JP2002284820A - Cycloolefin addition (co)polymer and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently eliminate the catalyst from a cycloolefin addition (co)polymer prepared by the addition polymerization of a specific cycloolefin compound in the presence of an addition polymerization catalyst containing a nickel or cobalt compound. SOLUTION: A specific cycloolefin compound alone or together with an α-olefin monomer copolymerizable therewith is subjected to addition polymerization in the presence of an addition polymerization catalyst containing a nickel compound and/or a cobalt compound to give a cyeloolefin addition (co)polymer having a glass transition point higher than of 200 deg.C. A solution of the (co)polymer is treated with an organic acid and water and then, if necessary, with a 1-12C alcohol compound; then, the catalyst component is removed by transferring it from the solution to an aqueous solution (aqueous phase).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an addition (co) polymer having a very low residual metal concentration, obtained by addition polymerization of a monomer containing a specific cyclic olefin. Further, the present invention relates to a method for removing a metal (hereinafter, simply referred to as “metal”) derived from a polymerization catalyst from a polymer solution after addition-polymerizing a monomer containing a specific cyclic olefin. More specifically, a polymer solution of a cycloolefin-based addition (co) polymer having excellent transparency and heat resistance is treated with an organic acid and water to transfer a metal to an aqueous phase, and contains a (co) polymer. The present invention relates to a method for removing a solvent by phase separation.

[0002]

2. Description of the Related Art Hitherto, as a material having excellent transparency,
The following hydrides and addition polymers of ring-opening polymers of cyclic olefin compounds have been proposed. (1) A hydride of a ring-opened polymer of a tetracyclododecene-based compound or a norbornene-based compound (JP-A-60-2602)
No. 4, Japanese Patent No. 3050196, JP-A-1-132
625, JP-A-1-132626, JP-A-5-214079, etc.) (2) Addition copolymer of ethylene and norbornene-based compound or tetracyclododecene-based compound [JP-A-61-2
No. 92601, Makromol. Chem. Macromol. Symp.
Vol. 47, 83 (1991) etc.) (3) Addition polymer of norbornene-based compound
JP-A-63807, JP-A-8-198919, JP-A-9-508649, JP-A-11-50588
No. 0) (4) Addition (co) polymer of a norbornene-based compound containing an alkoxysilyl group [AD Hennis et al., Am. Chem.
Soc. Polymer Preprints Vol. 40 (2), 782 (1999), JP-A-7-196736, International Patent Publication WO98 / 2.
0394 (EP Patent Publication 906588) and the like]

[0003] These transparent and heat-resistant resins are used in the fields of mounted parts such as semiconductors, parts using liquid crystal, optical parts, etc. in the form of thin films, films, sheets and the like. In addition to transparency and heat resistance, resins used in these fields may be subjected to secondary processing such as high-temperature processing or ultraviolet processing during the processing of parts, so that various durability is often required. If the resin contains a large amount of impurities such as metal ion species derived from the polymerization catalyst, it often causes color deterioration, and it is required that the amount of impurities be as small as possible.

[0004] In particular, a cyclic olefin compound addition polymer having high heat resistance has higher heat resistance than a conventional hydrogenated product of a ring-opening polymer and an addition polymer of ethylene and a cyclic olefin compound. Since the temperature is further increased, a higher degree of durability is required.

[0005] The method of removing the polymerization catalyst from the polymer solution of such a cyclic olefin compound addition polymer includes the following steps: (a) preparing a polymer solution containing a large amount of an inorganic acid such as hydrochloric acid or sulfuric acid if necessary; A method for removing the catalyst in a polymer by placing the polymer in methanol or acetone Example: JP-A-4-63807, U.S. Pat. No. 5,91
2,313, US Pat. No. 6,031,058, JP-A-8-198919 (b) A chelate compound such as 8-hydroquinoline is added to a polymer solution to form an insoluble metal chelate compound. Adsorption with adsorbents such as celite, and filtration and separation. Example: WO98 / 20394 Example 82 (c) A method of separating a polymerization catalyst and other foreign substances by filtering a polymer with a filter having a fine pore. Examples: WO 98/20394 Examples 100 to 103 are known.

