JP5672959B2 - Method for producing polymer and method for removing metal catalyst residue - Google Patents

Description

  The present invention relates to a method for producing a polymer from which a metal catalyst component has been removed, and a novel method for removing a metal catalyst residue. Specifically, by bringing a crude polymer solution containing a metal catalyst component into contact with a solvent constituting the crude polymer solution and an aprotic polar solvent capable of liquid-liquid separation, the metal catalyst component contained in the crude polymer solution is effective. The present invention relates to a method for producing a polymer that is removed and the content of the metal component is sufficiently reduced.

  There are many known methods for producing a polymer using a late transition metal such as palladium, nickel, cobalt, ruthenium, iron, rhodium, platinum, and an organoaluminum compound as a polymerization catalyst or a hydrogenation catalyst (from Patent Document 1). Patent Document 9, and Non-Patent Document 1 to Non-Patent Document 3). However, when the polymer obtained by these methods is used for an optical material or an electronic material, the remaining metal component causes a deterioration in the hue of the polymer, a decrease in transparency, a deterioration in electrical characteristics, a metal to other laminated materials. The deterioration of the performance of the laminated material due to movement of components becomes a problem.

  In order to solve such a problem, a method for effectively removing the metal component contained in the polymer is necessary. For example, an additive such as an acid or a chelating agent is added to the reaction mixture after polymerization, and the aggregate is removed. A method of filtration or centrifugation, a method of extraction and separation with water, alcohols, ketones or esters, a method of coagulating and separating a polymer, a method of treating with diatomaceous earth, silica, alumina, activated carbon, an ion exchange resin, or the like, or A combination of these methods is generally used (for example, Patent Document 10 to Patent Document 13). However, these methods may not be effective depending on the metal component to be removed.

  Several methods for removing metal components from low-molecular organic compounds and polymer solutions have been proposed, but in the case of mass production of polymers industrially due to the use of a large amount of solvent and long time. Often not suitable.

  Non-Patent Document 4 reports a ruthenium removal method using triphenylphosphine oxide or dimethyl sulfoxide. However, this document is a method of performing filtration after a reaction of 12 hours, and has a problem that it takes a long time.

Japanese Patent Laid-Open No. 2005-48060 JP 2003-327673 A JP 7-309941 A JP-A-1-168725 Japanese Patent No. 3259476 Japanese Patent Laid-Open No. 2-102221 JP-A-2-133413 Japanese Patent No. 2684796 Japanese Patent No. 30605532 JP 61-130304 A Japanese Patent No. 3072329 Japanese Patent No. 2518019 JP 2002-371090 A

Chem. Mater., Vol.16 1313 (2004) Macromolecules Vol.38, 658 (2005) J. Am. Chem. Soc. Vol.127, 10045 (2005) Org. Lett. Vol.3, No.9 (2001)

  The present invention has been made in order to address the above-described problems, and effectively removes the metal component contained in the polymer solution by a highly efficient and simple process, thereby reducing the weight of the metal component contained sufficiently. It aims at providing the manufacturing method of unification. It is another object of the present invention to provide a method for producing a polymer having good transparency that can withstand use as an optical material such as a lens.

（式（１）中、Ａ ¹ 〜Ａ ⁴ はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、あるいは炭素数１〜２０の酸素原子を含む炭化水素基、炭素数３〜１２のトリアルキルシリル基、炭素数０〜１２の加水分解性シリル基から選ばれた置換基であり、また、Ａ ¹ とＡ ² またはＡ ¹ とＡ ⁴ は互いに結合してアルキレン基、アリーレン基、酸無水物、ラクトンを形成していてもよい。ｍは０または１である。）
特に、上記非プロトン性極性溶媒と上記溶媒との大気圧下での沸点差が１０℃以上あることを特徴とする。
また、上記非プロトン性極性溶媒が、ジメチルスルホキシド（以下、ＤＭＳＯと略称する）、Ｎ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦと略称する）、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド（以下、ＤＭＡｃと略称する）、アセトニトリル、γ−ブチロラクトン、および／またはＮ−メチル−２−ピロリドン（以下、ＮＭＰ
と略称する）であることを特徴とする。 As a result of diligent research to achieve the above object, the present inventors removed a metal component in the crude polymer solution by bringing the crude polymer solution containing the specific aprotic polar solvent and the metal catalyst residue into liquid-liquid contact. The present invention has been completed.
That is, the method for producing a polymer of the present invention is a method for producing a polymer obtained by removing a metal catalyst residue from a crude polymer containing a metal catalyst residue, wherein the crude polymer is a ring-opened polymer of a cyclic olefin. A crude polymer having a structural unit represented by the following formula (1) obtained by the hydrogenation reaction of: a crude polymer solution in which the crude polymer is dissolved in a solvent; look including the step of liquid-liquid contact with a protic polar solvent, the said solvent is alicyclic hydrocarbon solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, ether or alcohol The solvent is a single solvent or a combination of two or more, and the residual amount of the metal component is 20 ppm or less in terms of metal atoms .

