JPH11279266A - Production of alpha-olefin-cyclic olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly purified α-olefin-cyclic olefin copolymer or a hydrogenated α-olefin-cyclic olefin copolymer substantially not containing a polymerization catalyst residue. SOLUTION: This method for producing a purified α-olefin-cyclic olefin copolymer comprises adding an active hydrogen-containing compound comprising an oxycarboxylic acid in an amount of 0.2-10 times the equivalent based on the oxidation number of the whole metal in a catalyst, water, and as necessary, alcohols to a uniform reaction solution containing an α-olefin-cyclic olefin copolymer to generate a precipitation substance mainly derived from the corresponding metal, separating and removing the precipitated substance from the reaction solution, then removing a solvent from the resultant reaction solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a purified α-olefin-cyclic olefin copolymer and a hydrogenated α-olefin.
The present invention relates to a method for producing an olefin-cyclic olefin copolymer. More specifically, the present invention relates to a method for producing the copolymer substantially containing no catalyst residue.

[0002]

2. Description of the Related Art An α-olefin-cyclic olefin copolymer obtained by addition copolymerization of an α-olefin and a cyclic olefin has transparency, heat resistance, weather resistance, chemical resistance, solvent resistance, dielectric properties, and the like. Synthetic resin excellent in various mechanical properties and widely used in various fields.

[0003] The present applicant has reported that the α-olefin-dicyclopentadiene copolymer obtained when the cyclic olefin is dicyclopentadiene does not contain a dicyclopentadiene chain, has high chemical homogeneity, and further has a high water content. It has been found that the added α-olefin-dicyclopentadiene copolymer is particularly excellent in optical homogeneity and transparency, and is suitable for use in optical materials such as optical disc substrate materials.
As previously proposed (Japanese Patent Application Nos. Hei 9-18491 and Hei 9-5)
No. 1638).

These α-olefin-cyclic olefin copolymers are generally used in the presence of a metallocene and a co-catalyst, or by addition copolymerization of an α-olefin and a cyclic olefin in a hydrocarbon solvent such as toluene, cyclohexane, hexane or heptane. It is manufactured by.

[0005] In the production process of an α-olefin-cyclic olefin copolymer, removal of a catalyst metal is a very important step in maintaining characteristics such as transparency, weather resistance and heat resistance of a resin. (1) to (4)
Have been proposed.

(1) A method in which a polymer solution is poured into a large amount of a poor solvent to precipitate a copolymer precipitate, and the precipitate is washed with a poor solvent.

(2) A method of washing the polymer solution with water containing concentrated hydrochloric acid to extract and remove the catalyst residue (JP-A-3-2588)
No. 15, JP-A-4-45103).

(3) A method in which the polymer solution is washed with water containing alcohol to extract and remove the catalyst residue (JP-A-6-228).
235, JP-A-6-228236).

(4) It is not a copolymerization of α-olefin and cyclic olefin, but a small amount of alcohol or organic acid is added to a polymer solution obtained by ring-opening polymerization of a norbornene monomer using a metathesis catalyst. After that, a method of filtering off with a filter aid has been proposed (Japanese Patent Laid-Open No. 2-2).
4319, JP-A-3-66724, JP-A-4-161421).

In the case of (1), the poor solvent must be used at least several times the amount of the polymer solution. In industrial practice, including the recovery of the poor solvent, a heavy burden is imposed on equipment and cost. Also, the purification efficiency was not good. Further, regarding (2) and (3), a waste liquid containing a relatively large amount of catalyst metal is generated, and thus there is a large problem in treating the waste liquid. The method (4) does not generate a large amount of waste liquid,
Unless a large amount of a filter aid is used, it is difficult to perform smooth filtration. Therefore, there arises an unfavorable problem in the treatment of the filter aid and the recovery rate of the polymer. The same can be said for the copolymerization of α-olefin-cyclic olefin. That is, in the copolymerization of an α-olefin and a cyclic olefin using a metallocene catalyst, an organoaluminum compound such as aluminoxane or trialkylaluminum is generally used as an alkylating agent or a cocatalyst. Moreover, their use is much higher than metallocene catalysts. These organoaluminum compounds react very easily with water, alcohols, organic acids, etc., and become insoluble in the hydrocarbon solvent used in the polymerization reaction. However,
The reaction product generally separates as a gel containing a large amount of solvent, and in many cases is a homogeneous solution to the naked eye. Therefore, even if the filtration is performed as it is, the filter medium is clogged and smooth filtration is almost impossible. Therefore, in many cases, a filter aid must be used in combination.

When a copolymer of an α-olefin and a cyclic olefin containing two or more carbon-carbon double bonds is synthesized, the copolymer remains in the copolymer in order to improve heat resistance, weather resistance and light resistance. The carbon-carbon double bond must be saturated by hydrogenation.

Usually, hydrogenation of the polymer is achieved by reacting the copolymer with hydrogen in the presence of a heterogeneous or homogeneous catalyst. When a heterogeneous hydrogenation catalyst is used, the catalyst residue has the advantage of being easily removed by filtration.On the other hand, it requires a large amount of catalyst, requires high temperature and high pressure, and has low hydrogenation selectivity. There are also disadvantages such as the solvent being hydrogenated depending on the solvent used. On the other hand, when a homogeneous hydrogenation catalyst is used, it may be used in a small amount and has a high hydrogenation selectivity, but has a disadvantage that it is difficult to remove the catalyst. Specific examples of the method for removing the homogeneous hydrogenation catalyst include the following (5) to (8).
A method has been proposed.

(5) A method in which the polymer solution is poured into a large amount of a poor solvent to precipitate a copolymer precipitate, and the precipitate is separated by filtration and washed with a poor solvent.

(6) A method in which a polymer solution is brought into direct contact with an adsorbent to adsorb and remove catalyst residues.

(7) A method of washing the polymer solution with acid-containing water or alcohol to extract and remove the catalyst residue.

(8) A method of adding an oxidizing agent to a polymer solution and extracting and removing a catalyst residue with a poor solvent, and / or a method of adding a basic compound and extracting and removing a catalyst residue with a poor solvent (particularly, JP-A-7-109310).

As for the method (5), as in the method (1) for purifying the α-olefin-cyclic olefin copolymer, a large amount of a poor solvent must be used, and the removal efficiency is poor. Unless the operation of dissolution in a solvent and precipitation with a poor solvent was repeated several times, the polymer could not be purified. Although (6) is a simple method, a large amount of adsorbent must be used to completely remove the catalyst residue, and a large amount of catalyst is adsorbed by the adsorbent. There is a problem that the reproduction is not easy and the cost is high. Regarding (7) and (8), there was a problem of waste liquid treatment after extraction.

Further, as a homogeneous catalyst used for hydrogenation,
Ziegl such as so-called tris (acetylacetonato) cobalt and bis (acetylacetonato) nickel
An er type catalyst is preferably used because of its high activity.
In these catalyst systems, an organoaluminum such as a trialkylaluminum is used as an alkylating agent. The problem of removing the catalyst in such a case is the same as the problem encountered in removing the polymerization catalyst of the ring-opened polymer described above. However, unlike the polymerization reaction, the hydrogenation reaction is generally performed at a high temperature. Therefore, a side reaction occurs between the metal acetylacetonate and the organic alkylaluminum in addition to the catalyst species generation reaction (alkylation reaction), and tris (acetylacetonato) aluminum is generated. This compound is extremely stable and does not readily decompose in water, alcohols, and common organic acids. Further, disadvantageously, the compound also dissolves in hydrocarbon solvents such as toluene and cyclohexane which are preferably used in hydrogenation reactions. Therefore, even if water, alcohol and ordinary organic acids are added to decompose and precipitate the catalytically active species and can be filtered off together with the filter aid, the compound cannot be filtered off.

