaction product of a reaction between the metallocene and the lactic acid and / or water are formed at from the polymerization catalyst. A triphenylmethyl compound containing triphenylmethane is formed from the cationic component of tritiltetra (pentafluorophenyl) borate which is a cocatalyst, while boric acid [HB) C6Fs)] is formed from the anionic component. An alkane and Al (OLc) n (OH) 3_n [OLc is the same as above and n is an integer from 0 to 3] and / or a condensate thereof are formed from triisobutylaluminum. In general terms, condensate gel formation is promoted as its degree of condensation rises. Among these, a decomposition product containing zirconium, a decomposition product containing aluminum, hydrogen halide, boric acid and the like are highly organic and are separated from the hydrocarbon-based polymer solution having a low polarity. Since the decomposition product of the metallocene and boric acid are extremely small in quantity, it is difficult to isolate and precipitate each of them almost completely. However, since they are encompassed in a decomposition product derived from triisobutylaluminum which exists in large quantities, it is possible to separate them from a polymer solution very efficiently. A triisobutylaluminum compound is especially preferable because it can become a decomposition product having a high degree of condensation and, therefore, easily includes the decomposition product of metalocene and boric acid. (removal of hydrogenation catalyst) tris (acetylacetonate) cobalt, which is one of the typical Ziegler-based hydrogenation catalysts, does not have a catalytic hydrogenation function per se and has a catalytic function as an active species when reduced by triisobutylaluminum and move a compound that contains an isobutyl group. Since the compound is alkylated, it reacts extremely easily with the active hydrogen-containing compound employed in the present invention and becomes a decomposition product insoluble in a solvent of hydrocarbon-based polymers. The decomposition product is precipitated together with a decomposition product derived from triisobutylaluminum or by the fact that it is comprised in the decomposition product according to that described above. However, since a hydrogenation reaction is carried out at high temperatures, an acetylacetonate group is exchanged between tris (acetylacetonate) cobalt and triisobutylaluminum, whereby tris (acetylacetonate) aluminum is a by-product. This compound itself is very stable and can not be decomposed by water, alcohols or ordinary carboxylic acid. In addition, since the acetylacetonate group encompasses aluminum which is the central metal and the methyl group is aligned to the outside, the compound has a low polarity, dissolves in a non-polar hydrocarbon solvent and is not easily adsorbed and included in a product of decomposition derived from triisobutylaluminum having a high polarity. Nevertheless, since lactic acid is a stronger chelating agent than acetylacetone, it offers a compound having a higher polarity [for example, Al (OLc) 3: It is the same as above] exchanging a chelate up to tris (acetylacetonate) aluminum. Therefore, the by-product can be precipitated and separated efficiently. At least some of the organic substances (a derivative of the group isopropylidene (9-fluorenyl) (cyclopentadienyl), an organic substance derived from a ligand such as for example acetylacetone, alkane, triphenylmethane derived from a trityl group, and an excess of a compound of active hydrogen) which are components other than metal components and inorganic substances remain in a polymer solution. However, they can be removed when the solvent and residual cyclic olefin or a hydrogenated compound thereof are removed. The precipitated metal catalyst residue can be removed from the polymer solution by filtration or using a common method such as centrifugation.

In the present invention, to remove the catalyst metal residue and a decolorization component as much as possible and as efficiently as possible, the active hydrogen compound is added to cause a decomposition reaction and then a reaction solution. It can be treated with an adsorbent. The adsorbent is not particularly limited but is preferably acid clay, active clay, activated carbon, diatomaceous earth, silica gel, alumina, silica gel alumina, zeolite or the like. The treatment method can be a method comprising the steps of adding an adsorbent to the polymer solution, stirring the resulting polymer solution to mix and remove a catalyst by filtration or the like or it can comprise the step of forcing a polymer solution to pass through a packed phase (packed column) of an adsorbent. Since metal components derived from the polymer solution are almost completely removed in the previous step, the amount of the adsorbent is very small in the above method while the number of times of change of the packed phase and its regeneration is small in the second method. The method comprising the step of forcing the polymer solution to pass through the packaged phase of the adsorbent is industrially beneficial. When the polymer solution is washed with an aqueous solution, an acidic, neutral or basic aqueous solution can be used. Among these, an aqueous solution can be used or two or more different aqueous solutions can be used, stepwise. In this case, even when a waste washing solution is produced, the disposal of the residual solution does not cause problems because the metal components derived from the polymer solution have been almost completely removed in the previous stage. The total amount of transition metal, aluminum and lithium contained in the cyclic olefin polymer obtained in this way is preferably 5 ppm or less, more preferably 3 ppm or less, particularly preferably 2 ppm or less. The amount of the transition metal is preferably 2 ppm or less, particularly preferably 1 ppm or less. The amount of aluminum is preferably 