(In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group containing an oxygen atom having 1 to 20 carbon atoms, or 3 carbon atoms. Or a substituent selected from a hydrolyzable silyl group having 0 to 12 carbon atoms, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an alkylene group or an arylene group. A group, an acid anhydride, or a lactone may be formed, and m is 0 or 1.)
In particular, the difference in boiling point between the aprotic polar solvent and the solvent at atmospheric pressure is 10 ° C. or more.
The aprotic polar solvent is dimethyl sulfoxide (hereinafter abbreviated as DMSO), N, N-dimethylformamide (hereinafter abbreviated as DMF), N, N-diethylformamide, N, N-dimethylacetamide ( Hereinafter abbreviated as DMAc), acetonitrile, γ-butyrolactone, and / or N-methyl-2-pyrrolidone (hereinafter referred to as NMP).
It is abbreviated as).

The metal catalyst serving as the metal catalyst residue is a ring-opening polymerization catalyst or a polymer hydrogenation catalyst. Further, the metal catalyst is a catalyst containing a metal of Group 4 to 13 element of the periodic table.
In particular, the group 4-13 element metal of the periodic table is at least one metal selected from tungsten, titanium, nickel, cobalt, aluminum, and ruthenium.
The polymer in the polymer production method of the present invention is characterized in that it contains a cyclic olefin polymer.

  The method for removing a metal catalyst residue in a polymer solution of the present invention comprises a crude polymer solution obtained by dissolving a crude polymer containing a metal catalyst residue in a solvent, and an aprotic polar solvent capable of liquid-liquid separation from the solvent. It is characterized by being brought into liquid-liquid contact.

  The method for producing the polymer of the present invention includes a step of bringing the solvent of the crude polymer solution into contact with the liquid-liquid separation of the aprotic polar solvent capable of liquid-liquid separation. It is possible to effectively remove the metal catalyst residue contained in the coalescence solution and sufficiently reduce the contained metal catalyst residue. Moreover, the metal catalyst residue removal method can remove a metal catalyst residue from a crude polymer containing a metal catalyst residue by a simple method.

  In the polymer production method of the present invention, the metal catalyst residue contained in the crude polymer is a metal-containing catalyst used for polymerizing a polymer or a polymer reaction after polymerization, a metal ion derived from the metal-containing catalyst, or This metal-containing catalyst, such as a complex of metal ions, and all metal components derived from this catalyst are included. A preferred polymerization method for the polymer is a ring-opening polymerization method, and a preferred polymer reaction after the polymerization is a hydrogenation reaction of the polymer.

  Examples of the metal component include lithium, magnesium, zinc, iron, tungsten, titanium, nickel, cobalt, aluminum, ruthenium, rhodium, iridium, palladium, and platinum. In particular, the metal catalyst is preferably a catalyst containing a metal of Group 4 to 13 element of the periodic table, and among the metals of Group 4 to 13 element of the periodic table, it is selected from tungsten, titanium, nickel, cobalt, aluminum, and ruthenium. Preferably, at least one metal. Catalysts containing these metals include, for example, cyclic olefin addition polymerization, methylenecyclopropane ring-opening polymerization, polyphenylene ethynylene polymerization, polyphenylene vinylene polymerization, olefin addition polymerization, alternating olefin and carbon monoxide copolymerization, cyclic polymerization It is used for ring-opening polymerization of olefins, hydrogenation reactions of cyclic olefin ring-opening polymers, hydrosilylation reactions of polymers, and the like. The metal component removal method of the present invention is suitably applied to a polymer solution containing a crude polymer obtained by the above polymerization or the like. Among them, cyclic olefin addition polymerization, cyclic olefin addition polymerization obtained by cyclic olefin ring-opening polymerization and subsequent hydrogenation reaction, and cyclic olefin ring-opening polymer hydride have excellent transparency, heat resistance and low water absorption. In order to reduce the content of the metal component derived from the polymerization catalyst or the hydrogenation catalyst, the polymer solution containing the crude polymer is used in the applications of optical materials and electronic materials because of its properties and low dielectric properties. The method for producing the polymer or the method for removing the metal catalyst residue in the polymer solution is preferably applied.

