JP2008156569A - Method of purifying norbornene compound polymer hydrogenated substance, norbornene compound polymer hydrogenated substance prepared thereby, molding material made therefrom and its molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of removing impurities such as catalyst residue, particularly, impurities containing metals from a norbornene compound polymer hydrogenated substance solution in high removing efficiency without damaging the productivity, even in the case where the molecular weight of the polymer hydrogenated substance is high or the viscosity of the polymer solution is high. <P>SOLUTION: In the method of purifying the norbornene compound polymer hydrogenated substance, an alcohol, water and a basic compound of an amount necessary to make the water basic are added to the norbornene compound polymer hydrogenated substance solution obtained by hydrogenating a norbornene compound polymer by using a homogeneous hydrogenation catalyst, to remove insoluble matter produced. Also, the norbornene compound polymer hydrogenated substance obtained by this purifying method and the molding material and molding made therefrom are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for purifying a norbornene compound polymer hydrogenated product, a norbornene compound polymer hydrogenated product obtained by this method, a molding material comprising the same, and a molded product thereof. More specifically, a method for purifying a norbornene compound polymer hydrogenated product, characterized by treating the norbornene compound polymer hydrogenated product by a specific method, and in particular, by removing metal impurities from the norbornene compound polymer hydrogenated product to remove norbornene compound polymer hydrogenated product. The present invention relates to a method for purifying a compound polymer hydrogenated product, a norbornene compound polymer hydrogenated product obtained by this method, a molding material comprising the same, and a molded product thereof.

Since the polymer of norbornene compound is excellent in transparency and heat resistance, it is used in various fields such as mounting parts such as semiconductors, liquid crystal parts, and optical parts in the form of thin films, films, sheets and the like. .
In the norbornene compound polymer hydrogenated product obtained by hydrogenating the carbon-carbon unsaturated bond contained in the norbornene compound polymer, the above characteristics are further improved. In order to use the hydrogenated norbornene compound polymer for various purposes, it is necessary to remove the catalyst used in the hydrogenation reaction of the norbornene compound polymer.

  As a method for hydrogenating the norbornene compound polymer, the norbornene compound polymer solution is a heterogeneous hydrogenation catalyst, that is, a transition metal such as nickel or palladium supported on a carrier such as diatomaceous earth or alumina. A method is known in which hydrogenation is performed by adding a hydrogenation catalyst insoluble in a polymer solvent. When these heterogeneous hydrogenation catalysts are used, the heterogeneous hydrogenation catalyst can be easily removed from the norbornene compound polymer hydrogenated product by filtration after the completion of the hydrogenation reaction.

However, among the norbornene compound polymers, a polymer having an aromatic ring in the molecular skeleton, the aromatic ring is not hydrogenated but only a linear molecular chain is hydrogenated (selective hydrogenation), or a high molecular weight polymer. In the case of hydrogenation, a homogeneous hydrogenation catalyst is often used from the viewpoint of hydrogenation efficiency and the like.
In order to remove the hydrogenation catalyst from the reaction system after hydrogenating the norbornene compound polymer using a homogeneous hydrogenation catalyst, the hydrogenation catalyst is soluble in the solvent of the norbornene compound polymer and the amount used is also small. Therefore, the purpose cannot be achieved by filtration.

Of course, there is known a method of removing a catalyst residue from a polymer by adding a large amount of a poor solvent for the polymer to the polymer solution and precipitating the polymer, but it is necessary to use a large amount of the poor solvent. Therefore, it cannot be said that it is advantageous in terms of equipment and economy, and it is difficult to say that it is efficient.
An extraction method is known as a method for removing catalyst residues and the like without coagulating a polymer solution. This method is a method of extraction and removal using a solvent that is incompatible with the solvent of the polymer solution and dissolves the impurities, such as water. At this time, a method has also been proposed in which an acid such as an organic acid is added to convert the catalyst metal or the like into water-soluble (Patent Document 1).
However, this method cannot be said to remove impurities sufficiently and is not efficient.

In addition, a method is known in which an adsorbent is added to a polymer solution, a catalyst residue or the like is adsorbed on the adsorbent, and then removed by filtration or the like.
The present applicant previously reported a method of adding hydrogen to the norbornene compound polymer, adding isopropyl alcohol and activated clay to the reaction solution, stirring, and then filtering with filter paper using diatomaceous earth as a filter aid (patent) Reference 2).
However, this method can be applied to a polymer having a number average molecular weight of at most 20,000 to 30,000 as described in Patent Document 2, but the case where the molecular weight of the polymer is higher or the concentration of the polymer solution is high. In this case, the viscosity of the polymer solution becomes high, so that the adsorption efficiency by the adsorbent is lowered or the filtration rate is remarkably slowed, resulting in a problem that productivity is lowered.