[0019]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been developed in consideration of the above-described problems. An object of the present invention is to provide a method for producing an α-olefin-cyclic olefin copolymer from which residues have been removed and a hydrogenated product thereof. The problems to be solved are (1) the ability to remove metal derived from the catalyst, (2) the coloring of the filtrate,
(3) filtration speed. The favorable phenomena for each are summarized in the following three points.

(1) The catalyst used in the polymerization and / or hydrogenation reaction is efficiently decomposed, and the decomposed product containing the metal contained in the catalyst is insolubilized in the solvent used in the reaction to efficiently precipitate. Is generated.

(2) Colored decomposed products such as catalyst ligands by-produced by the decomposition reaction are not substantially formed. Alternatively, even if a colored decomposed product is by-produced, it is adsorbed on or included in the precipitate and filtered off.

(3) The precipitate is not a swollen gel but a solid, and can be easily filtered.

[0023]

SUMMARY OF THE INVENTION The present applicant has developed an α-olefin-cyclic olefin copolymer polymerized using a metallocene-based catalyst, and hydrogenated α-olefin obtained by hydrogenation using a homogeneous catalyst. As a result of intensive research on a method for removing a homogeneous catalyst contained in a reaction solution after polymerization and / or hydrogenation of an olefin-cyclic olefin copolymer, active hydrogen containing a specific small amount of oxycarboxylic acid and water as essential components When the mixture of the containing compounds is added, the alkylated metal compound forming one component of the catalyst as a co-catalyst and an alkylating agent reacts with the active hydrogen organic-containing compound to form a precipitate, and the other catalyst The components were also included in the precipitate and found to be almost precipitated from the polymer solution. Then, it is found that an α-olefin-cyclic olefin copolymer substantially free of residual metal derived from the catalyst and a hydrogenated product thereof can be obtained by separating the formed precipitate from the reaction solution and removing the solvent. Thus, the present invention has been completed.

To further expand, when a mixture of the active hydrogen compounds having a specific composition was added, the catalyst was decomposed very quickly, and a solid precipitate was formed in many cases. Further, the precipitate was able to be filtered off very quickly by a usual filtration method, and the degree of coloring of the polymer separated and recovered from the obtained filtrate was extremely low. Furthermore, no stable tris (acetylacetonato) aluminum which could not be completely removed without using the mixture of the active compounds was not detected in the filtrate.

That is, the present invention provides a homogeneous reaction solution according to any one of the following (1) to (3): (1) carbonizing an α-olefin having 2 or more carbon atoms and a cyclic olefin in the presence of a metallocene catalyst; Homogeneous solution containing α-olefin-cyclic olefin copolymer obtained by addition copolymerization in hydrogen solvent (1) (2) α-olefin having 2 or more carbon atoms and unsaturated carbon-carbon double bond Is subjected to a hydrogenation reaction in a hydrocarbon solvent in the presence of a homogeneous hydrogenation catalyst to hydrogenate unsaturated double bonds contained in the copolymer. Reaction solution (2) containing the α-olefin-cyclic olefin copolymer obtained by the above method (3). An α-olefin having 2 or more carbon atoms and a cyclic olefin having 2 or more unsaturated carbon-carbon double bonds. In the presence of a metallocene catalyst A homogeneous hydrogenation catalyst is added to a homogeneous polymerization reaction solution obtained by addition copolymerization in a hydrocarbon solvent, and the mixture is subjected to a hydrogenation reaction to remove unsaturated double bonds contained in the copolymer. Α-Olefin obtained by hydrogenation
The homogeneous reaction solution (3) containing the cyclic olefin copolymer is added with 0.2 to 1 of the equivalent of the oxidation number of all metals in the catalyst.
A mixture of an active hydrogen-containing compound composed of alcohols is added as necessary, and a precipitate mainly derived from the metal is generated. Characterized by separating and removing the reaction solution from the reaction solution and removing the solvent from the reaction solution thus obtained to obtain a purified copolymer,
This is a method for producing an olefin-cyclic olefin copolymer.

The cyclic olefin used here is preferably norbornene. Preferably, the α-olefin is ethylene and the cyclic olefin is dicyclopentadiene.

The metallocene catalyst is preferably a catalyst comprising a Group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and at least one cocatalyst.

It is more preferable that the transition metal compound in the metallocene catalyst is zirconium and the cocatalyst is aluminoxane.

It is further preferred that the transition metal compound in the metallocene catalyst is zirconium and the cocatalyst is an ionic boron compound and an alkylating agent such as alkylaluminum.

Further, the homogeneous hydrogenation catalyst is preferably a catalyst comprising a transition metal compound and an alkylating agent.

It is further preferred that the homogeneous hydrogenation catalyst is a catalyst comprising tris (acetylacetonato) cobalt or bis (acetylacetonato) nickel and an alkylaluminum compound.

The reaction solution from which the precipitate has been separated and removed is subjected to the following steps (1) and / or (2) (1) contacting with an adsorbent and (2) washing with an aqueous solution before removing the solvent. It is preferable to attach them.

Hereinafter, the present invention will be described in detail. (Homogeneous reaction solution (1)) The homogeneous reaction solution (1) in the present invention is an addition copolymerization of an α-olefin having 2 or more carbon atoms and a cyclic olefin in a hydrocarbon solvent in the presence of a metallocene catalyst. Manufactured by letting

The α-olefin having 2 or more carbon atoms specifically includes ethylene, propylene, 1-butene,
Examples thereof include α-olefins having 2 to 20 carbon atoms such as -pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, and 1-decene. Among these, ethylene and propylene are preferred from the viewpoint of polymerization activity and the molecular weight of the polymer, and ethylene is particularly preferred. These may be used alone or in combination of two or more.

The cyclic olefin used in the present invention is represented by the following general formulas (I) and (II).

[0036]

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In the formula (I), n is 0 or 1, m is 0 or a positive integer, p is 0 or 1, and R ^{1 to} R
²⁰ is the same or different and is a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms;
¹⁷ and R ¹⁸ or R ¹⁹ and R ²⁰ may form an alkylidene group, or R ¹⁷ or R ¹⁸ and R ¹⁹ or R ²⁰ may form a ring, Further, the ring may have a double bond or an aromatic ring. ]

[0038]

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[In the formula (II), q is an integer of 2 to 8.] As the cyclic olefin represented by the above formula (I),
The following compounds can be exemplified.