However, these methods for removing a polymerization catalyst are not always satisfactory. In the method (a),
The catalyst component metal is incorporated into the coagulating polymer, and the removal of the metal is insufficient. In addition, removal of the polymerization catalyst using an inorganic acid requires expensive glass-lined containers and stainless steel containers to prevent corrosion of the containers, and is not economical in industrial production. In the method (b) using a chelating agent and an adsorbent, a chelating agent corresponding to each metal component is required in a multi-component catalyst system, and a part of the polymer is adsorbed on the adsorbent in addition to the catalytic metal component, resulting in a heavy weight. This leads to a decrease in the yield of coalescence. In the filter having fine pores of (c), the solid catalyst component can be separated by filtration to some extent, but there is a limit in removing a catalyst dissolved in a solvent such as a homogeneous catalyst.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in view of the above-mentioned problem. It is an object of the present invention to provide an addition (co) polymer in which a metal is efficiently removed from a coalesced polymer and which has a very low residual metal concentration, and a method for producing the same.

[0008]

Means for Solving the Problems The inventors of the present invention have prepared a cyclic olefin compound represented by the following general formula (1), or a compound and an α-olefin monomer copolymerizable with the compound, with nickel and A polymer solution of a cyclic olefin addition (co) polymer, which is addition-polymerized in the presence of a cobalt compound, is treated with an organic acid and water to transfer metals in the polymer to an aqueous phase, and the (co) polymer The present inventors have found that a metal can be efficiently removed by phase separation with a solvent containing.

[0009]

Embedded image

[In the formula (1), A ¹ , A ² , A ³ and A ⁴ each independently represent a hydrogen atom, a halogen atom, a carbon number of 1 to 2;
0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an allyloxy group, a general formula-(CH ₂ ) _k -OC (O) R ^1- (CH _{2) k -C (O) -OR} 2 or - indicates a _{(CH 2) k -Si (R} 3) x (R 4) substituents expressed by _3-x. m shows the integer of 0-3.
(Where R ¹ and R ² are substituents selected from alkyl groups having 1 to 10 carbon atoms, alkenyl groups and allyl groups, and R ³ is selected from alkyl groups having 1 to 10 carbon atoms, halogen atoms and allyl groups) R ⁴ is a hydrogen atom, a halogen atom, a substituent selected from an alkoxy group and an allyloxy group, k is an integer of 0 to 3, and x is an integer of 0 to 3.)] The cyclic olefin compound represented by 1) is
At least one of the substituents A ¹ , A ² , A ³ and A ⁴ is — (CH ₂ ) _k —Si (R ³ ) _X (R ⁴ ) _{3-X wherein} R ³ is a group represented by the general formula (1) Similarly, R ⁴ represents an alkoxy group or an alloxy group. k represents an integer of 0 to 3,
x shows the integer of 0-2. ] It is preferable that it is a substituent represented by these. In the present invention, the cyclic olefin addition (co)
When treating a polymer solution of a polymer with an organic acid and water, it is preferable to further add an alcohol compound having 1 to 12 carbon atoms.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the cyclic olefin compound represented by the general formula (1) of the present invention include 2-norbornene, 5-methyl-2-norbornene, and 5-ethyl-2.
-Norbornene, 5-propyl-2-norbornene, 5
-Butyl-2-norbornene, 5-pentyl-2-norbornene, 5-hexyl-2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl −
2-norbornene, 5,6-dimethyl-2-norbornene, 5-methyl-5-ethyl-2-norbornene, 5-
Phenyl-2-norbornene, 5-cyclohexenyl-
2-norbornene, 5-indenyl-2-norbornene, 5,6-indane-2-norbornene, 2,5-norbornadiene, 5-methyl, 2,5-norbornadiene, 5-vinyl-2-norbornene, 5-allyl- 2-
Norbornene, 5-butenyl-2-norbornene, 5-
Methylidene-2-norbornene, 5-ethylidene-2-
Norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexyl-2-norbornene, 5-fluoro-2-norbornene, 5-chloro-2-norbornene, methyl 5-norbornene-2-carboxylate, 5-norbornene-2 Ethyl carboxylate, 5-norbornene-2-butyl carboxylate, 5-norbornene-2-methyl acrylate, 5-norbornene-2 methacrylate
-Methyl, methyl 2-methyl-5-norbornene-2-carboxylate, ethyl 2-methyl-5-norbornene-2-carboxylate, propyl 2-methyl-5-norbornene-2-carboxylate, 2-methyl-5 -Norbornene-2
-Butyl carboxylate, 2-ethyl-5-norbornene-
Methyl 2-carboxylate, trifluoroethyl 2-methyl-5-norbornene-2-carboxylate, 2-methyl-5
Ethyl norbornen-2-ylacetate, 5-norbornene-2-spiro-N-phenylsuccinimide, 5-norbornene-2-spiro-N-cyclohexylsuccinimide, 5-norbornene-2-spiro-N-methylsuccinimide, 5-norbornene -2,3-N-phenyldicarboximide, 5-norbornene-2,3-N-
Cyclohexyldicarboximide, acrylic acid-2-
Methyl-5-norbornene, 2-methyl-5-norbornene methacrylate, dimethyl 5-norbornene-2,3-dicarboxylate, diethyl 5-norbornene-2,3-dicarboxylate, 3-tricyclo [4.3.0 .
1 ^2,5 ] decene, 3,7-tricyclo [4.3.0.1
^2,5 ] decadiene (dicyclopentadiene) 3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene, 8-tetracycloacrylic acid [4.4.0.1 ^2,5 . 1
^7,10 ] dodecene-3-methyl, 8-methyl-3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodecene, 8-ethylidene-3-tetracyclo [4.4.0.1 ^2,5 1
^7,10] dodecene, 8-methyl-8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecene, 8-methyl-8-ethoxycarbonyl-3 tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecene 5
-Triethoxysilyl-2-norbornene, 5-monomethyldiethoxysilyl-2-norbornene, 5-monochlorodiethoxysilyl-2-norbornene, 5-dichloromonoethoxysilyl-2-norbornene 5-trimethoxysilyl-2-norbornene , 5-monomethyldimethoxysilyl-2-norbornene, 5-triisopropoxysilyl-2-norbornene, 5-trichlorosilyl-
2-norbornene, 5-trimethylsilyl-2-norbornene, 5-monomethyldichlorosilyl-2-norbornene, 8-triethoxysilyl-3-tetracyclo [4.4.0.1 ^2,5 . ^17,10 . ] Dodecene, 8-monomethyldiethoxysilyl-3-tetracyclo [4.4.
0.1 ^2,5 . ^17,10 . ] Dodecene, and the like. One of these cyclic olefin compounds may be used alone, or two or more thereof may be used in combination.