JP 2002-284820 A JP-A-10-139865

  Therefore, the object of the present invention is to reduce the productivity even if the molecular weight of the polymer hydrogenated product is high or the viscosity of the polymer solution is high, from the norbornene compound polymer hydrogenated solution. An object of the present invention is to provide a method for removing impurities such as catalyst residues, particularly impurities containing metal, with high removal efficiency.

As a result of diligent research to achieve the above object, the present inventor added alcohol and water to a norbornene compound polymer hydrogenated solution containing a hydrogenation catalyst residue, and further added calcium hydroxide thereto. As a result of the addition, it was found that the hydrogenation catalyst residue can be easily precipitated in a filterable state. Based on this, further research has been conducted and the present invention has been completed.
Thus, according to the present invention, alcohol, water, and water are made basic to a solution of a norbornene compound polymer hydrogenated product obtained by hydrogenating a norbornene compound polymer using a homogeneous hydrogenation catalyst. A method for purifying a norbornene compound polymer hydrogenated product is provided, which comprises adding a necessary amount of a basic compound to remove impurities generated.

In the purification method of the present invention, it is preferable to remove insoluble substances from the solution of the hydrogenated norbornene compound polymer by filtration.
In the purification method of the present invention, the basic compound preferably contains an alkaline earth metal.
In the purification method of the present invention, the insoluble material is preferably a substance containing a metal contained in a solution of a norbornene compound polymer hydrogenated product.
In the purification method of the present invention, the amount of alcohol and water to be added is 0.5 to 10 equivalents and 0.1 to 10 equivalents, respectively, with respect to the metal contained in the solution of the norbornene compound polymer hydrogenated product. It is preferable that

The purification method of the present invention is suitably applied to the purification of a norbornene compound polymer hydrogenated product having a weight average molecular weight of 50,000 or more.
Moreover, according to this invention, the norbornene compound polymer hydrogenated product obtained by the purification method of the norbornene compound polymer hydrogenated product of the said invention is provided.
Moreover, according to this invention, the molding material which consists of the norbornene compound polymer hydrogenated substance of the said invention is provided.
Furthermore, according to this invention, the molded object formed by shape | molding the molding material of the said invention is provided.

  According to the purification method of the present invention, from the norbornene compound polymer hydrogenated solution, even if the molecular weight of the polymer hydrogenated product is high or the viscosity of the polymer solution is high, the productivity is not impaired. With high removal efficiency, impurities such as catalyst residues, particularly impurities containing metals can be removed. Since the thus obtained norbornene compound polymer hydrogenated product is excellent in optical properties, mechanical properties, electrical / electronic properties, chemical properties, etc., it can be suitably used in various applications.

  The norbornene compound polymer hydrogenated product to which the purification method of the present invention is applied is obtained by hydrogenating a norbornene compound polymer obtained by polymerizing a norbornene compound. Examples of the norbornene compound polymer include a ring-opening (co) polymer of a norbornene compound, an addition type (co) polymer of a norbornene compound, and an addition type copolymer of a norbornene compound and an α-olefin.

The norbornene compound for obtaining the norbornene compound polymer is not particularly limited as long as it is a norbornene ring structure-containing cyclic olefin.
Specific examples thereof include bicyclo [2.2.1] hept-2-ene (common name: norbornene); 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl- Bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenyl-bicyclo [2.2.1] hept 2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-propenyl-bicyclo [2.2 .1] Bishi having a hydrocarbon substituent such as hept-2-ene B [2.2.1] hept-2-ene derivative;

  5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2 2.1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid Anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] A bicyclo [2.2.1] hept-2-ene derivative having a functional group such as hept-2-ene-5,6-dicarboxylic imide;

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] norbornene derivatives having 3 or more rings such as dodec-3-ene (common name: tetracyclododecene);

8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 1,4-methano-1,4,4a, 9a-norbornene derivative having three or more rings having a hydrocarbon substituent such as tetrahydrofluorene;

8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^{3, 6} . 0 ^2,7 . 0 ^{9, 13]} pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene and the like.

