JP2002003524A - Method for producing aromatic vinyl polymer hydrogenation product or cycloalkene vinyl polymer hydrogenation product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic vinyl polymer hydrogenation product or a cycloalkene vinyl polymer hydrogenation product whereby the utilities of hydrogenation catalyst and filtration auxiliary are increased, the waste is abolished and the productivity is improved. SOLUTION: The method, wherein the aromatic vinyl polymer or cycloalkene vinyl polymer is subjected to a hydrogenation reaction in the presence of hydrogenation catalyst obtain the aromatic vinyl polymer hydrogenation product or the cycloalkene vinyl polymer hydrogenation product, is characterized in that the reaction is carried out by adding the hydrogenation catalyst and the filtration auxiliary which are filtered and recovered from reaction solution after the reaction when the aromatic vinyl polymer or cycloalkene vinyl polymer is subjected to another hydrogenation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer. More specifically, the present invention relates to a method for increasing the utilization of a hydrogenation catalyst and a filter aid to reduce waste. The present invention relates to a method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer which has improved productivity.

[0002]

2. Description of the Related Art As a plastic material used for molding optical materials such as lenses and optical disks, polymers should have transparency, low water absorption, moldability, mechanical strength, chemical resistance, and heat resistance. In addition to the above, small birefringence can be mentioned. Although polystyrene is an excellent material having most of these properties, it has a disadvantage that birefringence tends to occur.

[0003] Birefringence is a phenomenon in which incident light is refracted in two or more directions at a boundary surface due to the optical anisotropy of a material. The optical anisotropy of a polymer mainly depends on the magnitude of the main polarizability difference between repeating units of the molecular structure. A benzene ring, a cyclopentene ring or the like has a large difference in polarizability between the planar direction and the vertical direction of the ring. Therefore, a polymer of a vinyl monomer having an unsaturated ring as a substituent easily causes birefringence.

As countermeasures against this, Japanese Patent Application Laid-Open Nos. 1-1706, 1-132603, 4-750 have been proposed.
No. 01 and the like disclose attempts to reduce the polarizability difference by hydrogenating a benzene ring to polystyrene in the presence of a hydrogenation catalyst. JP-A-63-43910 discloses a light transmittance of 85% containing 80 to 100% by weight of a vinylcyclohexane-based polymer and 0 to 20% by weight of a vinyl-aromatic polymer.
Above, water absorption of 0.1% by weight or less, and birefringence of 50 nm
An optical disk substrate made of the following amorphous thermoplastic resin is disclosed. The publication teaches hydrogenating a vinyl aromatic polymer as a method for producing a vinyl cyclohexane polymer. By hydrogenation of these aromatic rings,
The birefringence of the styrenic polymer can be reduced sufficiently.

[0005] However, these disclosed technologies require an enormous amount of time for filtering off the hydrogenation catalyst after the hydrogenation reaction,
There is a problem in industrial implementation because the hydrogenation catalyst is used in a large amount for each reaction, increasing the cost and wasting resources.

[0006]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention relates to a method for industrially performing a hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer, which is effective for the filtration of a hydrogenation catalyst by filtration. And to increase the utilization of the hydrogenation catalyst and the filter aid.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the hydrogenation catalyst has been filtered and recovered from the reaction solution after the hydrogenation reaction, and recovered by another hydrogenation reaction. By recycling, and by reusing the recovered hydrogenation catalyst with the filter aid used for speeding up the filtration being mixed, the aromatic vinyl polymer or cycloalkene vinyl polymer can be reused. It has been found that the catalyst consumption per product of the hydrogenation reaction can be reduced, and furthermore, the productivity of the hydrogenation reaction step and the filtration step is significantly improved, and based on this finding, the present invention has been completed. Was.

Thus, the present invention provides (1) a hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer by performing a hydrogenation reaction on an aromatic vinyl polymer or a cycloalkene vinyl polymer in the presence of a hydrogenation catalyst. In a method for producing a polymer hydrogenated product, a hydrogenation catalyst and a filter aid collected by filtration from a reaction solution after the hydrogenation reaction are used for another hydrogenation reaction of an aromatic vinyl polymer or a cycloalkenevinyl polymer. A method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer, characterized by performing a hydrogenation reaction by adding
And (2) in addition to the addition of the recovered hydrogenation catalyst and the filter aid during another hydrogenation reaction of the aromatic vinyl polymer or cycloalkenevinyl polymer, a new hydrogenation catalyst and / or a new It is intended to provide a method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer according to the above (1), characterized by adding a filter aid.

In a preferred embodiment, (3) prior to the hydrogenation reaction, the polymerization catalyst residue is removed from the organic solvent solution of the aromatic vinyl polymer or cycloalkene vinyl polymer after the anionic polymerization reaction. A method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer according to the above (1) or (2).

In the method of the present invention, the hydrogenation catalyst used in the hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer is separated by filtration and reused. Suspending the agent,
The basic element is that a filter aid is mixed in the recovered hydrogenation catalyst.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(Aromatic vinyl polymer or cycloalkene vinyl polymer) The aromatic vinyl polymer or cycloalkene vinyl polymer used in the present invention is a polymer of an aromatic vinyl compound or a cycloalkene vinyl compound alone, Alternatively, it is a copolymer of 50% by weight or more of an aromatic vinyl compound or a cycloalkene vinyl compound and 50% by weight or less of a monomer copolymerizable therewith.