The α-olefin monomers copolymerizable with the cyclic olefin compound represented by the general formula (1) include ethylene, propylene, 1-butene, 1-hexene, 1-octene, trimethylsilylethylene, Examples include triethylsilylethylene, trichlorosilylethylene, dichloromonomethylsilylethylene, chlorodimethylsilylethylene, trimethoxysilylethylene, triethoxysilylethylene, dimethoxymethylsilylethylene, diethoxymethylsilylethylene, and monohydridodimethylsilylethylene. These α-olefins can be used alone or in combination of two or more.

The proportion of the cyclic olefin compound and the α-olefin monomer used is 30
-100 mol%, preferably 50-100 mol%, α-
The olefin monomer is 70 to 0 mol%, preferably 50 to
0 mol% [however, the cyclic olefin compound + α-olefin monomer = 100 mol%]. When the use ratio of the cyclic olefin compound is less than 30 mol%, the glass transition temperature of the cyclic olefin-based addition (co) polymer is less than 200 ° C, and the heat resistance is low.

The glass transition temperature of the cyclic olefin addition (co) polymer obtained by using the cyclic olefin compound of the present invention or the cyclic olefin copolymer of a cyclic olefin compound and an α-olefin monomer is 200 ° C. If it exceeds, the heat resistance will be excellent. Glass transition temperature is 200
In order to make it exceed ℃, it can be easily adjusted by setting the usage ratio of the cyclic olefin compound and the α-olefin monomer within the above range. Incidentally, the number average molecular weight of the cyclic olefin addition (co) polymer of the present invention,
5,000 to 2,000,000, preferably 10,000
00 to 1,000,000, more preferably 30,0
00 to 500,000. The weight average molecular weight is 7,000 to 3,000,000, preferably 1
5,000 to 2,000,000, more preferably 5
It is between 000 and 1,000,000.