  Examples of the crude polymer containing the metal catalyst residue containing the metal component include a polymer obtained by a hydrogenation reaction of a cyclic olefin ring-opening polymer. The polymer preferably has at least one structural unit represented by the following formula (1).

式（１）中、Ａ¹〜Ａ⁴はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、あるいは炭素数１〜２０の酸素原子を含む炭化水素基、炭素数３〜１２のトリアルキルシリル基、炭素数０〜１２の加水分解性シリル基から選ばれた置換基であり、また、Ａ¹とＡ²またはＡ¹とＡ⁴は互いに結合してアルキレン基、アリーレン基、酸無水物、ラクトンを形成していてもよい。ｍは０または１である。

In formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing an oxygen atom having 1 to 20 carbon atoms, or 3 to 3 carbon atoms. 12 substituents selected from trialkylsilyl groups and hydrolyzable silyl groups having 0 to 12 carbon atoms, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an alkylene group or an arylene group. , Acid anhydrides and lactones may be formed. m is 0 or 1.

式（２）中、Ａ¹〜Ａ⁴およびｍは式（１）と同じである。 The structural unit represented by the above formula (1) can be formed by addition polymerization of a cyclic olefin compound represented by the following formula (2) or hydrogenation after ring opening polymerization.

In formula (2), A ^{1 to} A ⁴ and m are the same as in formula (1).

Specific examples of the cyclic olefin compound represented by the formula (2) include the following, but the present invention is not limited thereto.
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Propylbicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5 -Phenylbicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hepta-2 -Ene, 5,5-dimethylbicyclo [2.2.1] hept-2-ene , 5,6-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 9-ethylidene tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3,8-diene , Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate , T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, methyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methylbicyclo [2.2.1] Ethyl hepta-5-ene-2-carboxylate, 2-methylbicyclo [2.2.1] t-butyl hept-5-ene-2-carboxylate, bicyclo [2.2. 1] diethyl hept-5-ene-2,3-dicarboxylate, bicyclo [2.2.1] di-t-butyl hept-5-ene-2,3-dicarboxylate, 5-methylbicyclo [2.2. 1] methyl hept-2-en-5-yl acetate, tetracyclo [6 2.1.1 ^3,6. 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] t-butyl dodeca-9-ene-4-carboxylate, bicyclo [2.2.1] hept-5-en-2-yl acetate, 5-trimethylsilylbicyclo [2.2.1] hepta 2-ene, 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 5-trimethoxysilylmethylbicyclo [2.2.1] hept-2-ene, 5-triethoxysilylmethylbicyclo [2.2.1] hept-2-ene, 9-trimethoxysilyltetracyclo [6.2.1.1 ^{3, 6} ． 0 ^2,7 ] dodec-4-ene, 2-[(3-ethyloxetane-3-yl) methyl] bicyclo [2.2.1] hept-5-ene, 2-[(3-methyloxetane-3 -Yl) methoxy] bicyclo [2.2.1] hept-5-ene, 2-[(3-ethyloxetane-3-yl) methoxy] bicyclo [2.2.1] hept-5-ene, 2- [(Oxetane-3-yl) methoxymethyl] bicyclo [2.2.1] hept-5-ene, 2-[(3-methyloxetane-3-yl) methoxymethyl] bicyclo [2.2.1] hepta -5-ene, 2-[(3-ethyloxetane-3-yl) methoxymethyl] bicyclo [2.2.1] hept-5-ene, bicyclo [2.2.1] hept-5-ene-2 -Carboxylic acid [(Oxetane-3-yl) methyl], Bishi [2.2.1] hept-5-ene-2-carboxylic acid [(3-methyloxetane-3-yl) methyl], bicyclo [2.2.1] hept-5-ene-2-carboxylic acid [(3-Ethyloxetane-3-yl) methyl]
These may be used individually by 1 type and can also be used in combination of 2 or more type.

上記式（３）中、Ｒは水素原子、炭素数１から１０の炭化水素基、酸素原子および／またはケイ素原子を含む有機基から選ばれた置換基である。
式（３）で表される構造単位は、下記式（４）で表されるα−オレフィン化合物あるいは芳香族ビニル化合物を付加共重合することにより形成される。 The polymer obtained by addition polymerization of a cyclic olefin may further contain a structural unit represented by the following formula (3).

In the above formula (3), R is a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an organic group containing an oxygen atom and / or a silicon atom.
The structural unit represented by the formula (3) is formed by addition copolymerization of an α-olefin compound or an aromatic vinyl compound represented by the following formula (4).