  In the present invention, a monomer capable of metathesis polymerization with a norbornene compound, such as cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1 -Monocyclic cycloolefins such as methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene, 1,5-cyclooctazine and cyclododecene; acetylenes and acetylenes which are substituted acetylenes such as propyne and 1-butyne; 1 , 6-heptadiene and the like dienes having double bonds at both ends thereof; and the like may be copolymerized with a norbornene compound.

  If necessary, the norbornene compound polymer of the present invention contains an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrene hydrocarbon, an olefinic unsaturated bond and a hydrolyzable group by a known method. It may be modified with an organosilicon compound, an unsaturated epoxy monomer, or the like.

  Although the manufacturing method of a norbornene compound polymer is not specifically limited, For example, it can obtain by carrying out ring-opening polymerization of a norbornene compound in presence of a metathesis catalyst.

Ring-opening polymerization of a norbornene compound with a metathesis polymerization catalyst can be performed according to a known method.
The metathesis polymerization catalyst used is not particularly limited and may be a known one. Specifically, for example, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium, platinum and the like, and a reducing agent; titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a metal halide or acetylacetone compound selected from the group consisting of an organoaluminum compound as a cocatalyst; or a known Schrock-type or Grubbs-type living ring-opening disclosed in JP-A-7-179575 A metathesis catalyst or the like can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 1 / 1,000,000 to 1/10, preferably 1 / 100,000 to 1/1 in terms of the molar ratio to the total norbornene compound amount. 100.

  In the present invention, a polar compound can be further added to the catalyst system to enhance the polymerization activity and the selectivity of ring-opening polymerization. Examples of polar compounds include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and others And Lewis acid. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like. These polar compounds are used singly or in combination of two or more, and the amount used is appropriately selected, but the ratio with the metal in the catalyst, that is, the ratio of polar compound / metal (molar ratio). ), Usually in the range of 1 to 100,000, preferably 5 to 10,000.

The polymerization reaction may be performed by bulk polymerization without using a solvent, or may be performed in a solvent such as an organic solvent. The solvent is not particularly limited as long as it is inert to the polymerization reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane. Alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene; nitromethane, nitrobenzene, acetonitrile, benzonitrile, etc. Nitrogen-containing hydrocarbons; and the like. The polymerization temperature is usually −50 ° C. to + 100 ° C., preferably −30 ° C. to + 80 ° C., more preferably −20 ° C. to + 70 ° C., and the polymerization pressure is usually 0 to 50 kg / cm ² , preferably Is in the range of 0-20 kg / cm ² . The polymerization time is appropriately selected depending on the polymerization conditions, but is usually in the range of 30 minutes to 20 hours, preferably 1 to 10 hours.

  The method for hydrogenating the norbornene compound polymer is not particularly limited, and may be performed by bringing the norbornene compound polymer into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

As the hydrogenation catalyst, a homogeneous catalyst or a heterogeneous catalyst is usually used, but the purification method of the present invention is applied when hydrogenation is performed using a homogeneous catalyst.
Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so the addition amount may be small, and since they are active without high temperature and pressure, the polymer does not decompose or gel, and low cost and quality Excellent stability.

  The homogeneous catalyst is not particularly limited. For example, a Wilkinson complex, that is, chlorotris (triphenylphosphine) rhodium (I), dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (Triphenylphosphine) ruthenium; a catalyst comprising a combination of a transition metal compound and an alkyl metal compound, specifically, cobalt acetate / triethylaluminum, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, cobalt octenoate / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxy titanate The combination of such DOO / dimethyl magnesium.

The hydrogenation reaction is carried out in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the catalyst, but a hydrocarbon-based solvent is usually used because of the excellent solubility of the resulting hydrogenated product.
Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; saturated alicyclic hydrocarbons such as cyclohexane and decalin; Among these, cyclic aromatic hydrocarbons and saturated alicyclic hydrocarbons are preferable, and saturated alicyclic hydrocarbons are particularly preferable. These organic solvents can be used alone or in combination of two or more.
Usually, the same solvent as the polymerization reaction solvent may be used, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is to cause the reaction. The hydrogenation reaction can be carried out according to a conventional method, but the conditions may be set appropriately depending on the type of hydrogenation catalyst and the reaction temperature.