3 ppm or less, particularly preferably 1 ppm or less, (polymer recovery). A polymer is recovered through a solvent removal step of the polymer solution from which it has been removed. removed in the catalyst metal residue through the aforementioned process. The solvent is removed through a vacuum condenser, ventilated extruder heating and the like. The polymer can also be recovered by injecting the polymer solution into a usually poor solvent and by precipitation and separation of the polymer. Various additives such as an antioxidant can be added to the cyclic olefin polymer that is obtained through the present invention, as required. Illustrative examples of the antioxidant 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) ethylpropionate] 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. Since the cyclic olefin polymer obtained by the present invention substantially does not contain polymerization catalyst residue and has a very high purity, it exhibits excellent properties such as transparency, heat resistance, light resistance, dielectric characteristics and mechanical characteristics and can be used advantageously as optical material for optical disc substrates and camera lenses. That is, in accordance with the present invention, a cyclic olefin polymer having a total transition metal content is provided., aluminum and lithium of 5 ppm or less, a cyclic olefin polymer having an aluminum content of 3 ppm or less, and the use of these polymers as an optical material. In accordance with the present invention, a copolymer having extremely high purity can be obtained by removing the catalyst residue very efficiently from a cyclic olefin polymer solution obtained by using a metallocene catalyst or a copolymer solution of hydrogenated cyclic olefin obtained by the use of a homogeneous hydrogenation solvent by a simple method that does not generate a residual solution containing metals. EXAMPLES The following examples are provided for the purpose of further illustrating the present invention but in no way to limit it. The following examples were made in an inert atmosphere such as an atmosphere of argon or nitrogen unless otherwise stated. Toluene was used (solvent), dicyclopentadiene, norbornene, 8-ethylidentetracyclo [4.4.0.12'5.17'10] -3-dodecene and triethylamine which were purified by distillation and dried completely by a method usually employed. Isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was purchased from Boulder Scientific Co., Ltd. as a metallocene and used without further purification. Trityl-tetrakis (pentafluorophenyl) borate was purchased from Toso Akzo Co., Ltd. as an ion boron compound and used without further purification. Triisobutylaluminum was purchased from Toso Akzo Co., Ltd., in the form of a 2M toluene solution and used without further purification. Tris (acetylacetonate) cobalt, titanium tetrachloride, an aqueous solution of lactic acid and 2-hydroxy-2-methylpropionic acid were purchased from Wako Puré Chemical Industries, Ltd. and were used without further purification. Measurement elements in the examples were measured in accordance with the following methods. Glass transition temperature (Tg (° C)): was measured using 2920 DSC from TA Instruments Co., Ltd., at a temperature rise rate of 20 ° C / min. Molecular weight: the reduced viscosity was measured? Sp / c (dl / g) at 30 ° C in a toluene solution with a concentration of 0.5 g / d. Degree of hydrogenation: determined by means of 1 H-NMR using JNM-A-400 nuclear magnetic resonance absorber from JEOL Ltd. Concentration of residual metals in polymer: was determined by spectral analysis of ICP emissions. Infrared light absorption spectrum: measured by the KBr method, using the 1760X spectroscope of Perkin Elmer Co., Ltd. Ultraviolet visible absorption spectrum: it was measured using the U-320 spectroscope of Hitachi, Ltd., and a 1-cm. Toluene was injected into a compensation cell. 13C-NMR spectrum of solid: was measured using the DSX300WB from Bruker Co., Ltd. In the following examples and in the comparative examples, the number of moles of a compound represented by the formula (II), the number of moles of water and the number of moles of an added alcohol based on an equivalent of a total product of the number of moles of a transition metal component and the oxidation number of the transition metal and the product of an organic aluminum compound and the oxidation number of aluminum (3), and the product of the number of moles of an organolithium compound and the lithium oxidation number (1) as required are defined as fi, f2 and f3, respectively. Reference Example 1 0.97 g of tris (acetylacetonate) aluminum was dissolved in 300 g of toluene. The obtained solution was heated to a temperature of 100 ° C and 0.62 g (fi = 2.0) of 2-hydroxy-2-methylpropionic acid was added under stirring. Subsequently, the solution was stirred while being heated at the same temperature for 2 hours. The formed precipitate was separated by filtration to obtain 1.0 g of an achromatic solid powder. The infrared light absorption spectrum of this powder (figure 1) was compared with those of tris (acetylacetonate) aluminum (figure 2) and 2-hydroxy-2-methylpropionic acid (figure 3), which were raw materials. As it is evident from these figures, a strong peak that is around 1,540 cm-1 derived from tris (acetylacetonate) aluminum and a strong peak that is around 1,730 cm "1 derivative of 2-hydroxy-2- acid methylpropionic disappeared from a powdered spectrum and a strong peak based on the aluminum carbonyl group bound to 2-hydroxy-2-methylpropionic acid was observed at approximately 1.620 cm_1 It was found from the above that tris (acetylacetonate) aluminum was changed in aluminum 2-hydroxy-2-methylpropionate A precipitate was also obtained when the same experiment was carried out by the addition of 0.3 g of water in addition to the 2-hydroxy-2-methylpropionic acid employed above.