式（４）中、Ｒは式（３）と同じである。
上記式（４）で表されるα−オレフィンおよび芳香族ビニル化合物の具体例としては、例えば、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、１−デセン、スチレン、ビニルトリメチルシラン、トリメトキシビニルシラン、トリエトキシビニルシランなどが挙げられる。なお、本発明はこれらに限定されるものではない。

In Formula (4), R is the same as Formula (3).
Specific examples of the α-olefin and aromatic vinyl compound represented by the above formula (4) include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, styrene, vinyltrimethylsilane. , Trimethoxyvinylsilane, triethoxyvinylsilane and the like. The present invention is not limited to these.

As the polymerization catalyst used for the ring-opening polymerization of the cyclic olefin, a known catalyst containing the above metal component can be appropriately used. For example, a polymerization catalyst comprising a combination of tungsten, molybdenum, rhenium alkoxide, phenoxide, halide, oxyhalide and organolithium, organomagnesium, organoaluminum, organozinc, etc., tungsten, molybdenum, ruthenium Cyclobutane or a carbene complex can be suitably used, and a catalyst activity improver or the like may be combined as necessary.
The catalytic activity enhancer can suppress the formation of low molecular weight components (oligomers and the like), and is preferably at least one compound selected from the group consisting of amines, nitriles, ketones, ethers, and esters. Also, alcohol can be used in combination.

In hydrogenating the cyclic olefin ring-opening polymer, a known method can be appropriately used. Also, for example, 5-ethylidenebicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene, an olefinically unsaturated bond that does not participate in polymerization. In the case of using a compound having an unsaturated bond, the unsaturated bond may be hydrogenated after polymerization.

  The hydrogenation reaction of a polymer obtained by ring-opening polymerization of a cyclic olefin is usually carried out at a hydrogen pressure in the range of 1.0 to 15 MPa and a temperature in the range of 50 to 250 ° C. The hydrogenation reaction catalyst may be homogeneous or heterogeneous, and a catalyst containing a metal selected from cobalt, palladium, platinum, rhodium, iridium, ruthenium, nickel and titanium is preferably used. The hydrogenation catalyst is used in the range of 10 to 1,000 ppm with respect to the cyclic olefin ring-opening polymer in terms of transition metal atoms.

In the method for producing a polymer of the present invention, the average molecular weight of the polymer is 1,000,000 or less, preferably 500,000 or less, more preferably 300,000 or less in terms of weight average from the efficiency of metal component removal. If it exceeds 1,000,000, the removal efficiency may be reduced, or the modified separation process may be hindered. The concentration of the polymer contained in the solution is not particularly limited and is appropriately selected depending on the molecular weight of the polymer, the viscosity of the solution, etc., but is usually 80% by weight or less, preferably 1 to 50% by weight. . If it exceeds 80% by weight, the removal efficiency may decrease because the viscosity of the polymer solution becomes too high.
The average molecular weight is obtained as a standard polystyrene equivalent value by gel permeation chromatography.

  In the present invention, the solvent constituting the crude polymer solution is not particularly limited as long as it dissolves the polymer. Further, even if the polymer is not dissolved, it can be mixed and used within a range where the polymer does not precipitate. The crude polymer solution in the present invention may be used without removing the solvent used in the solution polymerization or hydrogenation reaction, or after the solvent is once removed from the polymer solution by a method such as coagulation, reduced pressure, or heating. It may be redissolved.

  Specific examples of the solvent include alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, benzene, xylene, and mesitylene. Solvent: ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,2-dimethoxyethane, ethylene glycol ethyl Ethers such as methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate Such system or an alcohol-based solvent can be used singly or in combination of two or more.

  In the present invention, the metal catalyst residue is aprotic by mixing the crude polymer solution with the solvent constituting the crude polymer solution and an aprotic polar solvent capable of liquid-liquid separation and bringing them into liquid-liquid contact with each other. The metal component can be removed from the polymer solution by moving to a polar solvent. Here, “liquid-liquid separation is possible” means that when the solvent of the polymer solution and the aprotic polar solvent are mixed for liquid-liquid contact, both can be visually separated into two layers. Preferably, the solubility of the aprotic polar solvent in the solvent of the polymer solution or the solubility of the solvent of the polymer solution in the aprotic polar solvent is extremely small, respectively, and more preferably when both are not mutually soluble. is there. By not dissolving each other, the metal catalyst component extracted into the aprotic polar solvent layer can be efficiently removed by liquid-liquid separation.

  The aprotic polar solvent that can be used for liquid-liquid separation and the solvent constituting the polymer solution preferably have a boiling point difference of 10 ° C. or higher under atmospheric pressure. The boiling point of the aprotic polar solvent may be 10 ° C. or more higher than the boiling point of the solvent of the polymer solution, or vice versa, and preferably in the process of recovering and purifying the solvent of the polymer solution. This is the case for the former.