Bicyclo [2.2.1] hept-2-ene (norbornene), 1-methylbicyclo [2.2.1] hept-2-
Ene, 6-methylbicyclo [2.2.1] hept-2-ene,
6-ethylbicyclo [2.2.1] hept-2-ene, 6-n
-Propylbicyclo [2.2.1] hept-2-ene, 6-isopropylbicyclo [2.2.1] hept-2-ene, 6-n
-Butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 6-ethylidenebicyclo [2.2.1] hept-2-ene, 6-propylidenebicyclo [ 2.2.1] Hept-2-ene, 6-isopropylidenebicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] bicyclo [2.
2.1] Hept-2-ene derivative, tricyclo [4.3.0.1 ^2.5 ]
-3-decene, 2-methyltricyclo [4.3.0.1 ^2.5 ] -3
- decene, 5-methyl-tricyclo [4.3.0.1 ^2.5] -3- decene, 10-methyl tricyclo [4.3.0.1 ^2.5] -3- tricyclo such decene [4.3.0.1 ^2.5] -3- decene derivatives,
Dicyclopentadiene, tricyclo [4.4.0.1 ^2.5 ] -3-
Undecene, 2-methyltricyclo [4.4.0.1 ^2.5 ] -3-
Undecene, 5-methyltricyclo [4.4.0.1 ^2.5 ] -3-
Undecene, 11-methyltricyclo [4.4.0.1 ^2.5 ] -3
- undecene tricyclo [4.4.0.1 ^2.5] -3- undecene derivatives such as tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3
- dodecene, 8-methyl tetracyclo [4.4.0.1 ^2.5 .1
^7.10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.
1 ^2.5 .1 ^7.10] -3-dodecene, 8-n-propyl-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-isopropyl-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene , 8-n-butyl tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -
3-dodecene, 8-isobutyltetracyclo [4.4.0.1
^2.5 .1 ^7.10] -3-dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-n-propylidene-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene , 8-isopropylidenetetracyclo [4.4.0.1 ^2.5 .
^7.10] -3-dodecene tetracyclo such [4.4.0.1 ^2.5 .1
^7.10 ] -3-dodecene derivative, pentacyclo [6.5.1.
1 ^3.6 2.0 ^2.7 2.0 ^9.13] -4-pentadecene, pentacyclo
^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} -4,10- penta octadecadienoic.

[0041] Among these, inexpensive and readily synthesized isolated bicyclo [2.2.1] from the viewpoint that it is possible hept-2-ene (norbornene) derivatives, dicyclopentadiene, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene derivatives are preferred, and norbornene and dicyclopentadiene are particularly preferred. These may be used alone or in combination of two or more.

The compounds represented by the formula (II) include the following. Cyclobutene, cyclopentene, cyclohexene, cyclooctene. The metallocene catalyst used in the present invention is composed of a metallocene and a cocatalyst. Metallocene has the following general formula (II
Those represented by I) are preferably used.

[0043]

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[In the formula (III), M is a metal selected from Group IV, R ²⁴ and R ²⁵ are the same or different and each is 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 an aryloxy group having 6 to 12 carbon atoms, R ²² and R ²³ are the same or different, monocyclic or can form a sandwich structure with the central metal M A polycyclic hydrocarbon group, R ²¹ is a bridge connecting the R ²² group and the R ²³ group,

[0045]

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In this case, R ^{26 to} R ²⁹ are the same or different and are a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carbon atom having 1 to 12 carbon atoms. 6 to 12 aryloxy groups,
Alternatively, R ²⁶ and R ²⁷ or R ²⁸ and R ²⁹ may form a ring. ]

In the metallocene represented by the above (III), the central metal M is most preferably zirconium from the viewpoint of catalytic activity. R ²⁴ and R ²⁵ may be the same or different, but are preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom (particularly a chlorine atom). R ²² and R ²³
Examples of the preferable cyclic hydrocarbon group include a cyclopentadienyl group, an indenyl group and a fluorenyl group. These may be substituted by a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group, a benzyl group, or the like. R ^{26 to} R ^{29 each} represent a hydrogen atom,
And R ²¹ is preferably a lower alkylene group such as a methylene group, an ethylene group or a propylene group, an alkylidene group such as isopropylidene, a substituted alkylene group such as diphenylmethylene, a silylene group or dimethylsilylene. And substituted silylene groups such as diphenylsilylene.

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

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

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

The concentration of such a metallocene may be determined according to its polymerization activity, but based on the cyclic olefin added to the polymerization reaction system, 10 ^-6 to 10 ^-2 mol, preferably 1 ^-6 mol to 1 mol of the cyclic olefin. Is 10 ^-5 to 10 ^-3 m
ol concentration. Aluminoxane which is an organic aluminum oxy compound is preferably used as the co-catalyst. Aluminoxanes have the general formula (I
V) and the cyclic structure can be exemplified by the general formula (V).

[0052]

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[0053]

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[In the formulas (IV) and (V), R ^{30 to} R
³⁵ is the same or different and is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group or a benzyl group, preferably a methyl group, an ethyl group, particularly preferably It is a methyl group. m is 2
It is an integer above, preferably an integer from 5 to 10. However, the exact structure of the aluminoxane is unknown.

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

The aluminoxane has the function of alkylating the metallocene and converting the metallocene into a cationic one, whereby the polymerization activity is obtained. The metallocene is activated in a solution, but it is preferable to dissolve the metallocene in a solution of aluminoxane. As a solvent used for such activation, an aliphatic hydrocarbon or an aromatic hydrocarbon is preferable, and among them, toluene is most preferable. The activation of the metallocene by the aluminoxane is usually carried out before it is used in the polymerization reaction, the activation time being from 1 minute to 10 hours, preferably from 3 minutes to 1 hour. Activation is from -40 to 11
The reaction is carried out at a temperature of 0 ° C., preferably 0 to 80 ° C.

The concentration of the aluminoxane solution is not particularly limited from 1% by weight to the concentration limit, but 5 to 30% by weight is preferably used. The ratio of aluminoxane to metallocene was 3 mol of aluminoxane per 1 mol of metallocene.
0-20,000 mol, preferably 100-5,000
0 mol is used. If the amount of aluminoxane relative to the metallocene is too small, sufficient polymerization activity cannot be obtained, which is not preferable. Conversely, if the amount of aluminoxane is too large,
Although the polymerization activity is high, it is not economical because a large amount of expensive aluminoxane is used, and it is not preferable because production after polymerization becomes difficult.

As co-catalysts preferably used other than aluminoxane, ionic boron compounds and alkylating agents can be mentioned.

The ionic boron compound specifically refers to a compound represented by the following general formulas (VI) to (IX). _{^{[R 36 3 C] + [}} BR 37 4] - ··· (VI) [R 36 x NH 4-x] + [BR 37 4] - ··· (VII) [R 36 x PH 4-x] _{^{+ [BR 37 4] - ···}} (IIX) Li + [BR 37 4] - in ··· (IX) [wherein (VI) ~ (IX), R 36 are identical or different,
It is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R ³⁷ is the same or different and is an aromatic hydrocarbon group having 6 to 18 carbon atoms. x is 1, 2, 3 or 4. ]

In the ionic boron compounds represented by the above (VI) to (IX), R ³⁸ is preferably the same, and an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a phenyl group or the like is preferred. R ³⁷ can be preferably exemplified. R ³⁷ is preferably the same,
Fluorinated or partially fluorinated aromatic hydrocarbon groups are preferred, and pentafluorophenyl groups are particularly preferred. x is preferably 3. Specific compounds include N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, trityl- (pentafluorophenyl) borate, and lithium-tetrakis (pentafluorophenyl) borate.

As the alkylating agent, alkyl lithium compounds and alkyl aluminum compounds are preferable, and specific examples include methyllithium, butyllithium, trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-butylaluminum. I can do it.

The ionic boron compound has a function of converting metallocene into a cation, and the alkylating agent has a function of alkylating metallocene. By combining both, polymerization activity can be obtained.

