JP2003212923A - Alicyclic-structure-containing polymer hydrogenate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alicyclic-structure-containing polymer hydrogenate having a very low small foreign matter content and to provide a method for efficiently producing the same. <P>SOLUTION: The method for producing an alicyclic-structure-containing polymer hydrogenate comprises hydrogenating the carbon-carbon double bonds of an alicyclic structure-containing polymer selected from the group consisting of a norbornene polymer, a vinyl cyclic hydrocarbon polymer, and a cyclic conjugated diene polymer by using a heterogeneous hydrogenation catalyst being one prepared by supporting a group 8-10 metal in the periodic table on a carrier and having a content of particles with particle diameters of at most 1 μm of at most 1 vol.% and a specific surface area of 50-300 m<SP>2</SP>/g to obtain an alicyclic structure-containing polymer hydrogenate and removing the hydrogenation catalyst therefrom. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alicyclic structure-containing polymer hydrogenated product and a method for producing the same, and more particularly to a high-quality alicyclic structure-containing polymer hydrogenated product having a small amount of foreign matter and its production. Regarding the method.

[0002]

2. Description of the Related Art Polymers containing alicyclic structures such as norbornene-based polymers are excellent in heat resistance, transparency, low hygroscopicity, and have birefringence by hydrogenating carbon-carbon double bonds in the polymer. Therefore, it is often used as a material for optical disc substrates, optical lenses, magnetic disc substrates, liquid crystal display materials, medical equipment, packaging materials, packing, gaskets, sealing materials, piping materials (flange, elbow, pipe, etc.). The application is being expanded to the field of.

Usually, when obtaining a hydrogenated product of an alicyclic structure-containing polymer, the hydrogenation reaction of the alicyclic structure-containing polymer is carried out in a solution, and then the hydrogenation catalyst is removed from the solution to give an alcohol, a ketone or the like. The polymer is coagulated by bringing it into contact with the poor solvent of (1), the polymer is separated by filtration, and dried. However, the removal of the hydrogenation catalyst is insufficient, foreign substances in the poor solvent are mixed in the hydrogenated product, and dust in the air is mixed in the separation / drying process.

Since these minute foreign substances are not compatible with the alicyclic structure-containing polymer, an alicyclic structure-containing polymer containing a large amount of these foreign substances is molded, and in particular, an optical disk substrate or a magnetic disk. When processed into a substrate such as a substrate for information recording medium, the performance and function of the obtained molded body are seriously adversely affected.

An optical disk reproduces or records information using a laser beam, but a large-capacity optical information recording medium such as a DVD has a recording density higher than that of a conventional CD, LD, etc. The spot diameter of the laser light used for writing and reading has also become extremely small.
Therefore, even if it is a minute foreign substance on the optical disk substrate,
It is prone to errors and the bit error rate tends to increase.

Further, in the case of a magnetic disk substrate such as a hard disk, when a large amount of minute foreign substances are present, these foreign substances appear as a large number of protrusions on the substrate surface. The surface protrusion is likely to come into contact with the magnetic head and cause a tracking error.

Therefore, the applicant of the present invention has filed Japanese Patent Application Laid-Open No. 10-600.
48, a cyclic olefin polymer having a particle size of 0.5 μm or more and a content of foreign matter of 3 × 10 ⁴ particles / g or less, and a filter having a charge trapping function for an organic solvent solution of the polymer. A method for producing a cyclic hydrocarbon-based polymer including a step of filtering is proposed. However, when trying to obtain a polymer with even smaller amounts of fine foreign matter, in the method of the above publication, the amount of fine foreign matter may vary, or filtration by a filter must be repeated a plurality of times, It was found that the efficiency of removing minute foreign matters was reduced.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to efficiently provide an alicyclic structure-containing polymer hydrogenated product in which the content of fine foreign matters is smaller than that conventionally known, and the hydrogenated product efficiently. It is to provide a stable manufacturing method. The present inventor, as a result of intensive studies to achieve the above object, a norbornene-based polymer, a vinyl cyclic hydrocarbon-based polymer, and in the alicyclic structure-containing polymer selected from the group consisting of cyclic conjugated diene-based polymer When hydrogenating a carbon-carbon double bond, hydrogenation is carried out using a heterogeneous hydrogenation catalyst having a specific particle size and a specific surface area to obtain a hydrogenated product after removal of the hydrogenation catalyst. It has been found that the content of minute foreign matter in the solution containing can be reduced, and the present invention has been completed based on these findings.

[0009]

Thus, according to the present invention: A heterogeneous hydrogenation catalyst in which a Group 8 to 10 transition metal of the periodic table is supported on a carrier, the content of particles having a particle diameter of 1 μm or less is 1 vol% or less, and a specific surface area is 50 to 3
In the alicyclic structure-containing polymer selected from the group consisting of norbornene-based polymers, vinyl cyclic hydrocarbon-based polymers, and cyclic conjugated diene-based polymers, using a heterogeneous hydrogenation catalyst of 00 m ² / g. 1. a method for producing an alicyclic structure-containing polymer hydrogenated product, which comprises a step of hydrogenating a carbon-carbon double bond to obtain an alicyclic structure-containing polymer hydrogenated product, and then removing the hydrogenation catalyst; The content of foreign particles with a particle size of 0.5 μm or more is 500 /
An alicyclic structure-containing polymer hydrogenated product having an amount of g or less is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention is as follows.
Heterogeneous hydrogenation catalyst in which a Group 0 transition metal is supported on a carrier, the content of particles having a particle size of 1 μm or less is 1% by volume or less, and the specific surface area is 50 to 300 m ² / g. The carbon-carbon double bond in the alicyclic structure-containing polymer selected from the group consisting of a norbornene-based polymer, a vinyl cyclic hydrocarbon-based polymer, and a cyclic conjugated diene-based polymer is hydrogenated by using a hydrogen-based catalyst. And alicyclic structure-containing polymer hydrogenated product, and then removing the hydrogenation catalyst.