The infrared light absorption spectrum of the precipitate (figure 4) was the same as the absorption spectrum of the aforementioned precipitate (figure 1). The same experiment was carried out by the addition of 1.3 g of ethylene glycol in place of the 2-hydroxy-2-methylpropionic acid employed above. However, no deposit of precipitate was observed at all. The same experiment was carried out by the addition of 0.4 g of acetic acid in place of the 2-hydroxy-2-methylpropionic acid employed above. However, the deposit of a precipitate was not observed at all. Reference Example 2 1.3 g of tris (acetylacetonate) aluminum was dissolved in 300 g of toluene. The solution obtained was heated to 100 ° C and 8.4 g of an aqueous solution containing 90% by weight of lactic acid were added to the solution, with stirring, dropwise. Then, the solution was stirred while heating at the same temperature for 2 hours. The formed precipitate was separated by filtration to obtain 0.8 g of an achromatic solid powder. The infrared light absorption spectrum of this powder (Figure 5) was compared with the infrared light absorption spectrum of tris (acetylacetonate) aluminum (Figure 2) which was a raw material. As is evident from these figures, while a strong peak disappeared at around 1,540 c "1 derived from the raw material of the dust spectrum, a strong peak based on the carbonyl group of aluminum lactate was observed around 1,620 cm" 1 instead. The infrared light absorption spectrum of the powder almost corresponded to the infrared light absorption spectrum of aluminum lactate. Peaks based on CH3 groups, > CH- and -COO- of aluminum lactate were observed at about 23 ppm, 63 ppm and 180 ppm in the spectrum measured by 13 C-NMR of powder solids, respectively. It was found from above that tris (acetylacetonate) aluminum was changed into an aluminum lactate. The same experiment was carried out by the addition of 1.3 g of ethylene glycol instead of the aqueous lactic acid solution used above. However, the deposit of a precipitate was not observed at all. The same experiment was carried out by the addition of 0.4 g of acetic acid instead of the aqueous lactic acid solution employed above. However, the deposit of precipitate was not observed at all. Reference Example 3 0.8 g of triisobutylaluminum in 300 g of toluene was dissolved. Subsequently, 0.30 g of cobalt tris (acetylacetylacetonate) was added to prepare a hydrogenation catalyst. The obtained solution was heated to 100 ° C and 8.4 g of an aqueous solution containing 90% by weight of lactic acid were added, drop by drop, to the solution, under stirring. Then, the solution was stirred while heating at the same temperature for 2 hours. The formed precipitate was separated by filtration to obtain 1.9 g of a light pink solid powder. The absorption spectrum of infrared light of this powder (figure 6) was compared with the spectrum of tris (acetylacetonate) aluminum (figure 2) and the spectrum of tris (acetylacetylacetonate) cobalt (figure 7) that were the raw materials. As is evident from these figures, while a peak about 1.540 cm "1 derived from tris (acetylacetonate) aluminum and a peak about 1.520 cm" 1 derived from tris (acetylacetylacetonate) cobalt disappeared from the dust spectrum, it was observed in place a peak based on aluminum lactate at approximately 1,620 cm-1. Reference Example 4 186 g of dicyclopentadiene, 1,320 g of toluene and 3.6 g of triisobutylaluminum were injected into a 3 liter stainless steel reactor. The inner part of the reactor was replaced with ethylene having a normal pressure, 119 mg of isoprene dichloride (9-fluorenyl) (cyclopentadienyl) zirconium and 252 mg of trityl tetrakis (pentafluoroborate) were added to carry out the polymerization to a temperature of 30 ° C. During the polymerizationethylene was supplied at normal pressure in a continuous manner, and 163 g of dicyclopentadiene was added at a rate such that the addition rate of dicyclopentadiene and the rate of ethylene consumption were 42:58. The ethylene supply was stopped when the ethylene consumption reached a polar amount that corresponded to 350 g of added dicyclopentadiene (150 minutes), thus ending the reaction. A polymer obtained by the assortment of a small amount of the obtained solution and purifying it in accordance with a commonly used method had a reduced viscosity (? Sp / c), in accordance with that measured at 30 ° C in a toluene solution at 0.5 %, of 0.58 dl / g and a glass transition temperature, measured by DSC, of 155 ° C. The reaction solution obtained (reaction solution a) was supplied in a 10 liter autoclave under pressure and 3.0 g of cobalt tris (acetylacetylacetonate) and 4.8 g of triisobutylaluminum were added to the reaction suspension. Then, a hydrogenation reaction was carried out at a hydrogen pressure of 45 atmospheres for 120 minutes to obtain a reaction solution b. A small amount of the reaction solution was stocked and precipitated in a large amount of methanol to prepare a measurement sample. It was found from the 1H-NMR spectrum of the sample that this polymer had a hydrogenation rate of 99.9% or more. The reduced viscosity (? Sp / c), measured at a temperature of 30 ° C in a 0.5% toluene solution, of the polymer, was 0.45 dl / g. The glass transition temperature, measured by DSC, of the polymer was 151 ° C. EXAMPLE 1 32.0 g of 2-hydroxy-2-methylpropionic acid (fi = 2.0) were added to the reaction solution b obtained in reference example 4 (according to what was defined as reaction solution 1-1 by discrimination) to a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid pink paste. The paste was then filtered with a cylindrical filter having a diameter of 11 cm. The filter used was prepared by placing Celite or Naslon NF-05 in a thickness of 5 cm and a flannel cloth in Celite. The filtration pressure was 4 kg / cm2 (meter pressure). The filtration was carried out very gently. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by means of ICP emission spectral analysis. As a result, the amount of Zr was 0.1 ppm or less, the amount of B was 0.2 ppm or less, the amount of Co was 0.4 ppm or less and the amount of Al was 0.8 ppm based on the polymer. It was found from this that the polymer had a very high purity. The unreacted product and the solvent were removed by distillation (washing) of the treated solution to obtain an achromatic polymer. In accordance with the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the polymer obtained, the solution had a transmittance at 500 nm of 99% or more. Example 2 32.0 of 2-hydroxy-2-methylpropionic acid and 2.8g of water (fi = 2.0, f2 = 1.0) were added to reaction solution b (defined as reaction solution 2-1 for discrimination) obtained by the method of Reference Example 4 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid pink paste. The paste was then filtered in the same manner as in Example 1. It was carried out very gently. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by ICP emission spectrum analysis. As a result, the amount of Zr was 0.1 ppm or less, the amount of B was 0.3 ppm or less, the amount of Co was 0.5 ppm or less and the amount of Al was 1.2 ppm based on the polymer. It was found from this that the polymer exhibited a very high purity. The unreacted product and the solvent were removed by distillation (washing) from the treated solution to obtain an achromatic polymer. According to the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer, the solution had a transmittance at 500 nm of 99% or more. Example 3 An aqueous solution of lactic acid comprising 28.9 g of lactic acid and 2.9 g of water (fi = 2.0, f2 = 1.0) was added to reaction solution b (defined as reaction solution 3-1 for discrimination) obtained by the method of Reference Example 4 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid pink paste (paste 3-2). The paste was then filtered in the same manner as in Example 1. The filtration pressure changed to 4 kg / cm 2 (meter pressure). Filtration proceeded very smoothly as shown in curve A of figure 8 and 1.6 kg of the paste could be treated in 90 minutes. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic transparent treated solution (treated solution 3-3). The residual metals of the solution were measured by ICP emission spectral analysis. As a result, the amount of Zr was 0.1 ppm or less, the amount of B was 0.1 ppm or less, the amount of Co was 0.3 ppm and the amount of Al was 0.7 ppm based on the polymer. It was found from this that the polymer had a very high purity and that the amount of Al in particular was very small. The unreacted product and the solvent were removed by distillation (washing) from the treated solution to obtain an achromatic clear polymer. (purified polymer 3-4). The sublimation of tris (acetylacetonate) aluminum was not observed during the treatment. No strong absorption based on tris (acetylacetonate) aluminum was observed in the visible ultraviolet absorption spectrum of a toluene solution containing 20% of the obtained polymer. Meanwhile, the precipitate (precipitate 3-5) was analyzed. While no absorption was observed at approximately 1,520 cm "1 and 1,540 cm" 1 based on tris (acetylacetonate) cobalt and tris (acetylacetonate) aluminum in the infrared light absorption spectrum of the precipitate (figure 9), strong absorption was observed based on a lactate. A peak based on a lactate was observed at approximately 23 ppm (CH3) 63 ppm (> CH ~) and 180 ppm (-C00-) in the 13C-NMR spectrum of the precipitate solid (Figure 10). These results show that the tris (acetylacetonate) cobalt and triisobutylaluminum which were catalyst components used in large quantities were effectively precipitated as lactates. Example 4 A solution comprising 21.7 g of lactic acid and 2.9 g of water (fi = 1.5, f2 = 1.0) was added to reaction solution b (defined as reaction solution 4-1 for discrimination) obtained by the method of Reference Example 4 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution of color -black coffee was transformed into a turbid pink paste (paste 4-2). The paste was then filtered in the same manner as in example 1. The filtration was carried out very gently as shown in curve B of figure 8. The obtained filtrate was adsorbed on basic alumina to obtain a treated solution achromatic (solution treated 4-3). The residual metals of the solution were measured by ICP emission spectral analysis. As a result, the amount of Zr was 0.1 ppm or less, the amount of B was 0.1 ppm less, the amount of Co was 0.6 ppm and the amount of Al was 0.9 ppm based on the polymer. It was found from this that the polymer had a very high purity. The unreacted product and the solvent were removed by distillation (washing) of the treated solution to obtain an achromatic polymer (purified polymer 4-4). The sublimation of tris (acetylacetonate) aluminum was not observed during the treatment. No strong absorption was observed based on tris (acetylacetonate) aluminum in the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer. The solution had a transmittance at 500 nm of 99% or more. Meanwhile, the precipitate was analyzed (precipitate 4-5). While no peak was observed at about 1,620 cm "1 based on tris (acetylacetonate) cobalt