  Examples of the aprotic polar solvent that can be used in the present invention include DMSO, DMF, N, N-diethylformamide, DMAc, acetonitrile, γ-butyrolactone, NMP, sulfolane, hexamethylphosphoric triamide, 1,3-dimethylimidazolidinone. And cyclohexanone, cyclopentanone, methyl benzoate, ethyl benzoate, isophorone and the like. Among these, DMSO, DMF, N, N-diethylformamide, DMAc, acetonitrile, γ-butyrolactone, and NMP can be easily liquid-liquid separated from a process solvent such as cyclohexane, which is a solvent constituting the crude polymer solution. A protic polar solvent is preferred because of its excellent ability to separate metal catalyst residues. These can be used alone or as a mixture.

As a method of mixing the solvent constituting the polymer solution and the aprotic polar solvent capable of liquid-liquid separation and bringing them into liquid-liquid contact with each other, the aprotic polar solvent may be added to the polymer solution, It may be charged directly into the reaction vessel.
In addition, the aprotic polar solvent needs to be added to the polymer solution and brought into liquid-liquid contact with the polymer solution, and then separated from the polymer solution together with the transferred metal component. Examples of the step of separating the aprotic polar solvent from the polymer solution together with the metal component include decantation and centrifugation.

  The contact temperature at the time of liquid-liquid contact is preferably 0 ° C. or higher, and more preferably 20 ° C. or higher. If the contact temperature is too low, the removal rate of the metal component is extremely reduced, and a sufficient effect may not be obtained. In addition, since it varies depending on the selection of the polymer and its molecular weight, it cannot be said unconditionally, but at low temperatures, the viscosity of the polymer solution becomes too high, so that sufficient contact efficiency may not be obtained. The upper limit of the contact temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower. When the contact temperature exceeds 200 ° C., side reactions such as molecular chain breakage of the polymer and thermal degradation may occur.

  The amount of the aprotic polar solvent used is appropriately selected depending on the amount of the metal catalyst contained in the crude polymer solution, and is preferably 0.05 g or more, more preferably 0.1 with respect to 1 mmol of the contained metal. Used over gram.

  By the method of the present invention, the required residual metal / hue (YI) / yield can be achieved by a simple operation. Moreover, there is a possibility that the equipment is burdened, and the metal component contained in the polymer is sufficiently reduced by using only a small amount of extraction solvent without using an acid that may cause deterioration of the resin. Can do. The allowable amount of the remaining metal component in the polymer after removal of the metal component from the crude polymer containing the metal catalyst residue is not defined unconditionally because it varies depending on the application, but sacrifices the hue (YI) and yield. The amount allowed without conversion is preferably 20 ppm or less, more preferably 10 ppm or less, and most preferably 5 ppm or less in terms of metal atoms.

  The polymer obtained by the production method of the present invention is excellent in hue, transparency, and electrical characteristics, and therefore requires a transparent conductive film such as ITO, an oxygen and / or water vapor barrier film, a hard coat, an antireflection film, and the like. Liquid crystal display element, organic EL element, plasma display and electronic paper, display color filter substrate, light guide plate, polarizing plate protective film, antireflection film, retardation film, near infrared cut film, liquid crystal backlight , Touch panel, optical waveguide, optical fiber, polarizing plate, transparent conductive film, surface protective film, OHP film, coat film, highly reflective film, transflective film, ND filter, dichroic filter, electromagnetic shielding film, beam splitter, light Communication filter Fresnel lenses, camera lenses, pickup lenses, F-theta lens, a prism, MD, CD, can be used such as an optical recording substrate, such as a DVD. Insulating layer materials for electronic parts, adhesives, as well as chemical packaging materials, sterilization containers, syringes, pipes, tubes, ampoules and other medical instruments, trays, carrier tapes, separation films, insulating films, printed circuit board materials, etc. Can also be used.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. The molecular weight, light transmittance and the proportion of structural units in the copolymer were measured or evaluated by the following methods.
(1) Number average molecular weight, weight average molecular weight Using HLC-8020 (GPC) manufactured by Tosoh Corporation, measurement was performed using tetrahydrofuran (THF) as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Amount of contained metal component Measured using an inductively coupled plasma mass spectrometer (ICP-MS: ELAN DRC plus manufactured by Perkin Elmer).
(3) Glass transition temperature (Tg)
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream. Tg is the tangent on the baseline starting from point B, with the differential peak scanning calorie maximum peak temperature (point A) and the temperature at −20 ° C. from the maximum peak temperature (point B) plotted on the differential scanning calorimetry curve. And the intersection of the tangent starting from point A.
(4) Intrinsic viscosity [η _inh ]
Using an Ubbelohde viscometer, the intrinsic viscosity was measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in chlorobenzene.
(5) Evaluation of yellowness difference ΔYI of polymerization solution The yellowness difference ΔYI is determined by using a 10% by weight resin cyclohexane solution as a test solution, and determining the yellowness (YI, yellow index) of the test solution according to JIS-K7103. Using a touch panel SM color computer SM-T45 manufactured by Tester Co., Ltd., the blank was measured as cyclohexane, and the value obtained by subtracting the yellowness YI of cyclohexane alone from the measured yellowness YI was the ΔYI of the resin solution. Asking. In addition, measurement is performed 3 times and the average value is evaluated.