The aromatic vinyl compound is not particularly limited as long as it has an aromatic ring and a polymerizable vinyl group. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α
-Propylstyrene, α-isopropylstyrene, α-
t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methyl Examples thereof include styrene, monochlorostyrene, dichlorostyrene, and monofluorostyrene. Among these, styrene, α-methylstyrene, α-ethylstyrene, α
-Propylstyrene, α-isopropylstyrene, α-
t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methyl Styrene is preferable, and styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, -T
-Butylstyrene and the like are particularly preferred.

The cycloalkene vinyl compound is not particularly limited as long as it is a compound having an aliphatic ring having 5 to 8 carbon atoms having a double bond and having a polymerizable vinyl group. The aliphatic ring may have an alkyl group having 1 to 4 carbon atoms or a halogen atom group as a substituent.

Examples of cycloalkene vinyl compounds include cyclopentene vinyl compounds such as 2-vinylcyclopentene, 2-methyl-4-vinylpentene, 3-vinylcyclopentene, and 3-t-butyl-4-vinylpentene; Cyclohexene, 4-isopropenylvinylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylvinylcyclohexene, 2-methyl-4-vinylcyclohexene,
Cyclohexene vinyl compounds such as 2-methyl-4-isopropenylvinylcyclohexene; 2-vinylcycloheptene, 3-vinylcycloheptene, 4-vinylcycloheptene, 3-methyl-6-vinylcycloheptene;
Cycloheptene vinyl compounds such as 4-ethyl-6-vinylcycloheptene and 3-t-butyl-5-vinylcycloheptene; 2-vinylcyclooctene; 3-vinylcyclooctene; 4-vinylcyclooctene; And cyclooctene vinyl compounds such as -methyl-5-vinylcyclooctene, 4-ethyl-6-vinylcyclooctene, and 3-t-butyl-7-vinylcyclooctene. Among these, a cyclopentene vinyl compound and a cyclohexene vinyl compound are preferable, and a cyclohexene vinyl compound is particularly preferable.

Of these compounds, aromatic vinyl compounds, cyclopentene vinyl compounds and cyclohexene vinyl compounds are preferred, and aromatic vinyl compounds and cyclohexene vinyl compounds are more preferred. They are,
Each can be used alone or in combination of two or more.

In the present invention, the aromatic vinyl polymer or cycloalkene vinyl polymer may be a copolymer with a monomer copolymerizable within a range where the repeating unit in the polymer is 50% by weight or less. good. The copolymerizable monomer is not particularly limited as long as it can be copolymerized by a polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization.

Examples of monomers (comonomers) copolymerizable with the aromatic vinyl compound or the cycloalkene vinyl compound include ethylene propylene, isobutene, 2-methyl-1-butene, and 2-methyl-1-pentene. Α-olefin monomers such as 1,4-methyl-1-pentene; cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethyl Cyclopentadiene-based monomers such as cyclopentadiene; cyclobutene, cyclopentene, cyclohexene,
Cyclic olefin monomers such as dicyclopentadiene;
Conjugated diene monomers such as butadiene, isoprene, 1,3-pentadiene, furan, thiophene and 1,3-hexadiene; acrylonitrile, methacrylonitrile,
nitrile monomers such as α-chloroacrylonitrile;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate,
Acrylate monomers such as ethyl acrylate, propyl acrylate and butyl acrylate; acrylic acid,
Unsaturated fatty acid monomers such as methacrylic acid and maleic anhydride; phenylmaleimide; cyclic ether monomers such as ethylene oxide, propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran Heterocyclic ring-containing vinyl compound monomers such as methyl vinyl ether, N-vinyl carbazole and N-vinyl-2-pyrrolidone.

The polymerization reaction for producing the aromatic vinyl polymer or cycloalkene vinyl polymer may be any of known methods such as radical polymerization, anionic polymerization and cationic polymerization, and may be suspension polymerization, solution polymerization or the like. And bulk polymerization.

When performing radical polymerization, a radical initiator such as azobisisobutyronitrile and benzoyl peroxide can be used as a polymerization catalyst. When performing cationic polymerization, BF ₃ and BF ₆ are used as polymerization catalysts.
Etc. can be used.

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

When a hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer is carried out after the polymerization reaction of the aromatic vinyl or cycloalkene vinyl, the polymerization reaction is carried out by solution polymerization in which the polymerization is carried out in an organic solvent. It is convenient to carry out the steps continuously. In order to obtain a polymer having a narrower molecular weight distribution as a polymer having a smaller birefringence, anionic polymerization is preferable.

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

The organic solvent is preferably a hydrocarbon solvent and does not harm the polymerization catalyst. Examples thereof include n-butane, n-pentane, isopentane, n-hexane, and n-hexane.
Aliphatic hydrocarbons such as heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran and dioxane. Among them, aliphatic hydrocarbons and alicyclic hydrocarbons are preferable because they can be used as a solvent for a hydrogenation reaction after the polymerization reaction. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is such that the monomer concentration is usually 1 to 40% by weight, preferably 10 to 30% by weight.