When the cyclic olefin compound (co) polymer of the present invention contains an alkoxysilyl group or an allyloxysilyl group, for example, a compound represented by the general formula (2)-(CH ₂ ) _k -Si (R ³ ) _x (R ⁴ ) _3-x general formula (2) wherein R ³ is the same as in general formula (1), and R ⁴ represents an alkoxy group or an allyloxy group. k represents an integer of 0 to 3;
Represents an integer of 0 to 2. When a structural unit derived from a cyclic olefin compound containing a group represented by the formula or a structural unit derived from an α-olefin monomer containing an alkoxysilyl group or an allyloxysilyl group is contained, an addition (co) obtained The polymer has excellent adhesiveness to other organic and inorganic material members. Although these functional groups are likely to be degraded in the step of removing the catalyst after the polymerization, the use of the method of the present invention makes it possible to remove the catalyst without deteriorating the functional groups in the polymer.

The cyclic olefin addition (co) polymer of the present invention can be prepared by using a single complex catalyst or a multi-component catalyst containing a nickel compound or a cobalt compound to form a hydrocarbon solvent,
In a solvent selected from a halogenated hydrocarbon solvent, an ester solvent, an ether solvent, a nitro compound solvent, etc., -2
A polymer solution is obtained by polymerizing the above-mentioned monomer in the range of 0 to 150 ° C., and thereafter, it is obtained by performing catalyst removal treatment, removal treatment of unreacted monomer, and drying.

As the polymerization catalyst of the present invention, 1) a compound represented by the following general formula: D.Ni (F) ₂ or D.Co
(F) Nickel complex or cobalt complex represented by ₂ (D represents an aromatic compound such as benzene, toluene, xylene, trimethylbenzene, naphthalene, anthracene, etc. F represents phenyl hexafluoride, 3,5-di-tri Fluorinated phenyl groups such as fluoromethyl-phenyl and 1,3,5-trifluorophenyl.),

2) a two-component catalyst comprising the following components a) and b): a) a compound selected from the group consisting of an organic acid salt of nickel or cobalt, a β-diketone compound, and a phosphine complex; Acetic acid, pentanoic acid, hexanoic acid,
Organic carboxylic acids such as octanoic acid, dodecanoic acid and versatic acid, organic phosphoric acids such as dioctyl phosphoric acid, dibutyl phosphoric acid, dibutyl phosphate and dioctyl phosphate, dodecyl benzene sulfonic acid, decyl sulfonic acid, dodecyl sulfonic acid and the like Organic sulfonic acid and the like can be mentioned. Compounds such as acetylacetone, ethyl acetoacetate, phenylacetoacetate and butylacetoacetate are used as β-diketones, and bis (triphenylphosphine) nickel dichloride and bis (triphenylphosphine) nickel dibromide are used as phosphine complexes of nickel and cobalt. , Bis (tolylphosphine) nickel dichloride, bis (tolylphosphine) nickel dibromide, bis (trixylylphosphine) nickel dichloride, bis (trixylylphosphine) nickel dibromide, bis (diphenylphosphino) ethane nickel dichloride, bis (Diphenylphosphino) ethane nickel dibromide, bis (triphenylphosphine) cobalt dichloride, bis (triphenylphosphine) cobal Dibromide, bis (tolylphosphine) cobalt dichloride, bis (tolylylphosphine) cobalt dibromide, bis (trixylylphosphine) cobalt dichloride, bis (trixylylphosphine) cobalt dibromide, bis (diphenylphosphino) ethanecobalt dichloride And bis (diphenylphosphino) ethanecobalt dibromide. B) Organoaluminum (where the organoaluminum is a mixture of alkylaluminum and methylalumoxane selected from methylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, tributylaluminum, butylalumoxane, alkylaluminum halide Etc.).