Synthesis Example 1: Preparation of hydrogenated product of cyclic olefin polymer 8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (5) [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene (hereinafter abbreviated as DNM) 75 parts by weight, dicyclopentadiene (hereinafter abbreviated as DCP) 24 parts by weight, 2-norbornene 1 part by weight, molecular weight regulator 1-he 9 parts by weight of xene and 200 parts by weight of cyclohexane were charged into a nitrogen-substituted reaction vessel and heated to 110 ° C. To this, 0.005 part by weight of triethylaluminum and 0.005 part of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 weight ratio) were added and reacted for 1 hour to obtain a polymer.

The obtained polymer solution was placed in an autoclave, and 200 parts by weight of cyclohexane was further added. Next, 0.006 part by weight of RuHCl (CO) [P (C ₆ H ₅ )] ₃ which is a hydrogenation catalyst is added and heated to 90 ° C., then hydrogen gas is charged into the reactor, and the pressure is set to 10 MPa. It was. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa to obtain a hydrogenated copolymer (1a).
The copolymer (1a) has a weight average molecular weight (Mw) = 7.2 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.3, an intrinsic viscosity (η _inh ) = 0.59, a glass transition temperature (Tg). ) = 143 ° C. In addition, when the hydrogenation rate of the copolymer (1a) was calculated | required by < ¹ > H-NMR measurement, the olefinic unsaturated bond was hydrogenated 99.9% or more. Further, the value of ΔYI of the copolymer (1a) was 2.5, and the total metal content of tungsten, aluminum and ruthenium was 5.3 ppm. Let this copolymer (1a) be the crude polymer (1) containing a metal catalyst residue.

Synthesis Example 2: Preparation of Hydrogenated Cyclic Olefin Polymer 75 parts by weight of DNM, 24 parts by weight of DCP, 1 part by weight of 2-norbornene, 9 parts by weight of 1-hexene as a molecular weight regulator and 200 parts by weight of cyclohexane were substituted with nitrogen. The reaction vessel was charged and heated to 100 ° C. To this, 0.005 part by weight of triisobutylaluminum and 0.003 part by weight of methanol were added, and further 0.005 part by weight of WCl ₆ was added and reacted for 1 hour to obtain a polymer.
The obtained polymer solution was placed in an autoclave, and 200 parts by weight of cyclohexane was further added. Next, 0.006 part by weight of RuHCl (CO) [P (C ₆ H ₅ )] ₃ as a hydrogenation catalyst was added and heated to 90 ° C., then hydrogen gas was charged into the reactor, and the pressure was 10 MPa. It was. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa to obtain a hydrogenated copolymer (2a).
The copolymer (2a) has a weight average molecular weight (Mw) = 5.2 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 2.6, an intrinsic viscosity (η _inh ) = 0.49, a glass transition temperature (Tg). ) = 143 ° C. In addition, when the hydrogenation rate of the copolymer (2a) was calculated | required by < ¹ > H-NMR measurement, the olefinic unsaturated bond was hydrogenated 99.9% or more. Further, the value of ΔYI of the copolymer (2a) was 2.9, and the total metal content of tungsten, aluminum and ruthenium was 7.3 ppm. Let this copolymer (2a) be the crude polymer (2) containing a metal catalyst residue.