The ratio of the ionic boron compound to the metallocene is 0.5 to 10 mol, preferably 0.8 to 3 mol per 1 mol of the metallocene.
ol, more preferably 0.9 to 1.5 mol. The alkylating agent is used in an amount of 2 to 5 based on 1 mol of the metallocene.
00 mol is used. Compared with the case where aluminoxane is used as the cocatalyst, the required amount of the ionic boron compound with respect to the metallocene can be significantly reduced, and the advantage is large in terms of economy and production after polymerization. These cocatalysts are usually used as they are, or are treated as a solvent of a hydrocarbon solvent (for example, toluene) as described above, but can be used by being supported on a carrier. A suitable carrier is an inorganic compound such as silica gel or alumina, or a polyolefin powder obtained by pulverizing polyethylene, polypropylene or the like.

In the present invention, the polymerization reaction is usually carried out using a hydrocarbon solvent. Specifically, pentane, hexane, octane, aliphatic hydrocarbons such as decane, cyclopentane, cyclohexane, cycloaliphatic hydrocarbons such as cyclooctane, benzene, toluene, and aromatic hydrogen such as xylene are exemplified. Among the hydrocarbon solvents, aromatic hydrocarbons are preferred, and toluene is particularly preferred.

(Homogeneous Reaction Solution (2) or (3)) The homogeneous reaction solution (2) in the present invention comprises an α-olefin having 2 or more carbon atoms and a cyclic olefin containing at least 2 carbon-carbon double bonds. To a hydrogenation reaction in a hydrocarbon solvent in the presence of a homogeneous catalyst to hydrogenate unsaturated double bonds contained in the copolymer.

Here, the α-olefin having 2 or more carbon atoms is as defined above.

The cyclic olefin containing two or more carbon-carbon double bonds is a compound having a norbornene skeleton and containing one or more carbon-carbon double bonds in addition to the norbornene moiety.
Specifically, 6-ethylidenebicyclo [2.2.1] hept-2
-Ene, 6-propylidenebicyclo [2.2.1] hept-2
- ene, 6-isopropylidene bicyclo [2.2.1] hept-2-bicyclo [2.2.1] hept-2-ene derivatives such as ene, dicyclopentadiene, 8-ethylidene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-n-propylidene-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene, 8-isopropylidene-tetracyclo [4.4.0.1 ^2.5 .1
^7.10] -3-dodecene tetracyclo such [4.4.0.1 ^2.5 .1
^7.10 ] -3-dodecene derivative, pentacyclo [6.5.1.
1 ^3.6 .0 ^2.7 .0 ^9.13] 4,10 penta octadecadienoic a can be exemplified.

Of these, dicyclopentadiene is preferred from the viewpoint of being inexpensive and easily available. These may be used alone or in combination of two or more.

The copolymer to be subjected to the hydrogenation reaction can be obtained, for example, by addition copolymerization in a hydrocarbon solvent in the presence of a metallocene catalyst, and this is dissolved in a hydrocarbon solvent and hydrogenated. Can be subjected to a reaction.

It is also convenient to supply the above addition reaction solvent as it is as a homogeneous reaction solution (3). In this case, the polymer solution contains a metallocene catalyst, but the metallocene catalyst does not have to be deactivated or removed before the hydrogenation reaction. The metallocene catalyst has no effect on the hydrogenation of the polymer and does not cause side reactions such as gelation of the polymer.

In the present invention, the hydrogenation catalyst used for hydrogenating the copolymer is a catalyst comprising a combination of a transition metal compound and an alkylating agent. As the transition metal compound, for example, vanadium, chromium, manganese,
Transition metal halides such as iron, ruthenium, cobalt, rhodium, nickel and palladium, acetylacetonate complexes, carboxylate complexes, naphthate complexes, trifluoroacetate complexes, stearate complexes, and the like. Dates, tris (acetylacetonato) chromium, tris (acetylacetonato) manganese, cobalt acetate, tris (acetylacetonato) cobalt, cobalt octenoate, bis (acetylacetonato) nickel and the like can be mentioned.
Examples of the alkylating agent include lithium, magnesium, aluminum, and zinc compounds, and specific examples include butyllithium, dimethylmagnesium, triethylaluminum, triisobutylaluminum, methylaluminoxane, and diethylzinc. Among these, from the viewpoint of catalytic activity, a combination of cobalt, a nickel compound and an alkylaluminum compound or an alkyllithium compound is preferable, and tris (acetylacetonato) cobalt or bis (acetylacetonato) nickel, triethylaluminum,
Combinations of alkyl aluminum compounds such as triisobutyl aluminum or methyl aluminoxane are particularly preferred.

When the copolymer solution to be subjected to the hydrogenation reaction is supplied as a homogeneous polymerization reaction solution obtained by addition copolymerization in a hydrocarbon solvent in the presence of a metallocene catalyst, The combined solution contains an aluminoxane or an alkylaluminum compound as a polymerization promoter. These may be considered to act as an alkylating agent of the hydrogenation catalyst as it is. Regarding the quantitative relationship between the transition metal compound and the alkylating agent, one mole of the metal component of the alkyl metal compound is added to 1 mole of the metal of the transition metal compound. 5
0 mol or less, preferably 10 mol or less.

The transition metal compound is converted to a transition metal compound which has been alkylated by an alkylating agent, and has a hydrogenation catalytic activity.

As the hydrogenation catalyst used for hydrogenating the copolymer, other than the above, there may be mentioned a catalyst comprising only a transition metal compound. Specifically, carbonylchlorohydridotris (triphenylphosphine) ruthenium, dihydridocarbonyltris (triphenylphosphine)
Ruthenium, dihydridotetrakis (triphenylphosphine) ruthenium, tetrahydridotris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, hydridecarbonyltris (triphenylphosphine) rhodium and the like can be exemplified. However, these catalysts are not preferable because they are extremely stable to active hydrogen-containing compounds, cannot increase the polarity of metal components by decomposition, and cannot be removed by the catalyst removal method of the present invention.

The concentration of the transition metal compound in the hydrogenation catalyst may be determined in accordance with the polymerization activity, and based on the carbon-carbon double bond in the polymer, one mole of the double bond is used.
Usually 10 ^-6 to 10 ^-2 mol, preferably 10 ^-5 to 10 ^-3 m
ol concentration. In the present invention, the hydrogenation reaction is usually performed using a hydrocarbon solvent. Specifically, pentane, hexane, octane, aliphatic hydrocarbons such as decane, cyclopentane, cyclohexane, alicyclic hydrocarbons such as cyclooctane, benzene, toluene,
Examples thereof include aromatic hydrocarbons such as xylene. Even when an aromatic hydrocarbon is used as a solvent, by controlling the hydrogenation reaction conditions, only the polymer can be selectively hydrogenated without hydrogenating the aromatic hydrocarbon solvent. The temperature, hydrogen pressure, and reaction time of the hydrogenation reaction of the copolymer may be determined according to the type of the monomer used for the addition copolymerization and the type of the hydrogenation catalyst. Usually, the temperature is 0 ° C or more and 200 ° C or less, preferably 20 ° C or more and 180 ° C or less, and the hydrogen pressure is 0.1 kgf / cm ² or more and 200 kg.
f / cm ² or less, preferably 1 kgf / cm ² or more, 10
0 kgf / cm ² or less, reaction time is 0.1 hour or more, 1
0 hours or less.