The heterogeneous hydrogenation catalyst used in the method of the present invention comprises a carrier carrying a transition metal of Groups 8 to 10 of the periodic table, and the content of particles having a particle size of 1 μm or less is 1 vol% or less. , Preferably 0.5% by volume or less and having a specific surface area of 50 to 300 m ² / g, preferably 100 to 300.
m ² / g. If the content of the heterogeneous hydrogenation catalyst having a particle size of 1 μm or less is larger than the above range, hydrogenation failure may occur or the amount of foreign matter in the alicyclic structure-containing polymer hydrogenated product tends to increase. It is in. Further, if the specific surface area of the catalyst is smaller than the above range, defective hydrogenation tends to occur.

As the transition metals of Groups 8 to 10 of the periodic table constituting the heterogeneous hydrogenation catalyst, nickel, cobalt,
Examples include iron, rhodium, palladium, platinum, ruthenium and the like. Among these, nickel is preferable in terms of catalyst cost and hydrogenation efficiency. Moreover, the said transition metal can be used individually or in combination of 2 or more types.

Carriers applicable to the method of the present invention include:
Activated carbon, diatomaceous earth, magnesia, silica, alumina,
Examples thereof include barium sulfate, silica-magnesia, silica-zirconia, diatomaceous earth-zirconia, and alumina-zirconia. The method of supporting the transition metal on the carrier includes, but is not limited to, a coprecipitation method, a deposition method (kneading method), and an impregnation method. The amount of the transition metal supported on the carrier supporting the transition metal applicable to the method of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more, based on the total weight of the carriers.

The heterogeneous hydrogenation catalyst used in the method of the present invention may be in the form of powder, granules, spheres, pellets or the like, but it is averaged from the viewpoint of storage stability, filterability and hydrogenation efficiency. The particle size is preferably 5 to 100 μm, more preferably 10 to 50 μm. If the average particle size is too small, the filterability of the hydrogenation catalyst will decrease, and conversely, if the average particle size is too large, the storage stability and hydrogenation efficiency of the hydrogenation catalyst will tend to decrease.

In the method of the present invention, the amount of the hydrogenation catalyst used is 100 parts by weight of the alicyclic structure-containing polymer.
Usually 0.01 to 100 parts by weight, preferably 0.1 to 50
Parts by weight, more preferably 1 to 30 parts by weight.
Further, the hydrogenation catalyst can be used alone or in combination of two or more kinds.

In the method of the present invention, when the hydrogenation catalyst and an inorganic compound having at least one element selected from the group consisting of silicon, aluminum and magnesium are mixed and used, the storage stability of the hydrogenation catalyst, It is preferable because the filterability at the time of removing the catalyst after the hydrogenation reaction is improved.

As the inorganic compound containing silicon,
Acidic acid [diatomaceous earth, opal, etc .: SiO_Two・ XH
_TwoO], anhydrous silicic acid [such as quartz, crystal, agate, silica sand
DO: SiO _Two] And other silica minerals; silicon nitride [Si_Three
N_Four]; Of binary compounds such as silicon carbide [SiC]
Orthoclase [KAlSi_ThreeO₈], Garnet [Ca_ThreeA
l_Two(SiO_Four)_Three], Mica [KH_Two(AlSiO_Four)
_Three ], Kaolinite [Al_TwoH_Four Si_TwoO₉], Serpent
Stone [Mg_ThreeH_FourSi_TwoO₉], Talc [Mg_ThreeH_TwoSi _Four
O₁₂], Asbestos [Mg_ThreeCaSi_FourO₁₂], Zeoli
To [Na_TwoO ・ Al_TwoO_Three(SiO_Two)_Three] Such as natural
Silicon compounds composed of multiple elements present in
It Among these inorganic compounds containing silicon,
Politic earth and zeolites are preferred.

Examples of the inorganic compound containing aluminum include aluminum oxide [alumina: Al ₂ O ₃ ], aluminum hydroxide [gybstone: Al (OH) ₃ ], aluminum chloride [AlCl ₃ ], aluminum carbide [Al ₄
C ₃ , Al ₂ C ₃ ] and other compounds, as well as spinel [Al
₂ O ₃ · MgO], Kaolinite [Al ₂ O ₃ · 2Si
O ₂ · 2H ₂ O], cryolite _[AlF 3 · 3NaF], perlite _{[SiO 2: 70~80%, Al 2} O 3: 10
˜20%, Na ₂ O, K ₂ O] and other naturally occurring silicon-containing aluminum compounds. Among these inorganic compounds containing aluminum, alumina, pearlite and aluminum hydroxide are preferable.