Examples of the organic alkali metal include n-butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium. Monoorganic lithium compounds such as phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-
Polyfunctional organic lithium compounds such as ethylcyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Of these, organolithium compounds are preferred, and monoorganic lithium is particularly preferred. These organic alkali metals are
They can be used alone or in combination of two or more. The amount of the organic alkali metal used is generally 0.05 to 100 mmol, preferably 0.10 to 50 mmol, more preferably 0.15 to 100 parts by weight of the monomer.
20 mmol.

As the Lewis base, diethyl ether,
Ether compounds such as dibutyl ether, methyl ethyl ether, dibenzyl ether and tetrahydrofuran:
Tertiary amine compounds such as tetramethylethylenediamine, triethylamine and pyridine; alkyl metal alkoxide compounds such as potassium-t-amyloxide and potassium-t-butyloxide; and phosphine compounds such as triphenylphosphine. Of these, ether compounds are particularly preferred because they form polymers having a narrow molecular weight distribution and do not adversely affect the hydrogenation reaction in the next step. These Lewis bases are compounds alone,
Alternatively, two or more kinds can be used in combination. The amount of the Lewis base compound to be used is generally from 0.001 to 10.0 mmol, preferably from 0.01 to 5.0 mmol, more preferably from 0.1 to 5.0 mmol, based on the organic alkali metal.
2.0 mmol.

The polymerization reaction may be either isothermal or adiabatic, usually at -70 to 150 ° C, preferably at -50 to 12 ° C.
Perform at 0 ° C. The polymerization time is usually 0.01 to 20 hours,
Preferably it is 0.1 to 10 hours.

The polymerization reaction is stopped when the polymerization addition rate is high and the monomer is almost gone, but an inactivating agent for the polymerization catalyst may be added for the purpose of preventing the solution after the polymerization reaction from gelling. . As the deactivator of the polymerization catalyst, water; alcohols such as methanol, ethanol, isopropyl alcohol, 1,2-butanediol, and glycerin; formic acid;
Carboxylic acids such as acetic acid, citric acid and phthalic acid; phenols such as phenol and cresol;

After the polymerization reaction, an aromatic vinyl polymer or a cycloalkene vinyl polymer is separated and recovered from the polymerization reaction solution and dissolved in a new solvent to prepare a solution of the aromatic vinyl polymer or the cycloalkene vinyl polymer. The hydrogenation reaction may be performed again, but it is preferable to use the same solvent for the solution polymerization as the solvent for the hydrogenation reaction because the polymer can be transferred to the hydrogenation reaction without separation and recovery after polymerization. When the polymerization reaction is an anion polymerization solution polymerization, there is an advantage that the polymerization reaction can be directly transferred to the hydrogenation reaction, and an advantage that the polymerization catalyst can be removed before the hydrogenation reaction is started to improve the hydrogenation reaction rate. There is. As a method of removing the polymerization catalyst after the solution polymerization reaction, a method of adding an adsorbent such as activated alumina, stirring and adsorbing the mixture under heating, and filtering the mixture, and adding a small amount of isopropyl alcohol or the like to remove the polymerization catalyst There is a method of precipitating and filtering off.

(Hydrogenation reaction) In the present invention, the aromatic vinyl polymer or cycloalkene vinyl polymer is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst. The method of the hydrogenation reaction of the aromatic vinyl polymer or cycloalkene vinyl polymer is not particularly limited, and can be performed according to a conventional method.

The hydrogenation catalyst contains at least one element selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium and rhenium. Among these, the nickel catalyst has a narrow molecular weight distribution, that is, the weight average molecular weight / number average molecular weight ratio M
This is preferred because it gives a polymer hydrogenated product with w / Mn close to 1. The hydrogenation catalyst may be either a heterogeneous catalyst or a homogeneous catalyst. The heterogeneous catalyst can be used as it is as a metal or a metal compound, or supported on a carrier.

As the carrier, activated carbon, diatomaceous earth, magnesia, silica, alumina, silica-magnesia, silica-zirconia, diatomaceous earth-zirconia, alumina-
Zirconia and the like can be mentioned. The amount of the metal supported on the support is usually 0.1 to 0.5 per catalyst body comprising the catalyst and the support.
It is from 0.01 to 80% by weight, preferably from 0.05 to 60% by weight.

As the homogeneous catalyst, a catalyst obtained by combining a metal compound such as nickel, cobalt, titanium or iron with an organic metal compound such as organoaluminum or organolithium; an organic catalyst such as rhodium, palladium, ruthenium or rhenium; A metal complex or the like can be used.

As the above-mentioned metal compound, acetylacetone salt, naphthenate, cyclopentadienyl compound, cyclopentadienyldichloro compound and the like of each metal are used. As the organic aluminum, alkyl aluminum such as triethyl aluminum and triisobutyl aluminum; alkyl aluminum halide such as diethyl aluminum chloride and ethyl aluminum dichloride; and alkyl aluminum hydride such as diisobutyl aluminum hydride are used.

As the organometallic complex, the γ-
Examples include a dichloro-π-benzene complex, a dichloro-tris (triphenylphosphine) complex, and a hydride-chloro-tris (triphenylphosphine) complex.