  The amount of the hydrogenation catalyst used may be appropriately selected according to the structure of the norbornene compound polymer, the target degree of hydrogenation, the hydrogenation conditions, etc., but is preferably based on 100 parts by weight of the norbornene compound polymer. 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, particularly preferably 0.1 to 20 parts by weight.

Conditions of the hydrogenation reaction is not particularly limited, usually, 0.1~80kg / cm ² hydrogen pressure, preferably 0.5~60kg / cm ^2, further preferably 1 to 50 kg / cm ^2. The reaction temperature of the hydrogenation reaction is usually −10 to + 200 ° C., preferably 0 to 180 ° C., more preferably 20 to 160 ° C.

The molecular weight of the norbornene compound polymer hydrogenated product obtained by hydrogenation is a polyisoprene equivalent number average molecular weight measured by gel permeation chromatography (GPC) method using cyclohexane as a solvent, and is usually 1,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 10,000 to 600,000, particularly preferably 35,000 to 600,000.
Further, the weight average molecular weight measured in the same manner is preferably 2,500 or more, more preferably 10,000 or more, and particularly preferably 50,000 or more.

The molecular weight distribution of the norbornene compound polymer hydrogenated product is appropriately selected according to the purpose of use, but the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polyisoprene conversion values measured by the GPC method using a cyclohexane solvent. )) (Mw / Mn) is usually 5.0 or less, preferably 3.0 or less, and more preferably 2.5 or less, because mechanical strength and formability are highly balanced and suitable. is there.
The glass transition temperature (Tg) of the norbornene compound polymer hydrogenated product may be appropriately selected according to the purpose of use, but is usually 70 ° C. or higher, preferably 90 ° C. or higher, more preferably 110 ° C. or higher. However, it is excellent in heat resistance and suitable.

After the hydrogenation reaction, alcohol and water are added to the hydrogenation reaction solution. Thereby, the catalyst contained in the reaction solution is insolubilized.
The alcohol preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably isopropanol. Specific examples of the alcohol include methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and the like.
The amount of alcohol is the catalyst contained in the hydrogenation reaction solution, that is, the metal component contained in the hydrogenation catalyst, or when the hydrogenation reaction is carried out in the same reaction system without being removed from the polymerization catalyst reaction system following the polymerization. Is preferably in the range of 0.5 to 10 equivalents, more preferably in the range of 1 to 8 equivalents, and in the range of 1.5 to 5 equivalents with respect to the metal component contained in the hydrogenation catalyst and the polymerization catalyst. Particularly preferred.
Here, 1 equivalent of alcohol is obtained by dividing the atomic weight of a certain metal by the valence of the metal to be 1 equivalent of that metal, and the equivalent number of catalytic metal contained in the reaction solution, that is, in the reaction solution. Corresponds to the value obtained by dividing the product of the weight of the catalyst metal and its valence by the atomic weight of the metal (when multiple types of catalyst metals are included, the total number of equivalents of each catalyst metal) The amount of alcohol in moles.
For example, in the case of tungsten, since the atomic weight is 183.8 and the valence is 6, when 183.8 mg of tungsten metal is contained in the reaction solution, the equivalent number is 0.1838 × 6 / 183.8 = 0.6.
If the amount of alcohol added is too small, the removal efficiency is lowered, and the filtration rate when the insoluble catalyst is removed by filtration is lowered. On the other hand, when there is too much quantity of alcohol, removal efficiency will fall.

The amount of water added to the hydrogenation reaction solution is the same as that of the catalyst contained in the hydrogenation reaction solution, that is, the metal component contained in the hydrogenation catalyst, or without being removed from the polymerization catalyst reaction system subsequent to the polymerization. When the hydrogenation reaction is performed in the system, the range of 0.1 to 10 equivalents is preferable with respect to the metal component contained in the hydrogenation catalyst and the polymerization catalyst, and the range of 0.5 to 7 equivalents is more preferable. A range of 1 to 5 equivalents is particularly preferred.
Here, 1 equivalent of water is obtained in the same manner as in the case of alcohol.

The method for adding alcohol and water is not particularly limited, and may be added separately or in combination. Further, the whole amount may be added in a lump or may be added in two or more portions.
After the addition of alcohol and water, the reaction solution is stirred for an appropriate time to disperse the alcohol and water uniformly in the reaction solution.