As the inorganic compound containing magnesium, magnesium oxide [magnesia: MgO], magnesium chloride [MgCl ₂ ], magnesium sulfate [MgS]
O ₄ ], magnesium nitrate [Mg (NO ₃ ) ₂ ] and other single compounds, as well as dolomite [CaMg (CO ₃ ) ₂ ] and the above-mentioned mica, serpentine, talc, and asbestos naturally occurring double salts. Is mentioned. Among these inorganic compounds containing magnesium, magnesia and magnesium hydroxide are preferable.

The shape of the inorganic compound may be any of powder, granule, sphere, pellet and the like, but from the viewpoint of storage stability and filterability, the average particle diameter is preferably 0.1 to 500 μm, It is particularly preferably from 0.5 to 250 μm. If the average particle size is too small, the filterability of the hydrogenation catalyst will decrease, and conversely, if the average particle size is too large, the storage stability of the hydrogenation catalyst will decrease.

The amount of the inorganic compound mixed is preferably 10/90 to 90/1 in terms of weight ratio to the heterogeneous hydrogenation catalyst.
0, and more preferably 30/70 to 70/30.
The method of mixing the inorganic compound and the heterogeneous hydrogenation catalyst is not particularly limited as long as it is a method of uniformly dispersing the both, but it is preferable to avoid high-speed stirring and mixing that involves frictional heat.

The alicyclic structure-containing polymer selected from the group consisting of norbornene-based polymers, vinyl cyclic hydrocarbon-based polymers, and cyclic conjugated diene-based polymers to which the method of the present invention can be applied has a main chain and / or side chain. Those having an alicyclic structure in the chain, and those having an alicyclic structure in the main chain are preferable from the viewpoint of mechanical strength, heat resistance and the like. The number of carbon atoms constituting the ring is usually 4 to 30, preferably 5 to 20, from the viewpoint of mechanical strength, heat resistance and molding processability of the polymer.
More preferably, it is in the range of 5 to 15. The proportion of repeating units having an alicyclic structure in the polymer may be appropriately selected according to the purpose of use, and is usually 50% by weight or more, preferably 70% by weight or more, based on all repeating units.
More preferably, it is 90% by weight or more. The proportion of the repeating unit having an alicyclic structure is preferably within the above range from the viewpoint of transparency and heat resistance of the molded product. Among these, norbornene-based polymers and vinyl cyclic hydrocarbon-based polymers are preferable from the viewpoint of heat resistance and mechanical strength, and norbornene-based polymers are more preferable.

(1) Norbornene-based polymer Norbornene-based polymers are ring-opening of norbornene-based monomers.
It is an addition polymer of a polymer and a norbornene-based monomer.
It Norbornene-based monomers are disclosed in JP-A-2-227424.
It is not known in Japanese Laid-Open Patent Publication No. 2-276842.
Monomers, eg norbornene; dicyclopenes
Tadiene, tricyclo [4.3.0.1^2,5 ] -De
Ca-3-ene, tricyclo [4.4.0.1^2,5 ]
-Undeca-3,7-diene or tricyclo [4.
4.0.1^2,5 ] -Undeca-3,8-diene,
Ricyclo [4.4.0.1^2,5 ] -Undeca-3-
Ene, tetracyclo [7.4.0.1 ^{10, 13}． 0
^2,7] -Trideca-2,4,6,11-tetraene
(1,4-methano-1,4,4a, 9a-tetrahydro
Fluorene), tetracyclo [8.4.0.1
^{11, 14}． 0^3,8 ] -Tetradeca-3,5,7,
12-tetraene (1,4-methano-1,4,4a,
Also known as 5,10,10a-hexahydroanthracene
Norbornene ring that does not have a norbornane ring such as
conductor;

Tetracyclododecene, 8-methyl-teto
Lacyclo [4.4.0.1^2,5． 1^{7, 10}] -Dode
Cap-3-ene, 8-ethyl-tetracyclo [4.4.
0.1 ^2,5． 1^{7, 10}] -Dodeca-3-ene, 8-
Cyclopentyl-tetracyclo [4.4.0.1^2,5
 ． 1^{7, 10}] -Dodeca-3-ene, 8-cyclohex
Syl-tetracyclo [4.4.0.1^2,5． 1
^{7, 10}] -Norbornane ring such as dodeca-3-ene
Norbornene derivatives incidental thereto; and the like. Well
In addition, these monomers have alkyl groups, alkenyl groups,
Hydrocarbon groups such as rukylidene group; nitrogen atom, oxygen atom,
A group containing a silicon atom, a phosphorus atom, or a sulfur atom; norbo
A double bond other than the double bond of the Runen ring;
Good.

The above norbornene-based monomers may be used alone or in combination of two or more. The proportion of the norbornene-based monomer is usually 50 to 100% by weight, preferably 70 to 10% by weight based on all the monomers.
It is 0% by weight, more preferably 90 to 100% by weight, and particularly preferably 100% by weight. By setting the ratio of the norbornene-based monomer in this range, the mechanical strength of the obtained molded product is improved.