nor a peak at about 1,640 cm" 1 based on tris (acetylacetonate) aluminum in the infrared light absorption spectrum of the precipitate, strong absorption based on a lactate at about 1620 cm "1 was observed in its place.These results show that tris (acetylacetonate) cobalt and triisobutylaluminum, which were catalyst components used in large quantities, were effectively precipitated as lactates. Example 5 A solution comprising 28.9 g of lactic acid and 2.9 g of water (fi = 2.0, f2 = 1.0) was added to reaction solution b (defined as reaction solution 5-1 for discrimination) obtained by the method of reference example 4 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. ~ The reaction solution of black coffee color turned into a turbid pink paste. The paste was then filtered in the same manner as in Example 1. The filtration was carried out very gently as in Example 1 and a filtrate was obtained. The residual metals of the solution were measured by spectral analysis of ICP emissions. As a result, the amount of Zr was 0.3 ppm or less, the amount of B was 0.4 ppm or less, the amount of Co was 0.8 ppm and the amount of Al was 2.7 ppm based on the polymer. It was found from this that the polymer had a very high purity. The unreacted product and the solvent were removed by distillation (washing) from the treated solution to obtain an achromatic polymer. The sublimation of tris (acetylacetonate) aluminum was not observed during the treatment. No strong absorption based on tris (acetylacetonate) aluminum was observed in the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer. Meanwhile, the precipitate was analyzed. No acetylacetonate-based absorption was observed but a strong lactate-based absorption in the infrared light absorption spectrum of the precipitate. These results show that tris (acetylacetonate) cobalt and triisobutylaluminum, which were catalyst components used in large quantities, were effectively precipitated as lactates. Example 6 A solution comprising 5.0 g of lactic acid, 1.0 g of water and 3.5 g of ethylene glycol (fi = 1.0, f2 = 1.0, f3 = 1.0) was added to the reaction solution a (defined as reaction solution 6- 1 for discrimination) obtained by the method of Reference Example 4 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The light yellow reaction solution was transformed into a turbid light yellow paste. The paste was then filtered in the same manner as in Example 1. The filtration was carried out very gently as in Example 1. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured through ICP emission spectral analysis. As a result, the amount of Zr was 0.1 ppm or less, the amount of B was 0.1 ppm or less, and the amount of Al was 0.5 ppm based on the polymer. It was found from this that the polymer exhibited a very high purity. The treated solution was added to a large amount of methanol to be precipitated there, and the precipitate obtained was then filtered off and dried to obtain an achromatic leaflet polymer. No strong absorption was observed in the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer, and the solution had a transmittance at 500 nm of 99% or more. Meanwhile, the precipitate was analyzed. No absorption based on acetylacetonate was observed but a strong absorption based on a lactate was observed in the infrared light absorption spectrum of the precipitate. Reference Example 5 The flake polymer obtained in Example 6 was dissolved in 1,320 g of toluene introduced into an autoclave. The air in the autoclave filled with the solution was completely replaced by a nitrogen gas. Then, 3.0 g of cobalt tris (acetylacetylacetonate) and 4.8 g of triisobutylaluminum were added to the solution. After, a hydrogenation reaction was carried out at a hydrogen pressure of 45 atmospheres for 120 minutes to obtain a reaction solution. A small amount of the reaction solution was stocked and precipitated in a large amount of methanol to prepare a measurement sample. It was found from the 1H-NMR spectrum of the sample that this polymer had a hydrogenation rate of 99.9 or more. The reduced viscosity (? Sp / c) measured at a temperature of 30 ° C in a 0.5% toluene solution, of the polymer was 0.47 dl / g. The glass transition temperature Tg, measured by DSC, of the polymer was 149 ° C. Example 7 A solution comprising 17.6 g of lactic acid and 1.8 g of water (fi = 2, f2 = 1) was added to the reaction solution obtained in Reference Example 5 at a temperature of 100 ° C under stirring to carry performed a reaction at the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid pink paste. The paste was then filtered in the same manner as in Example 1. The filtration was carried out very gently as in Example 1. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by means of ICP emission spectral analysis. As a result, the amount of Co was 0.4 ppm or less and the amount of Al was 0.7 ppm based on the polymer. It was found, from this, that the polymer had a very high purity. The unreacted product and the solvent were removed by distillation (washing) from the treated solution to obtain an achromatic polymer. The sublimation of tris (acetylacetonate) aluminum was not observed during the treatment. A strong absorption based on tris (acetylacetonate) aluminum was not observed in the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer. The solution had a transmittance at 500 nm of 99% or more. Meanwhile, the precipitate was analyzed. No absorption based on acetylacetonate was observed but a strong absorption based on a lactate was observed in the infrared light absorption spectrum of the precipitate. These