3) A three-component catalyst comprising the following components a), b) and c): a) an organic acid salt of nickel, a β-diketone compound or a nickel phosphine complex [here, an organic acid salt of nickel;
The β-diketone compound and the phosphine complex of nickel are the same as the compounds described in 2) a) above. These nickel compounds can be used by reacting in advance with the following super-strong acids. B) a fluorine compound selected from Lewis acidic boron fluoride, a protic fluorine compound and an ionic boron compound [here, the Lewis acidic boron fluoride compound includes boron trifluoride, tris (pentafluorophenyl) ) Borane,
Examples include ether, phenol, alcohol and amine complexes of boron trifluoride. Examples of the protic fluorine compound include acetylacetone hexafluoride and super strong acids such as hexafluoroantimonic acid, hexafluorophosphinic acid, tetrafluoroboric acid, and hydrogen fluoride. Further, as the ionic boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-di-trifluoromethyl-phenyl) borate, tributylammonium tetraphenylborate, trimethylammonium Tetrakis (pentafluorophenyl) borate,
Tributylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl)
Borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-trifluoromethyl-phenyl) borate and the like. C) an organometallic compound selected from organoaluminum compounds, organomagnesium compounds, organozinc compounds and organolithium compounds (here, the organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, diisobutyl Aluminum hydride,
And methylalumoxane. Examples of the organic magnesium, organic zinc, and organic lithium compounds include dibutyl magnesium, diethyl magnesium, diethyl zinc, butyl lithium, and hexyl lithium. )

The amount of these catalysts is
0.001 to 10 milliequivalent nickel or cobalt atom range, preferably 0.01 to 1.0 milliequivalent nickel or cobalt atom, more preferably 0.05 to 0.5 milliequivalent nickel atom Or it is used in the range of cobalt atoms.

The concentration of the (co) polymer obtained by the polymerization varies depending on the ratio of the monomer to the polymerization solvent and the conversion to the (co) polymer. Usually, the polymerization solvent is used in the range of 200 to 1,000 parts by weight based on 100 parts by weight of the monomer.
The conversion to (co) polymer depends on the polymerization time, amount of catalyst, polymerization temperature, monomer concentration, etc., but to reduce the load of removing unreacted monomers, Conversion rate of 8
It is preferably 0% or more.

The removal of the catalyst component is performed by bringing the polymer solution into contact with an organic acid. As organic acids, formic acid, acetic acid, propionic acid, valeric acid, acrylic acid, octanoic acid, lactic acid, butyric acid, isobutyric acid, aliphatic monocarboxylic acids such as glycolic acid, oxalic acid, malonic acid, fumaric acid, maleic acid, Aliphatic dicarboxylic acids such as itaconic acid, malic acid, adipic acid, succinic acid, tartaric acid, etc., cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanetetracarboxylic acid, hymic acid Aromatics such as alicyclic carboxylic acids such as benzoic acid, benzoic acid, phthalic acid, terephthalic acid, isophthalic acid, salicylic acid, and pyromellitic acid; 5-norbornene-2-carboxylic acid, 2-methyl-5-norbornene-2-carboxylic acid Aromatic carboxylic acid, p-methylbenzenesulfonic acid m-dimethylbenzenesulfonic acid, organic sulfonic acid such as dodecylbenzenesulfonic acid, decylsulfonic acid, dodecylsulfonic acid, dibutylmonophosphoric acid, dioctylmonophosphoric acid, mono- or di-phosphate ester of polyalkylene glycol, butyl phosphate ester, Organic phosphoric acids such as octyl phosphate and dioctyl phosphate are used. Among these organic acids, organic carboxylic acids having 1 to 6 carbon atoms are preferable because they have low solubility in the polymer and can remove the catalyst component without remaining.