In the method of the present invention, in addition to the above norbornene-based monomer, as a copolymerizable monomer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and the like having 2 carbon atoms. Α- with ~ 20
Olefin; cyclobutene, cyclopentene, cyclohexene, and other cycloolefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, and other non-conjugated dienes can be used in an amount of 50% by weight or less based on the total amount of the monomers. These copolymerizable monomers can be used alone or in combination of two or more kinds.

The ring-opening polymer of a norbornene-based monomer is a norbornene-based monomer in the presence of a ring-opening polymerization catalyst in an organic solvent or without a solvent, usually at a polymerization temperature of −50 to 100 ° C., 0 It can be obtained by ring-opening polymerization at a polymerization pressure of 5 MPa.

As the ring-opening polymerization catalyst, (1) ruthenium, rhodium, palladium, osmium, iridium,
Alternatively, a catalyst including a metal halide such as platinum, a nitrate, or an acetylacetone compound, and a reducing agent,
(2) A catalyst including a metal halide such as titanium, vanadium, zirconium, tungsten, or molybdenum, or an acetylacetone compound and an organoaluminum compound as a cocatalyst.

The addition polymer of the norbornene-based monomer and the addition copolymer of the norbornene-based monomer and the above-mentioned copolymerizable monomer can be obtained by adding the monomer component in an organic solvent or without a solvent to titanium. A halide of a metal such as, zirconium, or vanadium, or an acetylacetone compound,
It can be usually obtained by a method of copolymerizing in the presence of a catalyst composed of an organoaluminum compound at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0 to 5 MPa.

(2) Vinyl cyclic hydrocarbon polymer As the vinyl cyclic hydrocarbon polymer, polymers of alicyclic vinyl monomers such as vinylcyclohexene and vinylcyclopentene; styrene, α-methylstyrene, etc. Polymers of aromatic vinyl monomers; and the like can be used. The polymerization reaction for producing the vinyl cyclic hydrocarbon-based polymer may be any known method such as radical polymerization, anionic polymerization or cationic polymerization, and may be suspension polymerization, solution polymerization or bulk polymerization.

When radical polymerization is carried out, a radical initiator such as azobisisobutyronitrile or benzoyl peroxide can be used as a polymerization catalyst.

When performing cationic polymerization, Lewis acids such as BF ₃ and BF ₆ can be used as a polymerization catalyst.

In the anionic polymerization, specifically, an organic alkali metal compound can be used as a polymerization catalyst in an organic solvent. A Lewis base is added to obtain a polymer having a narrow molecular weight distribution for the purpose of ensuring mechanical strength and heat resistance.

Examples of the organic alkali metal compound in the case of performing anionic polymerization include monoorganolithium compounds such as n-butyllithium and sec-butyllithium; polyfunctional organolithium compounds such as dilithiomethane and 1,4-dilithiobutane; sodium naphthalene. , Potassium naphthalene, and the like. Among these, organolithium compounds are preferable. The amount of organic alkali metal compound used is
The amount is usually 0.05 to 100 mmol, preferably 0.1 to 50 mmol, per 100 parts by weight of the monomer.

As the Lewis base, diethyl ether,
Examples thereof include ether compounds such as dibutyl ether; tertiary amine compounds such as triethylamine and pyridine; alkali metal alkoxide compounds; phosphine compounds. Of these, ether compounds are particularly preferable because they produce a polymer having a narrow molecular weight distribution and do not adversely affect the hydrogenation reaction in the next step.

The polymerization temperature is usually -70 to 150 ° C, preferably -50 to 120 ° C. The polymerization time is usually 0.
It is 01 to 20 hours, preferably 0.1 to 10 hours.

(3) Cyclic Conjugated Diene Polymer As the cyclic conjugated diene polymer, a cycloconjugated diene monomer such as cyclopentadiene or cyclohexadiene can be prepared, for example, from JP-A-6-136057 and JP-A-7-.
According to the method taught in Japanese Patent No. 258318, 1,2-
Alternatively, a polymer obtained by 1,4-addition polymerization can be used.

In the method of the present invention, when the hydrogenation reaction of the polymer is continuously carried out after the polymerization reaction, if the polymerization reaction is carried out by so-called solution polymerization in which the polymerization is carried out in an organic solvent, the steps of polymerization and hydrogenation are carried out. It is convenient to carry out continuously.

The organic solvent is preferably a hydrocarbon solvent, which does not impair the polymerization catalyst, and includes, for example, aliphatic hydrocarbons such as n-pentane, n-hexane and isooctane; alicyclic compounds such as cyclopentane and cyclohexane. Hydrocarbons; aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran and dioxane. The amount of the organic solvent used is usually the monomer concentration,
The amount is 1 to 40% by weight, preferably 10 to 30% by weight.

The polymerization reaction is stopped when the polymerization conversion rate becomes high and almost no monomer is present, but a deactivator for the polymerization catalyst may be added for the purpose of preventing gelation of the solution after the polymerization reaction. . Examples of the polymerization catalyst deactivator include water; alcohols such as methanol and ethanol; carboxylic acids such as formic acid and acetic acid; and phenols such as phenol and cresol.