In the method for purifying a norbornene compound polymer hydrogenated product of the present invention, it is essential to use water together with alcohol.
After the hydrogenation reaction, when an alcohol is added to a system containing a metal-containing homogeneous hydrogenation catalyst, the metal in the hydrogenation catalyst is alkoxylated. As the degree of alkoxylation increases, the ratio of hydrocarbon groups increases, so that the solubility of the alkoxylated metal increases, that is, it becomes difficult to deposit and remove the metal from the system. In addition, some alkoxylated metals (metal alkoxides) may crosslink via oxygen of the alcohol hydroxyl group and become insolubilized by crosslinking. When viewed, most metal alkoxides remain dissolved and the efficiency of removal decreases.
If water is present during this alkoxylation, the alkoxylated metal eventually becomes a metal hydroxide and precipitates from the system. Thereby, it becomes easy to remove the metal by filtration, so that the removal efficiency is improved.
In addition, since compatibility with a solvent and water improves because alcohol exists, conversion from the alkoxylated metal (metal alkoxide) to a metal hydroxide advances rapidly.

In the purification method of the present invention, it is essential to add a basic compound together with alcohol and water to the hydrogenation reaction solution.
The basic compound is not particularly limited, and specific examples thereof include metal hydroxides and oxides and carbonates, ammonia, amines, etc., preferably metal hydroxides, More preferred are alkali metal or alkaline earth metal hydroxides, and particularly preferred are alkaline earth metal hydroxides.
Alkali earth metal hydroxides are not particularly limited, but calcium, magnesium and barium hydroxides are preferred from the standpoint of availability and economy.
The amount of basic compound added is such that the water added to the hydrogenation reaction solution is made basic (i.e., when the basic compound is added to the same amount of water added to the hydrogenation reaction solution) It is sufficient if the amount is sufficient for the pH of water to exceed 7.0).

By adding alcohol, water, and a basic compound to the hydrogenation reaction solution, an insoluble matter containing a metal in the solution is precipitated from the solution, and thus the insoluble matter is removed from the hydrogenation reaction solution.
The removal method is not particularly limited as long as it is a conventionally known method such as centrifugation or filtration, but filtration is simple.

The method of filtration is not particularly limited, and filtration under pressure or suction filtration may be used.
The filter medium is not particularly limited and may be any of paper or plastic filter paper, metal filter, ceramic filter, and the like, but from the viewpoint of strength and durability, it is preferable to use a metal filter or a ceramic filter. Further, the shape of the filter medium is not particularly limited.
The coarseness of the filter medium is not particularly limited, but usually the pore size of the filter is usually 50 μm or less, preferably 1 μm or less, more preferably 0.3 μm or less.

During filtration, a filter aid may be added to improve filtration efficiency.
Examples of filter aids include diatomaceous earth and perlite.

A norbornene compound polymer hydrogenated product can be obtained by a conventional method from a hydrogenation reaction solution from which an insoluble material containing a metal in the solution has been removed.
The norbornene compound polymer hydride obtained by the purification method of the present invention has a very low metal content, and the total metal content is 1 ppm by weight or less, preferably 100 ppm by weight or less.

  The norbornene compound polymer hydrogenated product of the present invention has excellent transparency, moisture resistance, heat resistance, impact resistance, mechanical strength, gas barrier property, chemical resistance, low inherently contained in the norbornene compound polymer hydrogenated product. Since the low dielectric constant, low dielectric loss, etc. are further improved while maintaining water absorption, etc., it is useful as a molding material for various molded products.

  In addition to the norbornene-based polymer, the molding material of the present invention can be blended with other polymer materials, various additives, and the like depending on the application field. Examples of other polymer materials include rubber polymers and other thermoplastic resins.

Various additives can be blended in the molding material of the present invention as necessary.
Examples of such additives include stabilizers, lubricants, UV absorbers, antistatic agents, slip agents, antifogging agents, dyes, pigments, natural oils, synthetic oils, waxes, crystal nucleating agents, hydrochloric acid absorbers, Examples include flame retardants, flame retardant aids, compatibilizers, crosslinking agents, crosslinking aids, plasticizers, organic or inorganic fillers, and the like.
Furthermore, for the purpose of adjusting mechanical properties and the like, different types of thermoplastic resins such as polycarbonate, polystyrene, polyphenylene sulfide, polyetherimide, polyester, polyamide, polyarylate, polysulfone, and polyethersulfone may be blended. .