The amount of the organic acid used is 2 to 100, based on 1 equivalent of nickel or cobalt atom used in the polymerization.
It is used in the range of 000 equivalents, preferably 50 to 10,000 equivalents. The concentration of the polymer solution used for the decatalyst is 5 to 35% by weight, preferably 10 to 25% by weight in terms of the solid content of the polymer. In the present invention, after treating the polymer solution with an organic acid, the polymer solution is brought into contact with water to transfer the catalyst component to an aqueous phase.
At this time, the amount of water used for the decatalyst depends on the amount of the polymer solution 10
It is 10 to 1,000 parts by weight, preferably 30 to 500 parts by weight, based on 0 parts by weight. The contact between the polymer solution and the organic acid (solution) and / or water is carried out using a stirrer with excellent stirring efficiency, such as a vessel-type reactor equipped with an ordinary stirrer, a static mixer, a line mixer homomixer, etc.
The method is carried out by, for example, introducing a polymer solution and an organic acid (solution), or a polymer solution treated with an organic acid (solution) and water and stirring and mixing. The contact time between the polymer solution and the organic acid (solution), or the polymer solution treated with the organic acid (solution) and water depends on the stirring efficiency of the stirrer,
Usually, it is 1 minute to 3 hours, preferably 10 to 100 minutes, and the contact temperature is usually 20 to 70 ° C. After stirring and mixing the polymer solution and the aqueous solution containing the organic acid to contact,
By allowing to stand, the solution phase containing the (co) polymer and the catalyst component are separated into the aqueous phase extracted by the organic acid.
The aqueous phase is removed, and the (co) polymer solution phase is washed with alkaline or neutral water as necessary to remove trace amounts of organic acids from the (co) polymer solution phase. You.

It is important to separate the interface between the (co) polymer solution from which the catalyst component has been extracted and removed and the liquid phase (aqueous phase) containing the organic acid. In this case, the loss of the (co) polymer solution, that is, the (co) polymer is caused, or the removal of the catalyst component is insufficient. As described above, improving the interface separation between the (co) polymer solution and the aqueous phase enables separation in a short time,
It is economically significant to increase the efficiency of removing the catalyst components. In order to promote the interface separation between the (co) polymer solution and the aqueous phase, alcohols such as isopropanol, butanol, amyl alcohol, hexanol, octanol, decanol and dodecanol, which are alcohols having 1 to 12 carbon atoms, are used. The addition is effective. The alcohol may be added to the polymer solution at the same time as the organic acid, or may be added after decatalyzing with the organic acid. When treating with an organic acid, it is usually used as an alcohol solution of the organic acid to which the alcohol is added (organic acid solution). The amount of the alcohol to be added is 0.1 to 15% by weight, preferably 0.5 to 7% by weight, based on the water used.

The (co) polymer is recovered from the (co) polymer solution from which the above-mentioned catalyst component has been removed by the following method or the like. That is, a method of coagulating the (co) polymer by putting the (co) polymer solution in a large amount of alcohol and recovering the coagulated product by drying, or heating the (co) polymer solution to directly remove the solvent A method of collecting by evaporating and removing can be used. Furthermore, as another method,
The (co) polymer solution can be cast on a support and recovered in the form of thin films, sheets and films.

Thus, the metal concentration in the cycloolefin addition (co) polymer of the present invention from which the catalyst component has been removed is as follows:
That is, the residual transition metal concentration is 2 ppm or less, preferably 1.5 ppm or less, and the residual aluminum concentration is 5 p.
pm or less, preferably 3 ppm or less, and is excellent in transparency and heat resistance.

[0027]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples. The molecular weight of the (co) polymer,
The glass transition temperature of the (co) polymer, the analysis of metals in the (co) polymer, and the analysis of anions were measured by the following methods.

(1) Weight-average molecular weight, number-average molecular weight: o-dichlorobenzene using a 150C type gel permeation chromatography (GPC) apparatus manufactured by WATERS using an H-type column manufactured by Tosoh Corporation. 1 as a solvent
It was measured at 20 ° C. The obtained molecular weight indicates a standard polystyrene equivalent value.

(2) Glass transition temperature: Leovibron D
Using DV-01FP (manufactured by Orientec), frequency 1
The glass transition temperature was defined as the peak temperature of the temperature dispersion of Tan δ obtained under the conditions of 0 Hz, a heating rate of 4 ° C./min, a vibration mode of a single waveform and a vibration amplitude of 2.5 μm.

(3) Metals (Ni, Al,
Sb) Analysis: As an atomic absorption spectrometer, Hitachi Model Z9000 was used. A standard aqueous solution of each metal was diluted to prepare a calibration curve by atomic absorption spectrometry, and the sample was measured with a 1% by weight (co) polymer solid solution in toluene. (4) Measurement of anion (F ⁻ ) Measurement was performed using an ion chromatograph.