The molecular weight of the alicyclic structure-containing polymer to which the method of the present invention is applicable is appropriately selected according to the purpose of use.
Polyisoprene-equivalent weight average molecular weight measured by gel permeation chromatography using cyclohexane as a solvent (toluene solvent when the polymer does not dissolve), usually 5,000 to 500,000, preferably 8,000. ~ 200,000, more preferably 10,
It is in the range of 000 to 100,000. By setting the molecular weight of the alicyclic structure-containing polymer in the above range, the mechanical strength and molding processability of the molded article are highly balanced with oil resistance,
It is suitable. The glass transition temperature (Tg) of the alicyclic structure-containing polymer to which the production method of the present invention can be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C, preferably 60 to 200 ° C, and more preferably It is 70 to 150 ° C.

In the method of the present invention, the carbon-carbon double bond in the alicyclic structure-containing polymer is hydrogenated using the above heterogeneous hydrogenation catalyst. Here, the carbon-carbon double bond in the alicyclic structure-containing polymer means a non-conjugated double bond and / or an aromatic double bond in the main chain and / or the side chain.

The hydrogenation reaction occurs by bringing the alicyclic structure-containing polymer and hydrogen into contact with each other in the presence of a hydrogenation catalyst. Hydrogen pressure is the gauge pressure in the reactor, usually 0.1M
Pa to 30 MPa, preferably 1 MPa to 20 MPa,
It is more preferably set to 2 MPa to 10 MPa.

Hydrogenation is usually carried out by dissolving the alicyclic structure-containing polymer in an organic solvent. Examples of the organic solvent in the hydrogenation of these alicyclic structure-containing polymers include aliphatic hydrocarbons such as n-pentane, n-hexane and isooctane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; benzene, toluene and the like. Aromatic hydrocarbons; ethers such as tetrahydrofuran and dioxane; and the like. The amount of the organic solvent used is usually such that the concentration of the alicyclic structure-containing polymer becomes 1 to 30% by weight.

The temperature condition for the hydrogenation reaction is usually 10 to 2
Although it is 50 ° C., it is preferably 5 for the reason that the hydrogenation rate can be increased and the polymer chain cleavage reaction can be reduced.
The temperature is 0 to 200 ° C, more preferably 80 to 180 ° C.
The hydrogenation reaction time is usually 1 to 20 hours.

In the method of the present invention, in the hydrogenation reaction, (1) a hydrogenation catalyst is directly added to the polymer solution,
A method of stirring and mixing in a reactor to introduce hydrogen (so-called suspension reaction method), and (2) a method of passing a polymer solution and hydrogen through a fixed bed reactor filled with a hydrogenation catalyst (so-called fixed) Any of the bed reaction methods) can be used.

The hydrogenation rate of the alicyclic structure-containing polymer hydrogenated product is preferably 95% or more, more preferably 99% or more, particularly preferably 99.% or more, from the viewpoint of suppressing birefringence and improving light deterioration resistance. It is 5% or more. If the hydrogenation rate is too small, the birefringence may not be sufficiently reduced. The hydrogenation rate can be determined by ¹ H-NMR.

When the alicyclic structure-containing polymer has an aromatic ring, the residual rate of the aromatic ring is preferably 80% or less, more preferably 50% or less, and particularly preferably 30% or less, from the viewpoint of light resistance and the like. . The hydrogenation rate of the non-conjugated unsaturated bond is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. If the hydrogenation rate is low, oxidative deterioration and molecular cleavage are likely to occur, resulting in poor color tone, low transparency, and low mechanical strength.

When the alicyclic structure-containing polymer has a repeating unit having an aromatic ring, the aromatic ring structure can be left in the hydrogenation reaction, but it may be completely hydrogenated. Absent. The unsaturated bond of the aromatic ring can be recognized separately from other unsaturated bonds by ¹ H-NMR analysis.

In the method of the present invention, the hydrogenation catalyst is removed from the obtained solution containing the hydrogenated product. The method of removing the catalyst is not particularly limited, and examples thereof include a method of separating and recovering from the solution after the hydrogenation reaction by filtration or centrifugation.

The filtration is carried out by using a suitable filter, preferably by applying pressure or reducing pressure, to create a differential pressure between the in-side and the out-side of the reaction solution.

Examples of the filter include a paper filter, a synthetic resin filter, a fiber (cloth) filter, a metal filter, and the like, and the cloth filter is preferable in terms of strength and repeated use.

As a method of applying a differential pressure, a method of pressurizing the inside side, a method of depressurizing the outside side, or a combination thereof can be considered, but a method of pressurizing the inside side is preferable because of its simple structure.

As a method for pressurizing, the reaction solution itself is pressurized by a pump or the like to be fed and passed through a filter, or the reaction solution is put in a pressurizing vessel and pressurized gas such as compressed air or compressed nitrogen is used. There is a method of applying pressure.

The differential pressure during filtration is not particularly limited, but is usually 0.01 to 2 MPa in gauge pressure, preferably 0.02 to 1.5 MP from the viewpoint of filtration efficiency and device simplicity.
a, particularly preferably 0.05 to 1 MPa. When the hydrogenation catalyst to be filtered during filtration is likely to cause clogging of the filter, it is also preferable to deposit a filter aid on the inside of the filter in advance.

As the filter aid, diatomaceous earth, silica,
Inert powders such as synthetic zeolite, perlite, and radiolite that are insoluble in solvents are suitable.