  The method for adding these various compounding agents is not particularly limited as long as these compounding agents are sufficiently dispersed in the norbornene compound polymer hydrogenated product. For example, whether the compounding agent is added in any process during the polymerization. Or it is performed by the method of adding in the arbitrary processes of melt extrusion. When a rubber polymer is used as a compounding agent, for example, a method of kneading a resin in a molten state with a ribbon blender, a Henschel mixer, a twin-screw kneader, etc., after dissolving and dispersing and mixing in an appropriate solvent, the solvent is added. There are methods such as a coagulation method, a casting method or a direct drying method.

  The molded body of the present invention can be produced by molding the molding material into a desired shape by a known molding method. Examples of molding methods include, for example, injection molding, extrusion blow molding, injection blow molding, two-stage blow molding, multilayer blow molding, connection blow molding, stretch blow molding, rotational molding, and vacuum molding. , Extrusion molding method, calender molding method, solution casting method, hot press molding method, inflation method and the like, but the molding is not limited to a specific molding method as much as possible.

The shape of the molded product of the present invention is not particularly limited.
The molded article of the present invention has transparency, moisture resistance, heat resistance, impact resistance, mechanical strength, solution stability, low dielectric constant, low dielectric loss tangent, low moisture permeability, gas barrier property, steam sterilization resistance, chemical resistance It has excellent properties and is useful in a wide range of fields as various molded products including optical materials. For example, optical disc, optical fiber, optical card, optical lens, optical mirror, light guide plate, light diffusion plate, polarizing film, retardation film, light diffusion sheet, prism sheet, color filter substrate, touch panel, transparent electrode substrate, CD, MD Optical recording substrates such as DVDs, TFT substrates, liquid crystal display substrates, organic EL display substrates, optical transmission waveguides, optical lenses, sealing materials, and other optical materials; medical equipment; electrical insulating materials; electronic components Processing equipment; Windows through electronic parts for light receiving elements; Structural materials and building materials such as windows, equipment parts, and housing; Automotive equipment such as bumpers, rearview mirrors, headlamp covers, tail lamp covers, and instrument panels; speaker cones Materials such as materials, vibration elements for speakers, and microwave containers; bottles, returnable bottles, baby bottles, etc. Packaging materials, such as wraps; article container film can be used in various applications such as a sheet.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples. The properties of the norbornene compound polymer hydrogenated product were measured by the following test methods.
“Parts”, “%” and “ppm” represent “parts by weight”, “wt%” and “weight ppm”, respectively, unless otherwise specified.
〔Glass-transition temperature〕
Measured by differential scanning calorimetry (DSC) method.
[Molecular weight]
Unless otherwise specified, it is a polyisoprene conversion value by gel permeation chromatography (GPC) using cyclohexane as a solvent.
[Hydrogenation rate of polymer]
^{It is} measured by ¹ H-NMR.
[Metal content in polymer hydrogenated product]
Measured by inductively coupled plasma optical emission spectrometry. The measurement limit is 0.01 ppm.
[Measurement of filtration operation and filtration time]
A filter bed is formed using 3 g of Radiolite # 500 (manufactured by Showa Chemical Industry Co., Ltd.) as a filter medium on a filter paper (Kiriyama filter paper No. 5B) using a cylindrical pressure filtration device having a diameter of 5 cm. 1.5 kg / cm ² of nitrogen pressure was applied, and the time taken to filter 100 g of the solution containing the catalyst after the hydrogenation reaction (polymer concentration 18%) was measured.
[Chlorine atomic weight]
100 mg of the polymer hydrogenated product is combusted with a Dorman combustor, absorbed in 5 ml of pure water, and analyzed by ion chromatography.