These hydrogenation catalysts can be used alone or in combination of two or more.
The amount of the hydrogenation catalyst used is usually per 100 parts by weight of the aromatic vinyl polymer or cycloalkene vinyl polymer,
It is 0.03 to 50 parts by weight, preferably 0.16 to 33 parts by weight, and more preferably 0.33 to 15 parts by weight. In the present invention, the hydrogenation catalyst is separated by filtration, recovered and reused,
It is not necessary to add a new catalyst in the above range each time the hydrogenation reaction is performed, and it is sufficient that the total of the reused hydrogenation catalyst and the newly replenished hydrogenation catalyst fall within the above range.

As the organic solvent used in the hydrogenation reaction,
In addition to the solvent used in the solution polymerization described above, alcohols may be used. These organic solvents can be used alone or in combination of two or more. The amount of organic solvent used is
The concentration of the aromatic vinyl polymer or cycloalkene vinyl polymer is usually 1 to 50% by weight, preferably 3 to 4% by weight.
The amount is 0% by weight.

The hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer is carried out by introducing hydrogen into a hydrogenation reaction solution. For example, the hydrogenation reaction is carried out while stirring an organic solvent solution of the polymer. Preferred is a method in which the hydrogen is sufficiently contacted with the polymer.

The temperature of the hydrogenation reaction is usually from 10 to 25.
0 ° C, preferably 50-200 ° C, more preferably 80 ° C.
１８０180 ° C. Hydrogen pressure is usually 1 to 30MPa
a, preferably 0.5 to 25 MPa, more preferably 1
２０20 MPa.

(Filtering and Recovery of the Hydrogenation Catalyst) In the method of the present invention, it is necessary to recover the hydrogenation catalyst by filtration from the reaction solution after the hydrogenation reaction of the aromatic vinyl polymer or cycloalkene vinyl polymer. However, a filter aid is added to the reaction solution in order to speed up the filtration.

The filter aid is a chemically inert porous particle used to prevent the material to be filtered from clogging the filter medium. As filter aid, diatomaceous earth,
Inert, solvent-insoluble powders such as silica, synthetic zeolite, perlite, radiolite, etc. are suitable. Examples of the use of the filter aid include a body feed method in which a filter aid is added to a suspension to be filtered in advance, and a precoat method in which a bed of the filter aid is formed in a filter medium and then filtration is performed. Is adopted. According to the body feed method, when the hydrogenation catalyst and the filter aid are repeatedly collected, the amount of the filter aid used does not increase for each reaction batch.

The time for adding the filter aid is such that, for the first hydrogenation reaction of the aromatic vinyl polymer or cycloalkene vinyl polymer, at the latest, the reaction solution is uniformly suspended in the solution before filtration. However, it may be put in a reactor before the hydrogenation reaction.

The amount of the filter aid used is 100 parts of a hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer.
Usually, 0.03 to 50 parts by weight, preferably 0.16 to 33 parts by weight, more preferably 0.33 to 1 part by weight per part by weight.
5 parts by weight. In the present invention, the filter aid is also separated by filtration, recovered and reused. Therefore, it is not necessary to add a new filter aid in the above range every time the hydrogenation reaction is performed, and the filter aid to be reused or a new supplement thereof is added. It is sufficient that the total of the filter aids to be used falls within the above range.

The filtration is carried out by using a suitable filter or strainer, preferably by increasing or decreasing the pressure, by applying a pressure difference between the in side and the out side of the reaction solution, or by centrifugation.

Examples of the filter material include a paper filter, a synthetic resin filter, a cloth filter (filter cloth), and a metal strainer. A cloth filter, a metal strainer, and the like are preferable in terms of strength and repetitive use. .

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

As a method of pressurizing, a method of pressurizing the reaction solution itself with a pump or the like and sending the solution to pass through a filter, a method of putting the reaction solution in a pressurized container, and using a pressurized gas such as compressed air or compressed nitrogen. There is a method of pressing.

The pressure to be applied is not particularly limited, but is usually 0.01 to 2 MPa from the viewpoint of filtration efficiency and simplicity of the apparatus.
, Preferably 0.02 to 1.5 MPa , More preferably 0.05 to 1 MPa.

To collect the filtered hydrogenation catalyst and filter aid, the cake is scraped off from the filter or washed with an organic solvent and collected. At this time, it is preferable to perform the reaction under an atmosphere of an inert gas such as nitrogen so that moisture in the air is not adsorbed by the hydrogenation catalyst and poisoned. The organic solvent is preferably the same as the solvent used for both the polymerization and the hydrogenation.

(Reuse of Hydrogenation Catalyst) The recovered hydrogenation catalyst and filter aid are further added with an organic solvent, if necessary, so as to have a solid concentration that can be easily handled, so as to be in a slurry state capable of stirring and flowing. Is preferred. Such an organic solvent is preferably the same organic solvent as the solvent for both the polymerization and hydrogenation reactions, and the mixture is uniformly stirred and sampled, and the amount of the recovered hydrogenation catalyst per solid content is measured. Although there is no particular limitation on the measuring method, for example, the nickel content in the solid content can be measured by an atomic absorption method. If the process is stabilized, the frequency of measuring the catalyst concentration per solid content can be reduced. Knowing the amount of catalyst per solid, the amount to be added to another hydrogenation reaction can be determined.

In the present invention, in another batch (batch) hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer, the recovered hydrogenation catalyst is mixed with hydrogen in a state in which a filter aid is mixed. Used as an additive catalyst. Although the cause is not clear, the reduction of the hydrogenation rate can be prevented by keeping the filter aid mixed. When the recovery rate of the catalyst or the filter aid is low, if necessary, replenish the reaction with a new hydrogenation catalyst or / and a filter aid in addition to the recovered hydrogenation catalyst and the filter aid. be able to.