The hydrogenation ratio (hydrogenation ratio of carbon-carbon double bond) of such a copolymer is at least 99%, preferably at least 99.5%, more preferably at least 99.9%. When the degree of hydrogenation is lower than 99%, the thermal stability is insufficient, coloring and the like are likely to occur during melt molding, and the glass transition temperature is greatly lowered by hydrogenation. However, in the case of the copolymer of the present invention, Since the carbon-carbon double bond is located in the side chain, the glass transition temperature hardly changes before and after hydrogenation, which is preferable.

(Removal of Catalyst) In the present invention, an active hydrogen-containing compound is added to the polymer solution after addition polymerization and / or hydrogenation in accordance with the equivalent number of oxidation of the metal in the metallocene catalyst and the hydrogenation catalyst. The catalyst is added to decompose and deactivate the catalyst, and at the same time, to precipitate a catalytic metal component.

The equivalent number (m) of the oxidation number of the metal in the metallocene catalyst and the hydrogenation catalyst is the product of the oxidation number of the metal of all the catalysts and cocatalysts contained in the polymer solution and the number of moles added. Is the sum of For example, the oxidation numbers of zirconium, aluminum, and cobalt are 4, 3, and 3, respectively.
Accordingly, when zirconium, aluminum, and cobalt are added in amounts of m ₁ , m ₂ , and m ₃ , respectively, the oxidation number equivalent (m) is calculated as m = 4 m ₁ +3 m ₂ +3 m ₂ . The amount of the active hydrogen-containing compound added accordingly is determined by the following formula. M ₁ = f ₁ xm M ₂ = f ₂ xm M ₃ = f ₃ xm [wherein M ₁ , M ₂ , and M ₃ are the amounts of added oxycarboxylic acid, water, and alcohol (mol), respectively] And f
₁ , f ₂ and f ₃ are the addition ratios of oxycarboxylic acid, water and alcohol added to the oxidation number reference equivalent. ]

However, in general, when a catalyst such as Co (acac) _{3 is} subjected to a hydrogenation reaction in combination with an alkylating agent such as trialkylaluminum, Co is reduced and the oxidation number of the metal is reduced. In this case, the oxidation number of Co (3) was used as the oxidation number of Co.

The addition ratio (F = f ₁ + f ₂ + f ₃ ) of the active hydrogen-containing compound to be added in the present invention is from 0.2 to 10, preferably from 0.5 to 5. The addition ratio (f ₁ ) of the oxycarboxylic acid is 0.2 to 5, preferably 0.3 to 5.
4. Addition ratio of water (f ₂₎ from 0.1 to 10, preferably from 0.2 to 5. The addition ratio (f ₃ ) of the alcohol added as required is 0 to 5, preferably 0 to 4. However, it goes without saying that the total sum (F) of the addition ratio of oxycarboxylic acid, water and alcohol is within the above range.

If the amount of the active hydrogen-containing compound is too small, it is not preferable because the precipitation of the catalyst component becomes incomplete. On the other hand, if the amount is too large, the polarity of the polymer solution increases, and it is not preferable because a part or all of the catalyst component is dissolved in the polymer solution while being supplemented by the dissolved active hydrogen-containing compound. Of course, if the content of the active hydrogen-containing compound is unnecessarily large, the compound will far deviate from the solubility in the polymer solution. Therefore, before performing the filtration process,
You have to separate. Such a state is not preferable because a waste liquid containing a large amount of metal is generated. Further, among the active hydrogen-containing compounds, α-oxyacid has a high boiling point, so that it is difficult to distill off the solvent from the filtrate.

The active hydrogen-containing compound used in the present invention will be described below. Examples of the oxycarboxylic acid include oxycarboxylic acids having 3 to 6 carbon atoms, such as glycolic acid, lactic acid, β-methyl-β-oxypropionic acid, γ-oxybutyric acid, and ε-oxycaproic acid. In general, carboxylic acids react with many of the catalysts and cocatalysts used in the present invention to form salts. The important points here are the reactivity of the carboxylic acid to the catalyst and the cocatalyst and the solubility of the salt formed in the hydrocarbon solvent. The oxycarboxylic acid has a high polarity because it contains a hydroxyl group in the molecule, and the formed salt hardly dissolves in a nonpolar hydrocarbon solvent. Among them, α-oxy acids such as glycolic acid and lactic acid are particularly highly reactive because they react with various metals to form chelates. As described above, even a stable compound such as tris (acetylacetonato) aluminum by-produced in the hydrogenation reaction easily reacts to form a lactate of aluminum. The solubility of the salt is different from that of tris (acetylacetonato) aluminum, which is preferable because it is insoluble in the hydrocarbon solvent used in the present invention. Among the α-oxy acids, glycolic acid and lactic acid are particularly preferred because they are available at low cost.

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

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

The active hydrogen-containing compounds to be added can be used alone or in combination of two or more.

The addition of the active hydrogen-containing compound to the polymer solution is from 0 to 200 ° C., preferably from 10 to 180 ° C., more preferably from room temperature to the boiling point of the solvent used. If the reaction temperature is too low, the reaction does not proceed sufficiently, and if it is too high, the precipitates are easily dissolved in the polymer solution, which is not preferable.

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

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

(Removal of polymerization catalyst)
From the metallocene, a lactic acid / water reactant of zirconium metal [Zr (OLc) _m (OH) _4-m : OLc represents a lactic acid residue, m is an integer of 0 to 4], a isopropylidene ligand ( 9-fluorenyl) (cyclopentadienyl)
Derivatives from the groups and hydrogen halides, as well as partial reactants of the metallocene with lactic acid and / or water, are formed. In addition, a trityl methyl compound containing trityl methane is generated from a cation component of trityl tetra (pentafluorophenyl) borate, which is a cocatalyst, and boric acid [HB (C ₆ F ₅ ) ₄ ] is generated from an anion component. From triisobutylaluminum, alkanes and Al (OLc) _n (O
H) _3-n [OLc is as described above, n is an integer of 0 to 3]
And / or a condensate thereof is formed. Generally, in the case of a condensate, the higher the degree of condensation, the more likely it is to form a gel.

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

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

Further, organic substances (the above-mentioned isopropylidene (9-fluorenyl)
Derivatives from (cyclopentadienyl) groups, organic substances derived from ligands such as acetylacetone, triphenylmethane derived from alkanes and trityl groups, and excess active hydrogen compounds)
Although at least a part of is left in the polymer solution, it can be removed when removing the solvent and residual cyclic olefin or its hydrogenated product.

The deposited catalyst metal residue can be removed from the polymer solution by a conventional method such as filtration or centrifugal separation.

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

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

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

The α-olefin-cycloolefin copolymer or the hydrogenated α-olefin-cycloolefin copolymer obtained according to the present invention may contain various additives, for example, an antioxidant, if necessary. Is also good. Examples of antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [2- (3,5-Di-tert-butyl-4-hydroxyphenyl) ethylpropionate] methane, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate], tris (2,4, -di-t-butylphenyl) phosphite,
Bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite and the like can be mentioned.

The α-olefin-cyclic olefin copolymer or hydrogenated α-olefin-cyclic olefin copolymer obtained according to the present invention has a very high purity with substantially no residue of the polymerization catalyst. Therefore, it is excellent in various properties such as transparency, heat resistance, light resistance, dielectric properties and opportunity properties, and can be suitably used as an optical material such as an optical disc substrate and a camera lens.