(Example 1)
(polymerization)
Under nitrogen atmosphere, 400 parts of dehydrated cyclohexane, 0.18 part of 1-hexene, 0.25 part of isopropyl ether, 0.18 part of isobutyl alcohol, 0.48 part of isobutylaluminum, and 0.77% tungsten hexachloride in cyclohexane solution 42 parts were placed in a polymerization reactor at room temperature and mixed. The polymerization reactor was then charged at 45 ° C. with 200 parts of a monomer mixture consisting of 30% tetracyclododecene and 70% 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, and tungsten hexachloride. 25 parts of a 0.77% cyclohexane solution was continuously added over 2 hours for polymerization.
(Hydrogenation)
333 parts of the resulting polymerization reaction solution was transferred to an autoclave equipped with a stirrer, and 207 parts of cyclohexane, 1 part of nickel acetylacetonate, and 15 parts of a cyclohexane solution containing 20% triisobutylaluminum were added. After the inside of the autoclave was replaced with hydrogen, the reaction was carried out for 3 hours under the reaction conditions of 180 ° C. and 4.5 MPa with stirring.
(Purification)
To 278 parts of the resulting norbornene compound polymer hydrogenated solution, 5 equivalents of isopropanol, 3 equivalents of water and calcium hydroxide 0.0009 parts relative to the metal in the catalyst used for polymerization and hydrogenation Were mixed at once and stirred at 80 ° C. for 1 hour.
Next, the norbornene compound polymer hydrogenated product was filtered using a cylindrical pressure filtration apparatus having a diameter of 5 cm. Filtration took 18 minutes.
The filtrate was poured into isopropanol under stirring to precipitate a norbornene compound polymer hydrogenated product, which was collected by filtration. Further, this was washed with acetone and then dried for 24 hours in a vacuum dryer set at 1 torr or less and 100 ° C. to obtain a hydrogenated norbornene compound polymer.

The resulting norbornene compound polymer hydrogenated product has a hydrogenation rate of carbon-carbon double bonds of the main chain and side chain of 99.9 mol%, and the hydrogenation rate of the aromatic ring is 99.8 mol%, The number average molecular weight (Mn) was 40,500, the weight average molecular weight (Mw) was 99,500, and the molecular weight distribution (Mw / Mn) was 2.46. The glass transition temperature was 161 ° C.
The amount of residual metal in the hydrogenated ring-opening copolymer was 0.01 ppm (detection limit) or less for tungsten atoms, 0.01 ppm (detection limit) or less for nickel atoms, 0.02 ppm for aluminum atoms, palladium Atoms were 0.01 ppm (detection limit) or less.
As a result, the chlorine atom amount was 0.02 ppm (detection limit) or less.
These results are shown in Table 1.

(Example 2)
The norbornene compound polymer hydrogenated product was purified in the same manner as in Example 1 except that the calcium hydroxide was changed to magnesium hydroxide.
Table 1 shows the results of measuring the properties and metal content of the obtained norbornene compound polymer hydrogenated product.

(Comparative Example 1)
A norbornene compound polymer hydrogenated product was purified in the same manner as in Example 1 except that calcium hydroxide was not added.
Table 1 shows the results of measuring the properties and metal content of the obtained norbornene compound polymer hydrogenated product.

(Comparative Example 2)
The norbornene compound polymer hydrogenated product was purified in the same manner as in Example 1 except that water was not added.
Table 1 shows the results of measuring the properties and metal content of the obtained norbornene compound polymer hydrogenated product.

Table 1 shows the following.
In Comparative Example 1 in which no basic compound was used and in Comparative Example 2 in which water was not added, (i) productivity was poor because of the long time required for filtration, (ii) metal removal was not sufficient, Furthermore, (iii) the residual amount of chlorine atoms was large.
On the other hand, in Example 1 and Example 2 satisfying the requirements of the present invention, the metal and chlorine atoms were sufficiently removed, and the productivity was good because the filtration time was short.

Claims (9)

  In the solution of the norbornene compound polymer hydrogenated product obtained by hydrogenating the norbornene compound polymer using a homogeneous hydrogenation catalyst, alcohol, water and the basic compound in an amount necessary to make the water basic And a method for purifying a norbornene compound polymer hydrogenated product, which comprises removing the insoluble matter produced.   The purification method according to claim 1, wherein the insoluble matter is removed from the solution of the norbornene compound polymer hydrogenated product by filtration.   The purification method according to claim 1 or 2, wherein the basic compound contains an alkaline earth metal.   The purification method according to any one of claims 1 to 3, wherein the insoluble matter is a substance containing a metal contained in a solution of a norbornene compound polymer hydrogenated product.   The amounts of alcohol and water to be added are 0.5 to 10 equivalents and 0.1 to 10 equivalents, respectively, with respect to the metal contained in the solution of the norbornene compound polymer hydrogenated product. The purification method according to any one of the above.   The purification method according to any one of claims 1 to 5, which is applied to purification of a hydrogenated norbornene compound polymer having a weight average molecular weight of 50,000 or more.   A norbornene compound polymer hydrogenated product obtained by the purification method according to any one of claims 1 to 6.   A molding material comprising the norbornene compound polymer hydrogenated product according to claim 7.   The molded object formed by shape | molding the molding material of Claim 8.