results show that tris (acetylacetonate) cobalt and triisobutylaluminum, which were catalyst components used in large quantities, were effectively precipitated as lactates. Reference Example 6 320 g of norbornene, 1,280 g of toluene and 44 ml of a 2M toluene solution of aluminoxane were injected into a 2 liter autoclave. The air in the autoclave was replaced by ethylene at normal pressure and then pressurized with 4 atmospheres of ethylene and 44 ml of a 2M aluminoxane solution containing 150 mg of isopropylidene- (9-fluorenyl) cyclopentadienyl) zirconium dichloride was added to carry out a polymerization at 30 ° C. During the polymerization, 3 atmospheres of ethylene were continuously supplied to obtain a reaction solution. The obtained ethylene-norbornene copolymer had a glass transition temperature of 182 ° C and a reduced viscosity of 1.23 dl / g and the mole fraction of norbornene units in the copolymer was 57%. Example 8 A lactic acid solution comprising 31.8 g of lactic acid and 3.2 g of water (fi = 2.0, f2 = 1.0) was added to the reaction solution obtained in reference example 6 at a temperature of 100 ° C under agitation to carry out a reaction at the same temperature for 2 hours. The reaction solution of light yellow color was transformed into a turbid light yellow paste. The paste was then filtered in the same manner as in Example 1. The filtration proceeded very smoothly as in Example 1. The obtained filtrate was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by ICP emission spectral analysis. As a result, the amount of Zr was 0.1 ppm or less and the amount of Al was 2.1 ppm based on the polymer. It was found from this that the polymer exhibited a very high purity. The unreacted product and the solvent were removed by distillation (washing) of the treated solution to obtain an achromatic polymer. In accordance with the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained copolymer, the solution had a transmittance at 500 nm of 99% or more. Meanwhile, the precipitate was analyzed. A peak based on a lactate was observed in the infrared light absorption spectrum of the precipitate. Comparative Example 1 A solution comprising 115.4 g of lactic acid and 11.6 g of water (fi reaction solution b (defined as reaction solution 7-1 for discrimination) obtained by the method of Reference Example 4 was added to a temperature of 100 ° C under agitation to carry out a reaction at the same temperature for 2 hours.The reaction solution of black coffee color was transformed into a remarkably turbid pink colored paste.The aqueous solution of supersaturated lactic acid was separated into The aqueous lactic acid solution was removed from the paste, and the toluene phase was filtered in the same manner as in Example 1. The filtration proceeded very smoothly, the filtrate obtained was adsorbed on basic alumina to obtain a solution treated achromatic.The residual metals of the solution were measured by spectral analysis of ICP emission.As a result, the amount of Zr was 5 ppm, the amount The amount of B was 8 ppm or less, the amount of Co was 15 ppm or less, and the amount of Al was 32 ppm based on the polymer. Thus, the purity of the polymer was not so high. The unreacted product and the solvent were removed by distillation (washing) from the treated solution to obtain a light brown polymer. Comparative Example 2 An aqueous lactic acid solution containing 0.75 g of lactic acid and 0.2 g of water (fi = 0.05, f2 = 0.05) was added to reaction solution b (defined as reaction solution 8-1 for discrimination) obtained by the method of Reference Example 3 at a temperature of 100 ° C under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution obtained remained brown. The paste was then filtered. However, the filtration was very difficult and the filtrate continued to remain brown. Reference Example 7 285 g of 8-ethylidentetracyclo [4.4.0.1 2.5 7.10] - 3-dodecene, 1,100 g of toluene, 4.2 g of l-hexene, 7.5 g of triethylamine and 15 g of triisobutylaluminum in a steel reactor were injected. 3 liter stainless steel, and 2.8 g of titanium tetrachloride were additionally added to carry out the polymerization at a temperature of -10 ° C for 2 hours in order to obtain a solution of a ring-opening polymer. A polymer obtained by the assortment of a small amount of the solution obtained and purifying it in accordance with a method usually employed had a reduced viscosity (? Sp / c), in accordance with that measured at a temperature of 30 ° C in a solution of toluene at 0.5%, of 0.65 dl / g and a glass transition temperature, measured by DSC, of 186 ° C. Example 9 7.8 g of lactic acid and 1.0 of water (fi = 0.30, f2 = 0.20) were added to the reaction solution obtained in Reference Example 7 at a temperature of 100 ° C under stirring to carry out a reaction to the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid black paste. The paste was then filtered in the same manner as in Example 1. The filtration was carried out very gently as in Example 1. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by ICP emission spectral analysis. As a result, the amount of Ti was 0.4 ppm or less and the amount of Al was 2.6 ppm based on the polymer. It was found from this that the polymer exhibited a very high purity. The treated solution was added to a large amount of ethanol to be precipitated, and the precipitate obtained was then filtered off and dried to obtain an achromatic flake type polymer. According to the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight_ of the polymer obtained, the solution had a transmittance at 500 nm of 99% or more.