In the method of the present invention, after a predetermined amount of a hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer is produced, the hydrogenated catalyst and a filter aid are once separated by filtration to dissolve the hydrogenated product. It is suitable for batch-type (batch-type) hydrogenation product production in which the organic solvent solution is transferred to a hydrogenation product recovery step, and another aromatic vinyl polymer or cycloalkene vinyl polymer is newly hydrogenated. .

(Recovery and Drying of Hydrogenated Product) A solution of a hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer in an organic solvent obtained by filtering off a hydrogenation catalyst and a filter aid may be, for example, a foreign material. The volatile components mainly composed of an organic solvent are removed in a hermetically closed state so as not to be mixed, and collected in a form close to a pure content.

As a method for removing volatile components, a known method such as a coagulation-solid-liquid separation method or a direct drying method can be employed.

The coagulation method is a method in which a hydrogenated solution is mixed with a poor solvent of a hydrogenated aromatic vinyl polymer or a cycloalkene vinyl polymer to precipitate a hydrogenated component. Varies depending on the type of hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer, for example, ethyl alcohol, n-
Examples include polar solvents such as alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate and butyl acetate.

The solid component obtained by coagulation and then solid-liquid separation by filtration, centrifugation or the like is dried, for example, by heating in a vacuum or in nitrogen or air to form a powder, It is preferable to extrude from a melt extruder in the form of a pellet and provide it for molding.

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

The hydrogenation rate of the unsaturated ring of the hydrogenated product of the aromatic vinyl polymer or cycloalkene vinyl polymer thus produced is determined by the vinyl substituent of the aromatic vinyl polymer or cycloalkene vinyl polymer. If 100% is defined as the case where all the double bonds are saturated by hydrogenation, there is a theoretical range of 0 to 100%, and the type and amount of hydrogenation catalyst, hydrogen pressure, reaction temperature, reaction time The concentration can be arbitrarily adjusted by changing the catalyst concentration and the like, but is preferably higher in order to suppress birefringence and improve light degradation resistance, and is usually 95% or more, preferably 99% or more. Preferably, hydrogen is added at 99.5% or more. An excessively low hydrogenation rate is not preferable because birefringence may not be sufficiently reduced. The hydrogenation rate of the unsaturated ring is ¹ H-NM by a conventional method.
It can be determined by the R measurement method.

The molecular weight of the hydrogenated product of the aromatic vinyl polymer or cycloalkene vinyl polymer is not particularly limited, but the weight average in terms of standard polystyrene measured by gel permeation chromatography (GPC) of a tetrahydrofuran solution. The molecular weight (Mw) is usually 10,
000-250,000, preferably 30,000-2
0000, more preferably 50,000 to 170,0
00, particularly preferably in the range of 80,000 to 150,000. In addition, the number average molecular weight (Mn) is also expressed in terms of standard polystyrene. If the weight average molecular weight is too large, the hydrogenation rate may be reduced. Conversely, if the weight average molecular weight is too small, the mechanical strength of the molded article may be deteriorated.

The ratio (Mw / M) between the weight average molecular weight (Mw) and the number average molecular weight (Mn), which is an index of the breadth of the molecular weight distribution, is shown.
n) is usually 2.0 or less, preferably 1.7 or less, more preferably 1.5 or less. If the Mw / Mn value is excessively large, the mechanical strength of the molded product may be reduced, and the glass transition temperature (Tg) may be reduced to deteriorate the heat resistance.

The Tg of the hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer is usually from 60 to 16
0 ° C., preferably 80-150 ° C., more preferably 10 ° C.
0-145 ° C. If the Tg is excessively high, the fluidity of the resin may be reduced during molding, and if it is excessively low, the heat resistance of the molded article may be deteriorated.

(Use of hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer) The hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer obtained according to the present invention has high transparency and low water absorption. It is suitable for optical materials such as plastic lenses and optical disks because it has a characteristic of low birefringence in addition to the properties, moldability, mechanical strength, chemical resistance, heat resistance and the like.

For molding such an optical material, a hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer is an essential component, and if necessary, other resins commonly used for plastic lenses and the like are used. Mix the ingredients.
Other resin components include polymethyl methacrylate, polycarbonate, poly 4-methyl-1 pentene, acrylonitrile-styrene copolymer (AS resin), norbornene ring-containing alicyclic monomer addition polymer, norbornene ring-containing alicycle. Group-opening polymers and the like.

The compounding agents usually used for thermoplastic resin materials can be added without any particular limitation. Examples of such compounding agents include antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, fluorescent brighteners, Examples include compounding agents such as a flame retardant, an anti-blocking agent, and a leveling agent.

The composition of the hydrogenated aromatic vinyl polymer or the hydrogenated cycloalkene vinyl polymer prepared by adding these compounding agents is pelletized by, for example, an extruder and used for processing a molded article. As a method of processing a molded product, for example, as a method of molding a plastic lens or an optical disk, an injection molding method, a press molding method, an extrusion molding method, or the like is applied. In addition, as a method for forming a polarizing film or a retardation film, injection molding, inflation molding, vacuum molding, cast molding, or the like is used.