[0099]

According to the present invention, an α-olefin-cyclic olefin copolymer solution obtained by using a metallocene catalyst or a hydrogenated α-olefin-cyclic copolymer obtained by using a homogeneous hydrogenated solvent is used. The catalyst residue can be efficiently removed from the olefin copolymer solution by a simple method that does not generate a waste liquid containing a metal, and a highly pure copolymer can be obtained.

[0100]

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

Examples were carried out under an inert atmosphere such as argon or nitrogen, unless otherwise specified. Toluene (solvent) and dicyclopentadiene used were purified by distillation according to a conventional method and sufficiently dried.

As the metallocene, isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was purchased from Boulder Scientific and used as it was.

As the ionic boron compound, trityl-tetrakis (pentafluorophenyl) borate was purchased from Tosoh Akzo Co., Ltd. and used as it was.

Triisobutylaluminum was purchased from Tosoh Akzo Co., Ltd. at a concentration of 2M in toluene and used as it was.

Tris (acetylacetonate) cobalt was purchased from Wako Pure Chemical Industries, Ltd. and used as it was.

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

Reference Example 1 1.3 g of tris (acetylacetonato) aluminum was dissolved in 300 g of toluene. The solution was heated to 100 ° C., and 8.4 g of a 90% by weight aqueous lactic acid solution was added dropwise with stirring. Thereafter, the mixture was heated and stirred at the same temperature for 2 hours. The generated precipitate was separated by filtration to obtain 0.8 g of a colorless solid powder. The infrared absorption spectrum of this powder (FIG. 1) was compared with the spectrum of the raw material tris (acetylacetonato) aluminum (FIG. 2). As is clear from the figure, 1540 cm
The strong peak near ^-1 disappeared, and instead a strong peak based on the carbonyl group of aluminum lactate was found to be 1620.
It was found near cm ^-1 . The infrared absorption spectrum of the obtained powder almost coincided with the infrared absorption spectrum of aluminum lactate. In the solid ¹³ C-NMR of the powder, peaks attributable to the CH3 group,> CH-group and -COO- group of aluminum lactate were observed at around 23 ppm, 63 ppm and 180 ppm, respectively. As is clear from the above, it was found that tris (acetylacetonato) aluminum was changed to aluminum lactate.

A similar experiment was conducted by adding 1.3 g of ethylene glycol instead of the lactic acid aqueous solution used above. However, no precipitation was observed.

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

[Reference Example 2] 0.8 g of triisobutylaluminum cobalt was dissolved in 300 g of toluene. Subsequently, 0.30 g of cobalt tris (acetylacetylacetonate) was added to prepare a hydrogenation catalyst. The solution is
Heat to 0 ° C. and stir with 8.4 g of 90% by weight lactic acid
Was added dropwise. Thereafter, the mixture was heated and stirred at the same temperature for 2 hours. The generated precipitate was separated by filtration to obtain 1.9 g of a light pink solid powder. The infrared absorption spectrum (FIG. 3) of this powder was compared with the spectrum of tris (acetylacetonato) aluminum (FIG. 2) and the spectrum of tris (acetylacetylacetonato) cobalt (FIG. 4). As can be seen, from the product powder has also disappeared peak of tris (acetylacetonate) peak of 1540 cm ^-1 vicinity from aluminum also tris (acetyl acetylacetonate) cobalt from the 1520 cm ^-1,
Instead, the peak based on aluminum lactate is 1620c
m- ¹ .

Reference Example 3 In a 3 L stainless steel reaction vessel, 186 g of dicyclopentadiene and 1 part of toluene
320 g and triisobutylaluminum 3.6 g
Was added. The inside of the container is replaced with normal pressure ethylene, and isopropylene (9-fluorenyl) (cyclopentadienyl)
119 mg of zirconium dichloride and 252 mg of trityl-tetrakis (pentafluoroborate) were added, and polymerization was carried out at 30 ° C. During the polymerization, ethylene at normal pressure was constantly supplied, and 163 g of dicyclopentadiene was added at a rate such that the ratio of the addition rate of dicyclopentadiene to the consumption rate of ethylene became 42:58. At a time (150 minutes) when the consumption of ethylene reached the molar amount corresponding to the total amount of added dicyclopentadiene of 1320 g (150 minutes), the supply of ethylene was stopped, and the reaction was terminated.

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

The obtained reaction liquid (reaction liquid 1) was fed under pressure to a 10 L autoclave, and 3.0 g of tris (acetylacetylacetonato) cobalt and 4.8 g of triisobutylaluminum were added to the reaction liquid. Thereafter, a hydrogenation reaction was performed at a hydrogen pressure of 45 atm for 120 minutes to obtain a reaction solution 3. A small amount of the reaction solution was collected and precipitated in a large amount of methanol to obtain a measurement sample. ^{From the 1} H-NMR spectrum, the hydrogenation rate of this polymer was 99.9 or more. The reduced viscosity (ηsp / c) measured at 30 ° C. using a 0.5% toluene solution was 0.45 dL / g. Also, D
Tg measured using SC was 151 ° C.

Example 1 28.9 g of lactic acid and 2.9 g of water (lactic acid / water addition) were added to the reaction solution 3 obtained in Reference Example 3 (defined as reaction solution 3-1 for distinction) at 100 ° C. Magnification: f
An aqueous solution of lactic acid containing (1 / f2 = 2.0 / 1.0) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution is
Black-brown to pink cloudy slurry (Slurry-4-
Changed to 1). The slurry was subsequently filtered. The apparatus used was a cylindrical filter having a diameter of 11 cm. The filter was 5 celite over Naslon NF-05.
cm filled and covered with a flannel fabric. The filtration pressure was 4 kg / cm ² (gauge pressure). FIG.
As shown in the curve A, the filtration proceeded very smoothly, and about 1.6 kg of the slurry could be processed in 90 minutes. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless and transparent treatment liquid (treatment liquid 5-1). The residual metal in the liquid was measured by ICP emission spectrometry. As a result, Zr: 0.1 ppm or less, B: 0.1 p
pm or less, Co: 0.3 ppm and Al: 0.7 pp
m. As a result, it was found that the purity was extremely high. In particular, it was found that the value of Al was also extremely low. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless and transparent polymer (purified polymer 6-1). During the treatment, tris (acetylacetonate)
No sublimation of aluminum was observed. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer (FIG. 6), no strong absorption based on tris (acetylacetonato) aluminum (FIG. 7) was observed. The sharp peak near 300 nm in FIG. 6 is based on a derivative derived from an isopropylidene (9-fluorenyl) (cyclopentadienyl) group which is a ligand of a metallocene catalyst. 500 nm of the solution
Was 99% or more.

On the other hand, the precipitate (precipitate 7-1) was analyzed. The infrared absorption spectrum of the precipitate (FIG. 8)
Tris absorption (acetylacetonate) cobalt and tris (acetylacetonate), respectively 1520 cm ^-1 and near 1540 cm ^-1 vicinity based on aluminum was not observed at all, a strong absorption based on lactate was observed instead. Also, in the solid ¹³ C-NMR spectrum of the precipitate (FIG. 9), the peak due to lactate was 23 ppm.
Neighborhood (CH3), around 63 ppm (> CH-) and 1
It was found near 80 ppm (-COO-). These results indicate that the catalytic components used in large quantities, tris (acetylacetonato) cobalt and triisobutylaluminum, are effectively precipitated as lactate.