Reference Example 8 The flake-type polymer obtained in Example 9 was dissolved in 1,100 g of toluene introduced into an autoclave. The air in the autoclave filled with the solution was completely replaced by nitrogen gas. Then, 3.0 g of cobalt tris (acetylacetonate) and 4.8 g of triisobutylaluminum were added to the solution to carry out a hydrogenation reaction at a hydrogen pressure of 45 atmospheres for 120 minutes in order to obtain a reaction solution. A polymer obtained by supplying a small amount of the obtained reaction solution and purifying it according to a commonly used method had a hydrogenation rate of 99.9% or more in accordance with its 1H-NMR spectrum. In addition, the polymer exhibited a reduced viscosity (? Sp / c), in accordance with that measured at a temperature of 30 ° C in a 5% toluene solution, of 0.53 dl / g, and a glass transition temperature, measured by DSC of 140 ° C. Example 10 An aqueous lactic acid solution comprising 17.6 g of lactic acid and 1.8 g of water (fi = 2.0, f2 = 1.0) was added to the reaction solution obtained in reference example 8 at a temperature of 100 ° C. under stirring to carry out a reaction at the same temperature for 2 hours. The reaction solution of black coffee color was transformed into a turbid pink paste. The paste was then filtered in the same manner as in Example 1. The filtration was carried out very gently as in Example 1. The filtrate obtained was adsorbed on basic alumina to obtain an achromatic treated solution. The residual metals of the solution were measured by ICP emission spectral analysis. As a result, the amount of Ti was 0.2 ppm or less, the amount of Co was 0.5 ppm or less, and the amount of Al was 0.8 ppm based on the polymer. It was found from this that the polymer had a very high purity. The unreacted product and the polymer were removed by distillation (washing) from the treated solution to obtain an achromatic polymer. In accordance with the visible ultraviolet absorption spectrum of a toluene solution containing 20% by weight of the obtained polymer, the solution had a transmittance at 500 nm of 99% or more.

Claims (29)

1. RESINS 1. A process for producing a cyclic olefin polymer in the presence of a transition metal catalyst component soluble in an organic solvent and an organic aluminum compound as a catalyst, comprising the steps of: adding at least one compound selected within of the group consisting of alpha-oxyacid and beta-oxyacid having a hydroxyl group and a carboxyl group in the molecule and derivatives obtained by replacing the hydroxyl group with an alkoxyl group, to a solution of a reaction product to precipitate compounds which they contain a transition metal and aluminum; and separating the precipitate by filtration.
2. 2. The process according to 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 metal component. Ziegler catalyst.
3. 3. The process according to claim 2, wherein the transition metal of the metallocene catalyst component is selected from the group consisting of zirconium, titanium and hafnium.
4. 4. The process according to 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 process according to claim 2, wherein the transition metal of the Ziegler catalyst component is selected from the group consisting of vanadium, cobalt and nickel.
6. The process according to claim 1, wherein the organic aluminum compound is selected from the group consisting of an alkylaluminum compound and an alkylaluminoxane compound.
7. The process according to claim 1, wherein the cyclic olefin polymer contains a polymerized unit derived from a cyclic Olefin represented by the following formula (I): where n is 0 or 1, m is 0 or a positive integer, p is 0 or 1, R1 to R20 are the same or different and are each a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having from 6 to 10 carbon atoms or aliphatic saturated or unsaturated hydrocarbon group having from 1 to 12 carbon atoms, and R 17 R18, or R19 and R20, can form an alkylidene group, R17 or R18, and R19 or R20 can form a ring, and the ring can have a double bond or it can be an aromatic ring.