The hydrogenated aromatic vinyl polymer or hydrogenated cycloalkene vinyl polymer obtained by the present invention is used as various molded articles including the following optical materials.

For example, an optical lens, an optical disk, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror,
Optical materials such as liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquids such as liquid medicine containers, ampules, vials, infusion bags, sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, etc. , Powder or solid drug containers; syringes, prefilled syringes,
Medical instruments and equipment such as medical infusion tubes;
Examples include a liquid crystal substrate and an optical memory.

[0068]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples. Parts and percentages in these examples are by weight unless otherwise specified. In addition, the measuring method of various physical properties is as follows.

(1) The weight average molecular weight was measured as a standard polystyrene equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

(2) The molecular weight distribution is determined by GPC measurement using THF as a developing solvent.
The value of the ratio (Mw / Mn) between w and the number average molecular weight (Mn) was used as an index.

(3) The glass transition temperature is JIS K7
121 (DSC method).

(4) The hydrogenation rate (nuclear hydrogenation rate) of the hydrogenated aromatic vinyl polymer or the hydrogenated cycloalkene vinyl polymer was calculated from ¹ H-NMR measurement.

(5) The polymerization addition rate was calculated based on the measurement by gas chromatography.

(6) The transparency was measured as a 15% cyclohexane solution of a polymer in a glass cell having an optical path length of 50 mm, and a wavelength of 400 to 800 nm was measured by a spectrophotometer (U-30, manufactured by JASCO Corporation). , The light transmittance (%) was measured while continuously changing the wavelength, and the minimum transmittance was measured as the light transmittance. The higher the light transmittance, the better the transparency.

Reference Example 1 (Polymerization) 320 parts of dehydrated cyclohexane, 4 parts of styrene, and 0.10 part of dibutyl ether were charged into a sufficiently dried, nitrogen-purged, stainless steel autoclave equipped with an electromagnetic stirrer and stirred. N-butyllithium solution (hexane solution containing 15%) at a temperature of 60 ° C.
The polymerization was started by adding a part. After conducting the polymerization under the same conditions for 0.5 hour (the addition rate at this point was 99%), 76 parts of the polymerization reaction solution in the autoclave was added while continuing the polymerization under the same conditions. Styrene was added continuously over 1 hour. After the addition was completed, 0.1 part of isopropyl alcohol was added to terminate the polymerization. After the completion of the reaction, the polymerization conversion was 100% and the Mw was 200,00.
0 and Mw / Mn were 1.05.

REFERENCE EXAMPLE 2 (Polymerization) In a stainless steel pressure vessel which has been sufficiently dried and purged with nitrogen, 72 parts of styrene (sometimes referred to as St) and 8 parts of isoprene (sometimes referred to as Ip) are sealed. By mixing and stirring, a monomer mixture having a composition of 90/10 in terms of St / Ip weight ratio was prepared.

The styrene in Reference Example 1 was changed to the above monomer mixture, and 4 parts of the monomers initially charged had a polymerization conversion rate of 9%.
The polymerization reaction was carried out in the same manner as in Reference Example 1 except that the time to reach 9% was 0.5 hour and the time was 0.2 hour. After completion of the reaction, the polymerization conversion was 100%, Mw was 210,000, and Mw /
Mn was 1.09.

Example 1 (First Hydrogenation Reaction) 400 parts of the polymerization reaction solution obtained in Reference Example 1 was charged with a diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemicals, E22U, nickel support rate 58%) 8.0. And 80 parts of cyclohexane.
A hydrogenation reaction was performed at 0 ° C. and a hydrogen pressure of 44 MPa for 6 hours.

7. A diatomaceous earth filter aid (Radiolite 500 manufactured by Showa Chemical Industry Co., Ltd.) as a filter aid in this solution.
0 parts were added, and the temperature was 60 ° C. and the pressure was 0.2 MPa by a cylindrical pressure filter (manufactured by Sartreuse, filtration area 26 cm 2) equipped with a polypropylene filter cloth.
The mixture was filtered through a to separate the hydrogenation catalyst carrier and the filter aid from the polymer hydrogenated solution. The time required for the filtration was 2.0 hours.

The reaction solution containing the obtained hydrogenated polymer was poured into 1200 parts of isopropyl alcohol with stirring to precipitate the hydrogenated polymer, and the precipitate was collected by filtration.
After further washing with 200 parts of acetone, -100 kPa
The product was dried at 100 ° C. for 24 hours in a vacuum dryer having a reduced pressure to obtain 84 parts of a hydrogenated polymer.

Mw of the obtained hydrogenated polymer was 13
3,000, Mw / Mn is 1.25, Tg is 145 ° C,
The transmittance was 99% and the hydrogenation rate was 99.5%.

Further, the hydrogenated catalyst carrier and the filter aid separated by filtration were scraped out from a filter under a nitrogen atmosphere and charged into 80 parts of cyclohexane. The solid content in the recovered cyclohexane slurry containing the hydrogenation catalyst carrier and the filter aid was 15.8 parts, and the nickel content in the solid content by atomic absorption spectrometry was 28.7%. From this, the recovered amount of the hydrogenation catalyst carrier was 7.82 parts (recovery rate 97.7 parts).
%) And 7.98 parts of the filter aid (recovery rate 99.8 parts).
%)Met.