Reference Example 1 (Preparation of Polymer Solution) In a reaction vessel purged with nitrogen, 2,000 g of toluene, 217 g of norbornene, 103 g of hexyl norbornene, and 1.2 g of 1-hexene as a molecular weight regulator were charged. Furthermore, 12 ml of a toluene solution of nickel 2-ethylhexylate having a concentration of 0.1 mol / L, triphenylcarbonium tetrakispentafluoroborate having a concentration of 0.05 mol / L, 35 ml of a toluene solution, and 5 ml of a toluene solution of triethylaluminum having a concentration of 1 mol / L were added. At 30 ° C. for 1 hour to obtain a polymer solution. The conversion to the polymer was 85%. The number average molecular weight of the obtained polymer is 220,000,
The weight average molecular weight was 300,000. The structural unit derived from hexyl norbornene in the polymer was 19.5 mol%, and the glass transition temperature was 270 ° C.

Example 1 An isopropyl alcohol solution of lactic acid having a concentration of 1 mol / L was added to 100 parts by weight of the polymer solution prepared in Reference Example 1.
After stirring at 60 ° C. for 30 minutes with a mixer, 100 parts by weight of water was further added. After stirring at 60 ° C. for 30 minutes, the mixture was allowed to stand, separated into an organic layer and an aqueous layer, and the aqueous layer was discarded. After repeating this operation, the organic layer was washed with 100 parts by weight of water for 2 hours.
Washed twice. The obtained polymer solution was coagulated with isopropyl alcohol and dried under vacuum, and nickel and aluminum in the polymer were quantified. Table 1 shows the results.

Example 2 The same operation was carried out except that 3 ml of a 1 mol / L lactic acid isopropyl alcohol solution used in Example 1 was changed to 6 ml. Table 1 shows the results.

Example 3 The same operation was performed except that 3 ml of a 1 mol / L isopropyl alcohol solution of lactic acid used in Example 1 was changed to 3 ml of a 1 mol / L acetic acid isopropyl alcohol solution. Table 1 shows the results.

Example 4 An isopropyl alcohol solution of lactic acid having a concentration of 1 mol / L was added to 100 parts by weight of the polymer solution prepared in Reference Example 1.
After stirring at 60 ° C. for 30 minutes with a mixer, 100 parts by weight of water was further added, and the mixture was stirred at 60 ° C. for 30 minutes and allowed to stand to separate into an organic layer and an aqueous layer. At this time, 3 ml of isopropyl alcohol was added to the aqueous layer to further improve the separation. Then, the aqueous layer was discarded. After repeating this operation further,
The organic layer was washed twice with 100 parts by weight of water. At this time, 3 ml of isopropyl alcohol was added to further improve the separation between the polymer solution (organic layer) and water. The obtained polymer solution was coagulated with isopropyl alcohol and dried in vacuum, and nickel and aluminum in the polymer were quantified. Table 1 shows the results.

Example 5 The same operation was carried out as in Example 4, except that isopropyl alcohol was added to improve the separation of the organic layer and the aqueous layer from octanol. Table 1 shows the results.

Comparative Example 1 The same operation was performed without using the lactic acid used in Example 1. Table 1 shows the results.

[0038]

[Table 1]

Reference Example 2 In Reference Example 1, 2-norbornene 25 was used as a monomer.
Using 2.7 g and 36.1 g of 5-triethoxysilyl-2-norbornene, modified nickel nickel 2-ethylhexanoate (1.2 mol of HSbF ₆ at −30 ° C. with respect to 1 mol of Ni-ethylhexanoate) was used as a polymerization catalyst. Reaction product) 0.708 mmol equivalent Ni, boron trifluoride ethyl etherate 6.368 mmol, triethyl aluminum 7.
A polymer solution was prepared in the same manner as in Reference Example 1 except that 080 mmol was used. The conversion of the monomer into the polymer was 95%. The ratio of structural units derived from 5-triethoxysilyl-2-norbornene in the polymer obtained by coagulating this polymer solution with isopropanol and drying was 4.8 mol%, the weight average molecular weight was 265,000, and the number average molecular weight was 26,000. Is 178,0
00. The glass transition temperature of the polymer is 350
° C.