In the method of the present invention, the solution containing the hydrogenated product after removing the hydrogenation catalyst may be filtered with a mechanical filter or a filter having a charge trapping function. For the method of filtering with a filter, see JP-A-10-
It can be carried out by the method described in Japanese Patent No. 60048.

After removing the hydrogenation catalyst, volatile components such as an organic solvent in the hydrogenated product are removed and the alicyclic structure-containing polymer hydrogenated product is recovered.

As a method for removing the volatile components, known methods such as a coagulation method and a direct drying method can be adopted. The coagulation method is a method of precipitating the hydrogenated product by mixing the solution after filtration with the poor solvent of the alicyclic structure-containing polymer hydrogenated product, and the type of the poor solvent changes depending on the type of the polymer. Examples include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol or isopropyl alcohol; ketones such as acetone or methyl ethyl ketone; esters such as ethyl acetate or butyl acetate. The component containing the powdery alicyclic structure-containing polymer hydrogenated product obtained by coagulation is dried by heating, for example, in vacuum or in nitrogen or air, and further extruded from a melt extruder as necessary. It is preferably used in the form of pellets.

The direct drying method is a method of heating the solution under reduced pressure to remove the solvent. This method can be performed using a known device such as a centrifugal thin film continuous evaporation dryer, a scraped surface heat exchange type continuous reactor type dryer, and a high viscosity reactor device. The degree of vacuum and the temperature are appropriately selected depending on the device and are not limited.

When removing volatile components, additives such as antioxidants, light stabilizers, and ultraviolet absorbers may be added, if necessary. That is, these additives can be uniformly dissolved in the polymer solution before the removal of the volatile components before the removal of the volatile components.

The hydrogenated product of an alicyclic structure-containing polymer of the present invention has a content of foreign matters having a particle size of 0.5 μm or more of 500 /
g or less, preferably 300 / g or less, particularly preferably 200 / g or less. Further, the content of foreign matter having a particle size of 0.2 μm or more and less than 0.5 μm is preferably 5,000.
It is 0 / g or less. Here, the foreign substance means a substance which is not compatibilized with the alicyclic structure-containing polymer such as impurities mixed in from the outside and catalyst residue, gelation product, and side reaction product. Particle size 0.5 μm or more and particle size 0.2 μm or more 0.5
The content of foreign matter of less than μm is a value measured by using a light scattering type fine particle detector in an organic solvent solution having a concentration of the alicyclic structure-containing polymer of 1.5% by weight. The shape of the foreign matter is usually granular, but is not limited thereto.

The alicyclic structure-containing polymer hydrogenated product of the present invention has a glass transition temperature (Tg) of usually 80 to 300 ° C., preferably 100 to 280 ° C., more preferably 120 to 2
It is in the range of 50 ° C., and the weight average molecular weight (Mw) according to the polyisoprene conversion value measured by gel permeation chromatography (GPC) is usually 5,000 to.
500,000, preferably 8,000-200,000
The range is 0, more preferably 10,000 to 100,000. By setting the weight average molecular weight (Mw) within the above range, various properties such as strength properties, moldability, and birefringence can be highly balanced. The molecular weight distribution (Mw / Mn) is usually 5.0 or less, preferably 4.0.
Or less, more preferably 3.0 or less, particularly preferably 2.
It is 0 or less.

The hydrogenated product of the alicyclic structure-containing polymer of the present invention is subjected to gel permeation chromatography (GP
The molecular weight measured in C) is 1000 in terms of polyisoprene.
The content of the following components is preferably 1% by weight or less. By setting the content of the component having a molecular weight of 1000 or less to 1% by weight or less, mechanical strength and heat resistance can be highly improved.

The hydrogenated product of the alicyclic structure-containing polymer of the present invention has transparency, low water absorption, moldability, mechanical strength, chemical resistance, heat resistance, etc. Therefore, it is particularly suitable for optical materials such as plastic lenses and optical disks. In order to obtain such a molded product, a compounding agent usually compounded in the thermoplastic resin material can be added as necessary without particular limitation. Such compounding agents include, for example, antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, antistatic agents, optical brighteners, and hardeners. Compounding agents such as a flame retardant and an anti-blocking agent may be mentioned.

The method of blending the above-mentioned compounding agent with the alicyclic structure-containing polymer hydrogenated product is, for example, a mixer, a twin-screw kneader, a roll, a Brabender, an extruder, etc. Examples thereof include a method in which the product is melted and kneaded with a compounding agent, and a method in which the product is dissolved and dispersed in an appropriate solvent to be solidified. When a twin-screw kneader is used, it is usually used after being kneaded, extruded in a molten state into a strand, and cut into pellets with a pelletizer.

The molding method is not particularly limited, but it is preferable to use the melt molding method in order to obtain a molded article excellent in low birefringence, mechanical strength and dimensional accuracy. Examples of the melt molding method include an injection molding method, an extrusion molding method, a press molding method and a blow molding method, and the injection molding method is preferable from the viewpoint of low birefringence and dimensional stability.

[0068]

EXAMPLES The present invention will be described in more detail below with reference to polymerization examples, examples and comparative examples, but the present invention is not limited thereto. Parts and% are based on weight unless otherwise specified. The methods for measuring various physical properties in the polymerization examples, examples and comparative examples are as follows.