Synthesis Example 3: Preparation of hydrogenated cyclic olefin polymer 71.9 parts by weight of tricyclopentadiene, 37.5 parts by weight of DNM, 22.1 parts by weight of 2-norbornene, 9 parts by weight of 1-hexene as a molecular weight regulator It added to 280 weight part and heated and stirred at 105 degreeC. Separately, 0.005 part by weight of triisobutylaluminum and 0.003 part by weight of methanol were added, and further 0.005 part by weight of WCl ₆ was added and reacted for 1 hour to obtain a polymer.
The obtained polymer solution was placed in an autoclave, and 200 parts by weight of cyclohexane was further added. Next, 0.006 part by weight of RuHCl (CO) [P (C ₆ H ₅ )] ₃ as a hydrogenation catalyst was added and heated to 90 ° C., then hydrogen gas was charged into the reactor, and the pressure was 10 MPa. It was. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa to obtain a hydrogenated copolymer (3a).
The copolymer (3a) has a weight average molecular weight (Mw) = 5.0 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 2.8, an intrinsic viscosity (η _inh ) = 0.48, a glass transition temperature (Tg). ) = 139 ° C. In addition, when the hydrogenation rate of the copolymer (3a) was calculated | required by < ¹ > H-NMR measurement, the olefinic unsaturated bond was hydrogenated 99.9% or more. Further, the value of ΔYI of the copolymer (3a) was 3.1, and the total metal content of tungsten, aluminum and ruthenium was 7.8 ppm. Let this copolymer (3a) be the crude polymer (3) containing a metal catalyst residue.

Synthesis Example 4: Preparation of hydrogenated product of cyclic olefin polymer The same as Synthesis Example 1 except that the hydrogenation catalyst of Synthesis Example 1 was changed to 0.06 parts by weight of nickel dinaphthenate and 0.12 parts by weight of triisobutylaluminum. Operation was performed to obtain a hydrogenated copolymer (4a).
The copolymer (4a) has a weight average molecular weight (Mw) = 7.0 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.3, an intrinsic viscosity (η _inh ) = 0.58, and a glass transition temperature (Tg). = 143 ° C. In addition, when the hydrogenation rate of the copolymer (4a) was calculated | required by < ¹ > H-NMR measurement, the olefinic unsaturated bond was hydrogenated 99.9% or more. Further, the value of ΔYI of the copolymer (4a) was 8.5, and the total metal content of tungsten, aluminum and nickel was 16.5 ppm. Let this copolymer (4a) be the crude polymer (4) containing a metal catalyst residue.

Example 1
10 parts by weight of DMSO was added to 100 parts by weight of a 20% by weight cyclohexane solution of the crude polymer (1) obtained in Synthesis Example 1, and the mixture was stirred at 50 ° C. for 2 hours. After stirring, by standing at room temperature, a transparent resin solution layer was observed in the upper layer, and a DMSO layer colored yellow in the lower layer was observed. The upper layer was recovered, and the total metal content of ΔYI and tungsten, aluminum, and ruthenium was evaluated. As a result, the value of ΔYI was 0.5 and the total metal content was 0.05 ppm. These values were satisfactory in actual use. The polymer yield in this dedetaching step was 97% by weight and was good. The results are listed in Table 1.

Example 2
Detachment examination was carried out in the same manner as in Example 1 except that the crude polymer (1) was replaced with the crude polymer (2) obtained in Synthesis Example 2. The obtained upper layer was collected, and the total metal content of ΔYI and tungsten, aluminum, and ruthenium was evaluated. As a result, the value of ΔYI was 0.4 and the total metal content was 0.08 ppm. These values were superior to those of the combined (2), and these values were satisfactory for actual use. The polymer yield in this dedetaching step was 96% by weight and was good. The results are listed in Table 1.

Example 3
Detachment examination was carried out in the same manner as in Example 1 except that the crude polymer (1) was replaced with the crude polymer (3) obtained in Synthesis Example 3. The obtained upper layer was collected, and the total metal content of ΔYI and tungsten, aluminum, and ruthenium was evaluated. As a result, the value of ΔYI was 0.4 and the total metal content was 0.07 ppm. These values were superior to those of the combined (3), and these values were satisfactory for actual use. The polymer yield in this dedetaching step was 98% by weight and was good. The results are listed in Table 1.

Example 4 to Example 7
Using the crude polymer (1), the aprotic polar solvent shown in Table 1 below was added, and the detackification examination was conducted in the same manner as in Example 1. The results are listed in Table 1.

Example 8
Detachment examination was carried out in the same manner as in Example 1 except that the crude polymer (1) was replaced with the crude polymer (4) obtained in Synthesis Example 2. The obtained upper layer was recovered, and the total metal content of ΔYI and tungsten, aluminum, and nickel was evaluated. As a result, the value of ΔYI was 0.5 and the total metal content was 0.12 ppm. These values were superior to those of the coalescence (4), and these values were satisfactory for actual use. The polymer yield in this dedetaching step was 97% by weight and was good. The results are listed in Table 1.