(Second Hydrogenation Reaction) The cyclohexane slurry containing 15.8 parts of the recovered hydrogenation catalyst carrier was mixed with the following polymer solution (second embodiment of Reference Example 1) 4
And then newly added 0.18 part of the same diatomaceous earth-supported nickel catalyst. The nickel content in the total of 15.98 parts of the total of 8.0 parts of the hydrogenation catalyst carrier and 7.98 parts of the filter aid was 29.03%. Others were performed similarly to the 1st hydrogenation reaction. After the completion of the hydrogenation reaction, filtration was carried out without adding a filter aid, and the hydrogenated workplace support and the filter aid were collected by filtration. The time required for the filtration was 2.1 hours.

Mw of the obtained hydrogenated polymer was 13
2,000, Mw / Mn is 1.25, Tg is 145 ° C.,
The transmittance was 99% and the hydrogenation rate was 99.6%.

The solid content of the recovered cyclohexane slurry containing the hydrogenation catalyst carrier and the filter aid was 15.9 parts, and the nickel content in the solid content was 28.9%. Thus, the recovered amount of the hydrogenation catalyst carrier was 7.92.
Parts (recovery rate 99.1%), the recovery amount of the filter aid is 7.98
Parts (recovery rate 100%).

(Third Hydrogenation Reaction) A cyclohexane slurry containing the recovered hydrogenation catalyst carrier and 15.9 parts of a filter aid was mixed with the following polymerization reaction solution (third reaction in Reference Example 1).
Second run) 400 parts, and 0.08 part of the same diatomaceous earth-supported nickel catalyst was newly added. 14. Total of 8.0 parts of the hydrogenation catalyst carrier and 7.98 parts of the filter aid in total.
The nickel content in 98 parts was 29.03%. Others were performed similarly to the 1st hydrogenation reaction. After completion of the hydrogenation reaction, filtration was performed without adding a filter aid, and the hydrogenation catalyst carrier and the filter aid were collected by filtration. The time required for the filtration was 2.1 hours.

The Mw of the obtained hydrogenated polymer was 13
3,000, Mw / Mn is 1.25, Tg is 145 ° C,
The transmittance was 99% and the hydrogenation rate was 99.6%.

The solid content of the recovered cyclohexanone slurry containing the hydrogenation catalyst carrier and the filter aid was 15.7.
And the nickel content in the solid content was 28.8%. From this, the recovered amount of the hydrogenation catalyst carrier was 7.80.
Parts (recovery rate 97.5%), the recovered amount of the filter aid was 7.90.
Parts (recovery rate 99.0%).

(Fourth to tenth hydrogenation reactions)
The cyclohexane slurry containing the hydrogenation catalyst carrier and the filter aid collected in the same manner as the third time was added to 400 parts of the next polymerization reaction solution (fourth to tenth times in Reference Example 1), and the same diatomaceous earth was newly added. The supported nickel catalyst was replenished so that the total amount of the catalyst support became 8.0 parts, and thereafter, the same operation as in the first hydrogenation reaction was performed.

Thus, the hydrogenation reaction was repeated 9 times in total.
The hydrogenation reaction was repeated a total of 10 times. In all cases, the reaction time was 6.0 hours and the hydrogenation rate was 99.5 to 99.5.
9% and 99.5% or more. From the second time on, the hydrogenation catalyst carrier is only newly added in an amount corresponding to the recovery loss, so that the consumption of the hydrogenation catalyst carrier in one reaction is 1.48 on average per 100 parts of the polymer. Department. On the other hand, no replenishment was made for the recovery loss of the filter aid, but the filtration time after the tenth hydrogenation reaction was 2.5 hours, and the filtration rate was only slightly reduced.

Example 2 A hydrogenation reaction and hydrogenation were carried out in the same manner as in Example 1 except that a palladium-on-alumina catalyst (G-58B, Nissan Sudohemie Catalysts, 0.05% palladium loading) was used as the hydrogenation catalyst. The hydrogenation reaction was repeated four times from the recovery of the added catalyst carrier and the filter aid, that is,
Using the same polymer solution as in Reference Example 1, a total of five hydrogenation reactions were performed.

Each hydrogenation reaction time was 4.5 hours,
The hydrogenation reaction could be performed in a short time. The hydrogenation rates were 99.5 to 99.9%, all of which were 99.5% or more, and there was no problem in reusing the hydrogenation catalyst. The filtration time after the fifth hydrogenation reaction was 2.4 hours, and there was no problem with the filtration speed.

Example 3 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the polymer solution of Reference Example 2 was used as the polymer solution, and the hydrogenation reaction was carried out again from the recovery of the hydrogenation catalyst carrier and the filter aid. Was repeated 9 times, that is, a hydrogenation reaction was performed 10 times in total using the same polymer solution as in Reference Example 2. Each hydrogenation reaction time was 6.0 hours, and the hydrogenation reaction could be performed in a short time. The hydrogenation rate is 99.5-99.
9% and 99.5% or more in each case, and there was no problem even if the hydrogenation catalyst was reused. The filtration time after the tenth hydrogenation reaction was 2.5 hours, and there was no problem with the filtration speed. The Tg of the hydrogenated polymer was 100 ° C.