(Particle size of hydrogenation catalyst) The particle size and particle size distribution of the hydrogenation catalyst are determined as follows. A dispersion of the hydrogenation catalyst in ion-exchanged water or cyclohexane was measured using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, product name "SALD-2000") with a refractive index of 1.60-0.20i. Measure under the conditions.

(Content of Transition Metal in Hydrogenation Catalyst) The content of transition metal in the hydrogenation catalyst is measured by a fluorescent X-ray analyzer.

(Molecular weight) The molecular weight is the polyisoprene conversion value by gel permeation chromatography (GPC) using cyclohexane as a solvent or the polystyrene conversion value by gel permeation chromatography (GPC) using toluene as a solvent. Measure as a value.

(Hydrogenation rate) The hydrogenation rate is ¹ H-NM
Measured by R.

(Particle size 0.5 μm or more and particle size 0.2 μm
(Amount of foreign matter of 0.5 μm or less) A solution having a concentration of 1.5% by dissolving a hydrogenated substance of an alicyclic structure-containing polymer in purified tetralin, and a light scattering type fine particle detector (manufactured by Lion Corporation, product name “KL -28B ") is used to measure the amount of foreign matter having a particle size of 0.5 μm or more and 0.2 μm or more and less than 0.5 μm.

Polymerization Example 1 400 parts of a solvent cyclohexane, 0.15 part of dibutyl ether and 0.3 part of triisobutylaluminum were added to a reactor equipped with a magnetic stirrer substituted with nitrogen, and the mixture was placed under a nitrogen atmosphere at 45 ° C. 8-methyl-tetracyclo [4.4.0.1 ^2,5
． 1 ^7,10 ] -dodeca-3-ene (also known as MTD) 1
Polymerization was carried out by adding 00 parts and 40 parts of a 0.7 wt% toluene solution of tungsten hexachloride over 2 hours. Next, 1.06 parts of butyl glycidyl ether and 0.52 parts of isopropyl alcohol were added to inactivate the polymerization catalyst, and the polymerization reaction was stopped to obtain a polymer solution. The molecular weight of the alicyclic structure-containing polymer in the obtained polymer solution was 20,000 in terms of weight average molecular weight Mw. Since the peak of the unreacted monomer was not detected by the analysis of this reaction solution by gas chromatography, the polymerization conversion rate was 1
It was confirmed to be 00%.

Example 1 The solution of the alicyclic structure-containing polymer obtained in Production Example 1 was transferred to a pressure resistant reaction vessel equipped with a stirrer, and 30 parts of cyclohexane was added. Then, in the reactor, as a heterogeneous hydrogenation catalyst, an average particle size of 12 μm,
2 parts of a nickel-supported diatomaceous earth hydrogenation catalyst having a particle size of 1 μm or less with a content of 0% by volume, a specific surface area of 170 m ² / g, and a nickel content of 50%, and diatomaceous earth (Radiolite # 5).
00, average particle diameter 13 μm, manufactured by Showa Chemical Industry Co., Ltd.) 2
What was prepared by thoroughly mixing the parts with a nitrogen atmosphere was added. Then, the inside of the reactor was replaced with hydrogen gas, hydrogen was supplied at 160 ° C. with stirring, and the hydrogen pressure was 5.4 MPa.
The hydrogenation reaction was carried out for 4 hours to obtain a solution containing an alicyclic structure-containing polymer hydrogenated product. This solution was subjected to pressure filtration (Funda filter, manufactured by Ishikawajima Harima Heavy Industries, Ltd.) using Radiolite # 500 as a filter bed, and the pressure was 0.25M.
A colorless transparent solution I was obtained by pressure filtration with Pa (differential pressure 0.15 MPa). The amount of foreign matter of 0.5 μm or more in the hydrogenated polymer at this stage was 700 / g.

The above solution I was further filtered through a metal fiber filter (caliber 3 μm, manufactured by Nichidai Co.) and then further filtered by a metal fiber filter (caliber 0.2 μm, manufactured by Nichidai Co.) to obtain solution II. Obtained. Solution II was used to remove cyclohexane, which is a solvent component, by a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.). First step: Temperature 280
C., system pressure 13 kPa, second stage: temperature 280.degree. C., system pressure 0.7 kPa. In a class 1000 clean room, a molten alicyclic structure-containing polymer hydrogenated product was extruded from a die, cooled with water, and then cut with a pelletizer (OSP-2, manufactured by Nagata Manufacturing Co., Ltd.) to obtain 18 parts of pellets. The obtained pellet was made into a 1.5% concentration solution using tetralin filtered and purified with a 0.2 μm cartridge filter, and a light scattering type particle detector (manufactured by Rion Co., product name “KL-28B”) was used. As a result of measuring the amount of foreign particles having a particle size of 0.5 μm or more and 0.2 μm or more and less than 0.5 μm, the amount of foreign particles having a particle size of 0.5 μm or more is 100 particles / g, and the particle size is 0.2 μm or more and less than 0.5 μm. The amount of foreign matter was 4,000 / g. Further, this hydrogenated product of alicyclic structure-containing polymer has a weight average molecular weight (Mw) of 3
8,000, content of less than 1000 molecular weight is 0.5%,
Hydrogenation rate is 99.9%, glass transition temperature is 134 ° C,
Mw / Mn was 2.0.