Comparative Example 1
The same operation as in Example 1 was performed except that the same amount of a 1% by weight hydrochloric acid aqueous solution was added in place of the aprotic polar solvent. The obtained resin solution layer was collected, and the total metal content of ΔYI and tungsten, aluminum, and ruthenium was evaluated. As a result, the value of ΔYI was 1.5 and the total metal content was 3.9 ppm. Both were less effective than Example 1. In addition, the polymer yield in this dedetaching step was 92%, which was good. The results are listed in Table 2.

Comparative Example 2
To 100 parts by weight of the 20% by weight cyclohexane solution of the crude polymer (1) obtained in Synthesis Example 1, 0.37 parts by weight of lactic acid was added and stirred at 60 ° C. for 30 minutes, and then 250 parts by weight of methanol was added. And stirred at 60 ° C. for 1 hour. Then, it cooled to room temperature, the poor solvent phase (methanol phase) and the good solvent phase (polymer containing phase) were isolate | separated, and the said good solvent phase was collect | recovered. As a result of evaluating the total metal content of ΔYI, tungsten, aluminum, and ruthenium, the value of ΔYI was 1.6 and the total metal content was 4.2 ppm, which was less effective than Example 1. The polymer yield in this dedetaching step was 81%. The results are listed in Table 2.

Comparative Example 3
To the good solvent phase containing the crude polymer (1) recovered in Comparative Example 2, 0.37 parts by weight of lactic acid and 50 parts by weight of methanol were added, stirred at 60 ° C. for 1 hour, and cooled to room temperature. Separated into a poor solvent phase and a good solvent phase. The good solvent phase was recovered, methanol was added again, the mixture was stirred at 60 ° C. for 1 hour, cooled to room temperature, and then the good solvent phase was recovered. As a result of evaluating the total metal content of ΔYI and tungsten, aluminum, and ruthenium, the value of ΔYI was 0.5 and the total metal content was 0.06 ppm, which was equivalent to that of Example 1. The polymer yield in this dedetaching step was as low as 70%. The results are listed in Table 2.

  According to the present invention, the metal component contained in the polymer solution is effectively removed by adding a simple process, and the polymer in which the content of the metal component is sufficiently reduced and the hue is improved is obtained in a high yield. Can be manufactured.

Claims (8)

A method for producing a polymer obtained by removing a metal catalyst residue from a crude polymer containing the metal catalyst residue,
The crude polymer is a crude polymer having a structural unit represented by the following formula (1) obtained by a hydrogenation reaction of a ring-opened polymer of a cyclic olefin, and a crude polymer solution in which the crude polymer is dissolved in a solvent; , look including the step of the solvent and liquid-liquid separation aprotic polar solvent capable of, the contacting liquid-liquid, wherein the solvent is an alicyclic hydrocarbon solvent, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ester Production of a polymer, characterized in that it is a single solvent, a ketone solvent, an ether solvent or an alcohol solvent, or a combination of two or more thereof, and the residual amount of the metal component is 20 ppm or less in terms of metal atoms Method.

(In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group containing an oxygen atom having 1 to 20 carbon atoms, or 3 carbon atoms. Or a substituent selected from a hydrolyzable silyl group having 0 to 12 carbon atoms, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an alkylene group or an arylene group. A group, an acid anhydride, or a lactone may be formed, and m is 0 or 1.)   The method for producing a polymer according to claim 1, wherein a difference in boiling point between the aprotic polar solvent and the solvent under atmospheric pressure is 10 ° C or more.   The aprotic polar solvent was selected from dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, acetonitrile, γ-butyrolactone, and N-methyl-2-pyrrolidone 3. The method for producing a polymer according to claim 1, wherein the polymer is at least one solvent.   4. The method for producing a polymer according to claim 1, wherein the metal catalyst serving as the metal catalyst residue is a ring-opening polymerization catalyst or a polymer hydrogenation catalyst.   The method for producing a polymer according to any one of claims 1 to 4, wherein the metal catalyst serving as the metal catalyst residue is a catalyst containing a metal of Group 4 to 13 element of the periodic table.   6. The method for producing a polymer according to claim 5, wherein the metal of Group 4 to 13 element of the periodic table is at least one metal selected from tungsten, titanium, nickel, cobalt, aluminum, and ruthenium.   The method for producing a polymer according to any one of claims 1 to 6, wherein the polymer contains a cyclic olefin polymer.   A metal in a polymer solution, wherein a crude polymer solution obtained by dissolving a crude polymer containing a metal catalyst residue in a solvent and an aprotic polar solvent capable of liquid-liquid separation are brought into liquid-liquid contact. Catalyst residue removal method.