Examples 4 and 5 Each time the hydrogenation reaction was repeated, a new hydrogenation catalyst was not replenished, and 2.0 parts of the hydrogenation catalyst carrier was recovered per 100 parts of the polymer solution. That is, the amount of the hydrogenation catalyst used per polymer was the same as in Examples 1 and 3 except for the recovered product each time, and the other conditions were the same as in Examples 1 and 3 for the hydrogenation reaction and the hydrogenation catalyst carrier. The hydrogenation reaction was repeated 9 times from the recovery of the filter aid to the hydrogenation reaction again, that is, 10 times each in total. Each hydrogenation reaction time was 6.0 hours, and the hydrogenation reaction could be performed in a short time. The hydrogenation rate is 99.5-9
At 9.9%, all were 99.5% or more, and there was no problem even if the hydrogenation catalyst was reused. In addition, the filtration time after the tenth hydrogenation reaction was both 2.5 hours, and the filtration speed was not a problem at all.

As a result, it was shown that there was no problem in the reaction time, the hydrogenation rate, the filterability, etc., even if the hydrogenation reaction was carried out using only the recovered product (containing a recovery filter aid) as the hydrogenation catalyst. .

Examples 6 and 7 The recovered cyclohexane slurry containing a hydrogenation catalyst carrier and a filter aid was used in a total amount of different hydrogenation reactions, and fresh catalyst and filter aid were used in amounts corresponding to the recovery loss. The hydrogenation reaction and the repetition of the hydrogenation reaction from the recovery of the hydrogenation catalyst support and the filter aid were repeated in the same manner as in Examples 1 and 3 except that 8.0 parts each was replenished each time. Nine times, that is, a total of ten hydrogenation reactions were performed. Each hydrogenation reaction time was 6.0 hours, and the hydrogenation reaction could be performed in a short time. The hydrogenation rates were 99.5 to 99.9%, all of which were 99.5% or more, and there was no problem in reusing the hydrogenation catalyst. The filtration time after the tenth hydrogenation reaction was 2.0 hours in both cases, and there was no problem with the filtration speed.

When the filter aid was added to the hydrogenation reaction system, there was no adverse effect on the reaction, and the tenth filtration time was shorter than in Examples 1 and 3 by the increased amount.

Examples 8 and 9 Prior to the hydrogenation reaction as in Examples 1 and 3, the polymerization catalyst residue in each polymerization reaction solution was removed in advance. That is, powdered activated alumina 5 was added to each 100 parts of the polymerization reaction solution.
Then, the polymerization catalyst was adsorbed at 60 ° C. for 2 hours and cooled to 30 ° C., and the solid content was separated by filtration and then used for the hydrogenation reaction. Except for the above, the hydrogenation reaction was repeated in the same manner as in Examples 1 and 3, and the hydrogenation reaction was repeated 9 times each from the recovery of the hydrogenation catalyst carrier and the filter aid,
That is, a total of 10 hydrogenation reactions were performed. Each hydrogenation reaction time was 5.0 hours, and the hydrogenation reaction could be performed in a short time. The hydrogenation rate is 99.5-99.9.
% In each case was 99.5% or more, and there was no problem even if the hydrogenation catalyst was reused. Further, the filtration time after the tenth hydrogenation reaction was 2.5 hours in both cases, and there was no problem with the filtration speed.

As described above, the removal rate of the polymerization catalyst from the polymer solution was able to increase the rate of the hydrogenation reaction.

Comparative Example 1 A hydrogenation reaction and a second hydrogenation reaction from the recovery of the hydrogenation catalyst carrier and the filter aid were performed in the same manner as in Example 1 except that no filter aid was added. However, in the first hydrogenation reaction, the hydrogenation rate was 99.5% in 6.0 hours, but in the second hydrogenation reaction, it was 75% in 6.0 hours.

The filtration time for recovering the hydrogenation catalyst was 10 hours for the first time and 15 hours for the second time.

In comparison with Example 1, it was shown that the use of the filter aid greatly improved the productivity of the hydrogenation catalyst by filtration. In addition, in the hydrogenation reaction for reusing the catalyst, it was shown that the reaction rate of the hydrogenation was reduced unless a filter aid was added.

Table 1 shows the results of the above Examples and Comparative Examples.

[0104]

[Table 1]

[0105]

Industrial Applicability According to the present invention, the production of hydrogenated aromatic vinyl polymer or cycloalkene vinyl polymer in which the utilization of a hydrogenation catalyst and a filter aid is increased to reduce waste and improve productivity is achieved. It is now possible.

Claims (2)

[Claims] 1. A hydrogenation reaction of an aromatic vinyl polymer or a cycloalkene vinyl polymer in the presence of a hydrogenation catalyst to obtain a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer. In the production method, a hydrogenation catalyst and a filter aid collected by filtration from the reaction solution after the hydrogenation reaction are added during another hydrogenation reaction of the aromatic vinyl polymer or the cycloalkenevinyl polymer to perform the hydrogenation reaction. A method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer. 2. In another hydrogenation reaction of the aromatic vinyl polymer or cycloalkene vinyl polymer, a new hydrogenation catalyst and / or a new hydrogenation catalyst are added in addition to the addition of the recovered hydrogenation catalyst and the filter aid. The method for producing a hydrogenated aromatic vinyl polymer or a hydrogenated cycloalkene vinyl polymer according to claim 1, wherein a filter aid is added.