(Comparative Example 1) In Example 1, as the heterogeneous hydrogenation catalyst, the average particle diameter was 11 μm and the particle diameter was 1 μm.
The content of the following is 3.4% by volume and the specific surface area is 116 m
^An alicyclic structure-containing polymer hydrogenated product was obtained in the same manner except that a nickel-supported diatomaceous earth hydrogenation catalyst having a nickel content of ² / g and a nickel content of 38% was used. Here, the amount of foreign matter of 0.5 μm or more in the hydrogenated product before passing through the filter was 10,000 particles / g. Further, as a result of measuring the amount of foreign matter having a particle size of 0.5 μm or more and a particle size of 0.2 μm or more and less than 0.5 μm, the obtained hydrogenated product of alicyclic structure-containing polymer was found to have a particle size of 0.5 μm.
The amount of foreign matter of m or more was 1,500 pieces / g, and the amount of foreign matter having a particle size of 0.2 μm or more and less than 0.5 μm was 20,000 pieces / g. The alicyclic structure-containing polymer has a weight average molecular weight (Mw) of 38,000 and a weight average molecular weight (Mw) of 100.
The content of 0 or less is 0.5%, the hydrogenation rate is 99.0%,
The glass transition temperature was 134 ° C. and Mw / Mn was 2.0.

The following can be seen from the above results. As in Example 1, the carbon-carbon double bond in the alicyclic structure-containing polymer was obtained by supporting a transition metal of Groups 8 to 10 of the periodic table on a carrier, and the content of particles having a particle size of 1 μm or less was obtained. 1% by volume
When hydrogenated below using a heterogeneous hydrogenation catalyst having a specific surface area of 50 to 300 m ² / g, the amount of minute foreign matter is extremely small (the amount of foreign matter having a particle size of 0.5 μm or more is 500).
The number of foreign matter having a number of particles / g or less and a particle diameter of 0.2 μm or more and less than 0.5 μm is 5000 pieces / g or less. On the other hand, when hydrogenation is performed using a heterogeneous hydrogenation catalyst in which the content of particles having a particle diameter of 1 μm or less is larger than 1% by volume as in Comparative Example 1, the amount of minute foreign matter after removal of the hydrogenation catalyst is large, and The amount of minute foreign substances in the hydrogenated product obtained in a large amount is also large.

[0079]

According to the production method of the present invention, it is possible to efficiently obtain an alicyclic structure-containing polymer hydrogenated product having a small amount of fine foreign matter (foreign matter of 0.2 μm or more). The alicyclic structure-containing polymer hydrogenated product of the present invention has transparency, low water absorption, moldability, mechanical strength, chemical resistance, heat resistance, and the like, and in addition, the content of fine foreign matters having a particle size of 0.5 μm or more. Since it is less than 500 pieces / g, such as optical disc substrates, optical lenses, magnetic disc substrates, liquid crystal display materials, medical equipment, packaging materials, packing, gaskets, sealing materials, piping materials (flange, elbow, pipe, etc.) It is suitable as a material in many fields, and particularly suitable for optical disk substrates, optical lenses, magnetic disk substrates, and the like.

Continued front page    F-term (reference) 4J100 AB02P AB03P AR11P AR21P                       AR22P AS01P AS15P BC02H                       BC03H BC04H BC07H BC08H                       BC22P BC23P CA01 HA04                       HA05 HB06 HB29 HB36 HB44                       HB52 HB61 HC83 HC84 HD22                       HE14 JA32 JA33 JA36 JA43                       JA50 JA58 JA67

Claims (6)

[Claims] 1. A heterogeneous hydrogenation catalyst in which a transition metal of Group 8 to 10 of the periodic table is supported on a carrier, having a particle diameter of 1 μm.
Using a heterogeneous hydrogenation catalyst having a content of m or less of 1 vol% or less and a specific surface area of 50 to 300 m ² / g, a norbornene-based polymer, a vinyl cyclic hydrocarbon-based polymer, and a cyclic The carbon-carbon double bond in the alicyclic structure-containing polymer selected from the group consisting of conjugated diene-based polymers is hydrogenated to obtain an alicyclic structure-containing polymer hydrogenated product, and then the hydrogenation catalyst is removed. A method for producing a hydrogenated product of an alicyclic structure-containing polymer, which comprises a step. 2. The periodic table Nos. 8 to 10 in the hydrogenation catalyst.
The method according to claim 1, wherein the amount of the group transition metal supported is 40% by weight or more. 3. The periodic table Nos. 8 to 10 in the hydrogenation catalyst.
The method of claim 1, wherein the group transition metal is nickel. 4. In the hydrogenation, an inorganic compound having at least one element selected from the group consisting of silicon, aluminum and magnesium is added in a weight ratio of 10/90 to 90/10 with respect to the hydrogenation catalyst. The method according to claim 1, which is used as a mixture. 5. A hydrogenated product containing an alicyclic structure-containing polymer, wherein the content of foreign matters having a particle size of 0.5 μm or more is 500 particles / g or less. 6. The alicyclic structure-containing polymer hydrogenated product according to claim 5, wherein the content of foreign matters having a particle size of 0.2 μm or more and less than 0.5 μm is 5000 particles / g or less.