Example 2 100 ° C. was applied to the reaction solution 3 obtained by the method of Reference Example 3 (defined as reaction solution 3-2 for distinction).
A solution containing 21.7 g of lactic acid and 2.9 g of water (lactic acid /
(The addition ratio of water: f1 / f2 = 1.5 / 1.0) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution is
Black-brown to pink cloudy slurry (Slurry-4-
Changed to 2). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. As shown by the curve B in FIG. 5, the filtration proceeded very smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-2). The residual metal in the solution was measured by ICP published analysis. As a result, based on the polymer, Zr: 0.1 ppm or less, B: 0.1 ppm
Hereinafter, Co was 0.6 ppm and Al was 0.9 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer (purified polymer 6-2). No sublimation of aluminum tris (acetylacetonate) was observed during the treatment. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. The transmittance of the solution at 500 nm was 99% or more.

On the other hand, the precipitate (precipitate 7-2) was analyzed. The infrared absorption spectrum of the precipitate showed that each of the precipitates was based on tris (acetylacetonato) cobalt and tris (acetylacetonato) aluminum.
Peak peak and 1640 cm ^-1 vicinity of 20 cm ^-1 vicinity was not observed at all, a strong absorption based on lactate was observed in the vicinity of 1620 cm ^-1 instead. These results indicate that the highly used catalyst components tris (acetylacetonato) cobalt and triisobutylaluminum are effectively precipitated as lactate.

Example 3 A reaction solution 3 obtained by the method of Reference Example 3 (defined as reaction solution 3-3 for distinction) was heated to 100 ° C.
A solution containing 57.8 g of lactic acid and 5.8 g of water (lactic acid /
(The addition ratio of water: f1 / f2 = 4.0 / 2.0) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution is
Black-brown to pink cloudy slurry (Slurry-4-
Changed to 3). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-3). The residual metal in the liquid was measured by ICP emission spectrometry. As a result, for the polymer, Z
r: 0.3 ppm or less, B: 0.2 ppm or less, Co:
0.34 ppm or less and Al: 2.4 ppm. As a result, it was found that the purity was extremely high. An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer (purified polymer 6-3).
No sublimation of aluminum tris (acetylacetonate) was observed during the treatment. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. The transmittance of the solution at 500 nm was 99% or more.

On the other hand, the precipitate (precipitate 7-3) was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed. These results show that the catalytic components used in large quantities, tris (acetylacetonato) cobalt and triisobutylaluminum,
It shows that it was effectively precipitated as lactate.

Example 4 100 ° C. was applied to the reaction solution 1 obtained by the method of Reference Example 3 (defined as reaction solution 3-4 for distinction).
And a solution containing 5.0 g of lactic acid, 1.0 g of water and 3.5 g of ethylene glycol (addition ratio of lactic acid / water / ethylene glycol: f1 / f2 / f3 = 1.0 / 1.0 / 1.
0) was added with stirring and reacted at the same temperature for 2 hours. The reaction solution changed from a pale yellow solution to a pale yellow cloudy slurry (slurry-4-4). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-4). The residual metal in the liquid was measured by ICP emission spectrometry. As a result, based on the polymer, Zr: 0.1 ppm or less, B: 0.1 ppm
Below and Al: 0.5 ppm. As a result, it was found that the purity was extremely high. The treated liquid was precipitated in a large amount of methanol, and the deposited precipitate was separated by filtration and dried to obtain a colorless flaky polymer (purified polymer 6-4). In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. The transmittance of the solution at 500 nm is 99%.
% Or more.

On the other hand, the precipitate (precipitate 7-4) was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed.

Reference Example 4 The flake polymer (purified polymer 6-4) obtained in Example 4 was dissolved in 1320 g of toluene introduced into an autoclave. The air in the autoclave containing the solution was sufficiently replaced with nitrogen gas. 3.0 g of tris (acetylacetylacetonato) cobalt and 4.8 g of triisobutylaluminum were added to the solution. Then, at a hydrogen pressure of 45 atm, 12
A hydrogenation reaction was performed for 0 minutes to obtain a reaction solution 2. A small amount of the reaction solution was collected and precipitated in a large amount of methanol to obtain a measurement sample. ^{From the 1} H-NMR spectrum, the hydrogenation rate of this polymer was 99.9 or more. Further, the reduced viscosity (ηsp / c) measured at 30 ° C. using a 0.5% toluene solution is 0.1.
It was 47 dL / g. The Tg measured by DSC was 149 ° C.

Example 5 1 was added to the reaction solution 2 obtained in Reference Example 4.
At 00 ° C., a solution containing 17.6 g of lactic acid and 1.8 g of water (addition ratio of lactic acid / water: f ₁ / f ₂ = 2/1) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution was converted from a black-brown solution to a cloudy pink slurry (Slurry-4-).
Changed to 5). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-5). The residual metal in the liquid was measured by ICP emission spectrometry. As a result, for the polymer, C
o: 0.4 ppm or less, and Al: 0.7 ppm. As a result, it was found that the purity was extremely high.
Unreacted substances and the solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer (purified polymer 6-5). During the treatment, tris (acetylacetonate)
No sublimation of aluminum was observed. In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, no strong absorption based on aluminum tris (acetylacetonate) was observed. The transmittance of the solution at 500 nm was 99% or more.

On the other hand, the precipitate (precipitate 7-5) was analyzed. In the infrared absorption spectrum of the precipitate, no absorption based on acetylacetonate was observed at all, and instead a strong absorption based on lactate was observed. These results show that the catalytic components used in large quantities, tris (acetylacetonato) cobalt and triisobutylaluminum,
It shows that it was effectively precipitated as lactate.

Reference Example 5 To a 2 L autoclave were added 320 g of norbornene, 1280 of toluene and 44 ml of a 2M toluene solution of aluminoxane. The air in the autoclave was pressurized with 4 atm of ethylene replaced with ethylene at normal pressure, and a 2M aluminoxane solution containing 150 mg of isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride 44 was used.
Then, polymerization was carried out at 30 ° C. During the polymerization, 3 atm of ethylene was constantly supplied to obtain a reaction solution. The Tg of the ethylene-norbornene copolymer obtained here was 182 ° C., the reduced viscosity was 1.23 dL / g, and the molar fraction of norbornene units in the copolymer was 57%.

Example 6 The reaction solution obtained in Reference Example 5
At 0 ° C., an aqueous lactic acid solution containing 31.8 g of lactic acid and 3.2 g of water (addition ratio of lactic acid / water: f ₁ / f ₂ = 2/1) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution is
From a pale yellow solution to a pale yellow cloudy slurry (Slurry-4-
Changed to 6). The slurry was subsequently filtered. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly as in Example 1. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-6). The residual metal in the solution was measured by ICP published analysis. As a result, for the polymer, Z
r: 0.1 ppm or less, and Al: 2.1 ppm. As a result, it was found that the purity was extremely high.
An unreacted substance and a solvent were distilled off (flushing treatment) from the treatment liquid to obtain a colorless polymer (purified polymer 6-6). In a UV-visible absorption spectrum of a 20 wt-% toluene solution of the obtained polymer, the transmittance of the solution at 500 nm was 99% or more.