8. The process according to claim 1, wherein the alpha-oxyacid and the beta-oxyacid have a hydroxyl group and a carboxyl group in the molecule and the derivatives obtained by the substitution of the hydroxyl group by an alkoxy group are represented by the following formula (II) where q is 0 or 1, R'1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R22, R23, R24 and R25 are the same or different and each represents a hydrogen atom , alkyl group having 1 to 6 carbon atoms, phenyl group or benzyl group.
9. 9. The process according to claim 1, wherein the compound represented by the above formula (II) has a boiling point of about 200 ° C or less at 10 mmHg.
10. The process according to claim 1, wherein the compound represented by the above formula (II) is added in an amount of 0.1 to 5 moles based on one equivalent of the total product of the number of moles of the catalyst component of transition metal and the oxidation number of the transition metal and the product of the number of moles of the organic aluminum compound and the oxidation number of aluminum (3), which is obtained for the transition metal catalyst component and organic aluminum contained in a reaction system.
11. 11. The method according to claim 1, wherein a compound selected from the group consisting of water and an alcohol is added in addition to the compound represented by the above formula (II).
12. The process according to claim 11, wherein water is added in an amount of 0 to 9.9 moles based on the same standard as in the case of claim 10.
13. 13. The method according to claim 11, wherein an alcohol is added to an amount of 0 to 5 moles based on the same standard as in the case of claim 10.
14. 14. The process according to claim 1, wherein a reaction to produce a cyclic olefin polymer. is an addition copolymerization reaction between an alpha-olefin having 2 or more carbon atoms and the cyclic olefin in a hydrocarbon solvent in the presence of a polymerization catalyst selected from the group consisting of a metallocene catalyst and Ziegler catalyst .
15. 15. The procedure in accordance with the claim 14, where after carrying out the aforementioned addition copolymerization reaction, a hydrogenation catalyst selected from the group consisting of a metallocene catalyst and Ziegler catalyst is added to the homogeneous polymerization reaction solution to carry out a hydrogenation
16. 16. The process according to claim 14, wherein the metallocene catalyst is a combination of a metallocene catalyst component, an ion boron compound and an alkylaluminum compound or a combination of metallocene catalyst component and an alkylaluminoxane.
17. 17. The procedure in accordance with the claim 15, wherein the metallocene catalyst contains a catalyst component of metalocene and organolithium.
18. 18. The procedure in accordance with the claim 17, where a compound represented by the above formula (II) and water in a total amount of 0.2 to 10 moles are added based on one equivalent of the total product of the number of moles of the transition metal catalyst component and the number of oxidation of the transition metal, the product of the number of moles of the organic aluminum compound and the oxidation number of aluminum (3) and the product of the number of moles of an alkyl lithium and the oxidation number of lithium (1), it is obtained from the transition metal catalyst component, composed of organic aluminum and alkyllithium contained in a reaction system. .
19. The process according to claim 15, wherein the Ziegler catalyst is a combination of an alkylaluminum and a Ziegler catalyst component selected from the group consisting of tris (acetylacetonate) cobalt and bis (acetylacetonate) nickel.
20. The process according to claim 1, wherein a reaction for producing the cyclic olefin polymer is the ring opening polymerization reaction of a cyclic olefin in a hydrocarbon solvent in the presence of a metathesis catalyst.
21. The process according to claim 20, wherein after carrying out ring-opening polymerization, a hydralling catalyst selected within the group consisting of metallocene catalyst and Ziegler catalyst is added to the homogeneous polymerization reaction solution. obtained to carry out the hydrogenation. .
22. The process according to claim 20, wherein the metathesis catalyst contains a metathesis catalyst component and an aluminum alkyl.
23. The process according to claim 21, wherein the metallocene catalyst contains a catalyst component of metalocene and organolithium.
24. The process according to claim 21, wherein a compound represented by the above formula (II) and water are added in a total amount of 0.2 to 10 moles based on one equivalent of the total product of the number of moles of the catalyst component transition metal and the oxidation number of the transition metal, the product of the number of moles of the organic aluminum compound and the oxidation number of aluminum (3) and the product of the number of moles of an alkyllithium and the oxidation number lithium (1), which is obtained for the transition metal catalyst component, composed of organic aluminum and alkyllithium contained in a reaction system.
25. The process according to claim 21, wherein the Ziegler catalyst is a combination of an alkylaluminum and a Ziegler catalyst component selected from the group consisting of tris (acetylacetonate) cobalt and bis (acetylacetonate) nickel.
26. 26. The process according to claim 1, wherein after filtering the precipitate, the reaction solution obtained is either (1) contacted with an adsorbent or (2) washed with an aqueous solution, and then the solvent of the reaction.
27. 27. A cyclic olefin polymer having a content. total of a transition metal, aluminum and lithium of 5 ppm or less.
28. 28. A cyclic olefin polymer having an aluminum content of 3 ppm or less.
29. 29. The use of the cyclic olefin polymer of claim 27 or claim 28 as optical material.