Example 6 Using the polymer solution prepared in Reference Example 2, decatalysis was carried out in the same manner as in Example 4, and Ni, Al, Sb and fluorine ions in the polymer were analyzed. Table 2 shows the results. After the decatalyst treatment, the proportion in the polymer derived from 5-triethoxysilyl-2-norbornene was 4.9 mol%, and the triethoxysilyl group was unchanged.

Example 7 The procedure of Example 6 was repeated, except that malic acid was used instead of lactic acid. Table 2 shows the results.

Comparative Example 2 The procedure of Example 6 was repeated except that no lactic acid was used. Table 2 shows the results.

[0043]

[Table 2]

[0044]

According to the present invention, the addition polymerization catalyst can be efficiently removed from the cycloolefin addition (co) polymer having a high glass transition temperature, and the cycloolefin addition (copolymer) having an extremely low residual metal concentration can be obtained. ) A polymer can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Noboru Oshima 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Corporation (reference) 4J015 DA09 4J028 AA01A AB00A AC47A AC48A BA00A BA01B BA02B BB00A BB00B BB01B BC01B BC04B BC05B BC09B BC12B BC14B BC15B BC18B BC25B CA17C EA01 EB17 EB18 EB26 EC01 EC02 FA02 FA07 GA19 4J100 AA02Q AA03Q AA04Q AA16Q AA19Q AP16Q AR05P AR11P AR21P AR22P AS15P AU21P BA15P BA16P BA71P BA71Q BA72Q BA77P BA77Q BB01P BB07P BB17P BC04P BC12P BC23P BC27P BC43P BC48P BC66P CA01 CA04 FA08 FA10 GA18 4J128 AA01 AB00 AC47 AC48 BA00A BA01B BA02B BB00A BB00B BB01B BC01B BC04B BC05B BC09B BC12B BC14B BC15B BC18B BC25B CA17C EA01 EB17 EB18 EB26 EC01 EC02 FA02 FA07 GA19

Claims (4)

[Claims] 1. Addition polymerization of a cyclic olefin compound represented by the following general formula (1), or this compound and an α-olefin monomer copolymerizable with the compound, in the presence of a nickel and / or cobalt compound. And a residual transition metal concentration of 2 ppm or less and a residual aluminum concentration of 5 ppm.
ppm or less
(Co) polymer. Embedded image [In the formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, Carbon number 1
20 alkoxy group, allyloxy group, the general formula _{- (CH 2) k -O-} C (O) R 1 - (CH 2) k -C (O) -OR 2 or - (CH _{2) k} -Si ( R ³ ) _x (R ⁴ ) represents a substituent represented by _3-x . m shows the integer of 0-3.
(Where R ¹ and R ² are substituents selected from alkyl groups having 1 to 10 carbon atoms, alkenyl groups and allyl groups, and R ³ is selected from alkyl groups having 1 to 10 carbon atoms, halogen atoms and allyl groups) R ⁴ represents a hydrogen atom, a halogen atom, a substituent selected from an alkoxy group and an allyloxy group, k represents an integer of 0 to 3, and x represents an integer of 0 to 3.) 2. Addition polymerization of a cyclic olefin compound represented by the above general formula (1), or this compound and an α-olefin monomer copolymerizable with the compound, in the presence of a nickel and / or cobalt compound. The polymer solution of a cycloolefin addition (co) polymer having a glass transition temperature exceeding 200 ° C. is treated with an organic acid and water to transfer a metal in the polymer to an aqueous phase. A process for producing the cyclic olefin addition (co) polymer according to the above. 3. The cyclic olefin compound represented by the general formula (1), wherein at least one of the substituents A ¹ , A ² , A ³ and A ⁴ has — (CH ₂ ) _k —Si (R ³ ) _X ( R ⁴ ) _{3-X wherein} R ³ is the same as in formula (1), and R ⁴ is an alkoxy group or an allyloxy group. k represents an integer of 0 to 3,
x shows the integer of 0-2. 3. The method for producing a cycloolefin addition (co) polymer according to claim 2, which is a substituent represented by the formula: 4. When a polymer solution of a cyclic olefin addition (co) polymer is treated with an organic acid and water, it further has 1 to 12 carbon atoms.
4. The method for producing a cycloolefin addition (co) polymer according to claim 2, wherein the alcohol compound is added.