On the other hand, the precipitate (precipitate 7-6) was analyzed. In the infrared absorption spectrum of the precipitate, a peak based on lactate was observed.

Comparative Example 1 100 ° C. was applied to the reaction solution 3 obtained by the method of Reference Example 3 (defined as reaction solution 3-7 for distinction).
, A solution containing 115.4 g of lactic acid and 11.6 g of water (addition ratio of lactic acid / water: f ₁ / f ₂ = 8/4) was added with stirring, and reacted at the same temperature for 2 hours. The reaction solution turned from black-brown to pink, and turned into a noticeably turbid slurry (slurry 4-7). In addition, a supersaturated lactic acid aqueous solution phase-separated. From the slurry, the lactic acid aqueous solution was looked into, and the toluene phase was subjected to a filtration treatment. Filtration was performed in the same manner as in Example 1. Filtration proceeded very smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless treatment liquid (treatment liquid 5-7). The residual metal in the solution was measured by ICP published analysis. As a result, for the polymer,
Zr: 5 ppm, B: 8 ppm or less, Co: 15 ppm
Below and Al: 32 ppm. The purity of the polymer obtained from this result was not always high. Unreacted substances and the solvent were distilled off (flushing treatment) from the treatment liquid to obtain a light brown polymer.

Comparative Example 2 100 ° C. was applied to the reaction solution 3 obtained by the method of Reference Example 3 (defined as reaction solution 3-7 for distinction).
A lactic acid aqueous solution containing 1.5 g of lactic acid and 0.2 g of water (addition ratio of lactic acid / water: f ₁ / f ₂ = 0.1 / 0.05) is added with stirring, and reacted at the same temperature for 2 hours. Was. However, the resulting reaction solution remained brown. The slurry was subsequently filtered. However, filtration was extremely difficult, and the filtrate still remained brown.

[Brief description of the drawings]

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

FIG. 2 Infrared absorption spectrum of tris (acetylacetonate) aluminum

FIG. 3 is an infrared absorption spectrum of a colorless solid obtained in Reference Example 2.

FIG. 4 Infrared absorption spectrum of tris (acetylacetonate) cobalt

FIG. 5 shows slurry 4 obtained in Examples 1 and 2 respectively.
1 and the filtration curves of Slurry 4-2. The curves A and B in the figure correspond to the slurry 4-1 and the slurry 4-, respectively.
2 is a filtration curve of Slurry 4-3.

FIG. 6 shows an ultraviolet-visible absorption spectrum of purified polymer 6-1 obtained in Example 1.

FIG. 7 is an ultraviolet-visible absorption spectrum of a toluene solution of tris (acetylacetonate) aluminum (3 × 10 ⁻³ M).

FIG. 8 is an infrared absorption spectrum of the precipitate (precipitate 7-1) obtained in Example 1.

FIG. 9 is a solid-state NMR spectrum of the precipitate (precipitate 7-1) obtained in Example 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaki Takeuchi 4-2-2 Asahigaoka, Hino-shi, Tokyo Teijin Incorporated Tokyo Research Center (72) Inventor Kaoru Iwata 4-2-2 Asahigaoka, Hino-shi, Tokyo Teijin Co., Ltd. Tokyo Research Center

Claims (14)

[Claims] 1. A homogeneous reaction solution according to any one of the following (1) to (3): (1) an α-olefin having 2 or more carbon atoms and a cyclic olefin in a hydrocarbon solvent in the presence of a metallocene catalyst; (1) (2) α-olefin having 2 or more carbon atoms and two or more unsaturated double bonds between carbon atoms containing an α-olefin-cyclic olefin copolymer obtained by addition copolymerization in water It is obtained by subjecting a copolymer with a cyclic olefin having a hydrogenation reaction in a hydrocarbon solvent in the presence of a homogeneous hydrogenation catalyst to hydrogenate unsaturated double bonds contained in the copolymer. Homogeneous reaction solution containing α-olefin-cyclic olefin copolymer (2) (3) Metallocene-based α-olefin having 2 or more carbon atoms and cyclic olefin having 2 or more unsaturated double bonds between carbon atoms Hydrocarbon-based in the presence of a catalyst To a homogeneous polymerization reaction solution obtained by addition copolymerization in a medium, a homogeneous hydrogenation catalyst is added, and the mixture is subjected to a hydrogenation reaction to hydrogenate unsaturated double bonds contained in the copolymer. Α-olefin obtained
The homogeneous reaction solution (3) containing the cyclic olefin copolymer is added with 0.2 to 1 of the equivalent of the oxidation number of all metals in the catalyst.
A mixture of an active hydrogen-containing compound composed of alcohols is added as necessary, and a precipitate mainly derived from the metal is generated. Characterized by separating and removing the reaction solution from the reaction solution and removing the solvent from the reaction solution thus obtained to obtain a purified copolymer,
A method for producing an olefin-cyclic olefin copolymer. 2. The method for producing an α-olefin-cycloolefin copolymer according to claim 1, wherein the cyclic olefin is norbornene. 3. The method for producing an α-olefin-cyclic olefin copolymer according to claim 1, wherein the α-olefin is ethylene and the cyclic olefin is dicyclopentadiene. 4. The α-catalyst according to claim 1, wherein the metallocene-based catalyst is a catalyst comprising a Group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and at least one cocatalyst. -A method for producing an olefin-cyclic olefin copolymer. 5. The method for producing an α-olefin-cyclic olefin copolymer according to claim 1, wherein the transition metal in the metallocene-based catalyst is zirconium, and the co-catalyst is aluminoxane. 6. The production of an α-olefin-cyclic olefin copolymer according to claim 1, wherein the transition metal in the metallocene catalyst is zirconium, and the cocatalyst is an ionic boron compound and an alkylating agent. Method. 7. The method for producing a hydrogenated α-olefin-cyclic olefin copolymer according to claim 1, wherein the homogeneous hydrogenation catalyst is a catalyst comprising a transition metal compound and an alkylating agent. 8. The hydrogenated α- according to claim 1, wherein the homogeneous hydrogenation catalyst is a catalyst comprising tris (acetylacetonato) cobalt or bis (acetylacetonato) nickel and an alkylaluminum compound.
A method for producing an olefin-cyclic olefin copolymer. 9. The method for producing an α-olefin-cyclic olefin copolymer according to claim 1, wherein the oxycarboxylic acid is α-oxycarboxylic acid. 10. The process for producing an α-olefin-cyclic olefin copolymer according to claim 1, wherein the oxycarboxylic acid is added in an amount of 0.2 to 5 times the molar equivalent of the oxidation standard of all metals. Method. 11. Oxidation standard equivalent of all metals 0.1 to 10
11. The method according to claim 1, wherein water is added in an amount of twice as much as water.
3. The method for producing an α-olefin-cyclic olefin copolymer according to item 1. 12. The method for producing an α-olefin-cyclic olefin copolymer according to claim 1, wherein the precipitate is in a solid state. 13. A method for producing an α-olefin-cyclic olefin copolymer, wherein the content of all metals contained in the purified copolymer according to claim 1 is 5 ppm or less. . 14. The reaction solution according to claim 1, wherein the reaction solution from which the precipitate has been separated / removed is subjected to (1) contact with an adsorbent and (2) washing with an aqueous solution before removing the solvent. The method for producing an α-olefin-cyclic olefin copolymer according to the above.