WO2002016447A1

WO2002016447A1 - Process for producing vinyl alicyclic hydrocarbon polymer and molded object

Info

Publication number: WO2002016447A1
Application number: PCT/JP2001/007273
Authority: WO
Inventors: Tsutomu Nagamune
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 2000-08-25
Filing date: 2001-08-24
Publication date: 2002-02-28

Abstract

A process for producing a vinyl alicyclic hydrocarbon polymer, characterized by heating a reaction solution containing a vinyl alicyclic hydrocarbon polymer at a pressure not higher than ordinary pressure to remove volatile matters by evaporation and recovering the polymer. By the process, the vinyl alicyclic hydrocarbon polymer obtained can be reduced in the content of residual volatile ingredients therein and inhibited from suffering a decrease in molecular weight.

Description

AKITODA-SHOU Method for producing bur alicyclic hydrocarbon polymer and molded article

The present invention relates to, for example, a method for producing a vinyl alicyclic hydrocarbon polymer suitable as a material for a molded article for optical use, a butyl alicyclic hydrocarbon polymer obtained thereby, and a molded article.

Background art

A bullet alicyclic hydrocarbon polymer obtained by hydrogenating an aromatic bullet polymer such as polystyrene is excellent in transparency, low water absorption, heat resistance, and the like, and is a material suitable for optical materials and the like. A vinyl alicyclic hydrocarbon polymer is produced by performing a polymerization reaction by solution polymerization using an organic solvent, and then hydrogenating it in a reaction solution as needed. After removing volatile components such as a solvent from the reaction solution, it is necessary to form a molded body by heat melting molding or the like.

Conventionally, as a method for recovering the polymer by removing volatile components from the reaction solution, in the case of an aromatic vinyl polymer such as polystyrene, the reaction solution is dissolved in a large amount of a solvent (poor solvent) that does not dissolve the polymer. , And the polymer was collected by filtration (coagulation drying method) and dried to obtain a molding material.

However, since the polymer recovered only by the coagulation drying method is in the form of particles containing volatile components such as solvents, the volatile components inside the particles cannot be completely removed even by drying. It was difficult to use it as a molded article for optical components because it caused molding defects such as streaks and microvoids. In addition, if the drying temperature is increased or the drying time is lengthened to solve the above problems, the polymer chains will be cut and the molecular weight will be reduced, which may cause the strength of the obtained molded article to be reduced. I was

Japanese Patent Application Laid-Open No. H11-132731 discloses that a reaction solution in which a metathesis ring-opening polymer is dissolved in an inert solvent is heated under reduced pressure to evaporate and remove the inert solvent. A method for producing a metathesis ring-opened polymer by recovering the polymer using a direct drying method Has been disclosed. However, the metathesis ring-opening polymer and the butyl alicyclic hydrocarbon polymer have completely different molecular structures and different mechanisms for reducing the molecular weight. The publication does not teach that this method is versatile enough to be applicable to other resins.

Disclosure of the invention

An object of the present invention is to provide a method for producing a vinyl alicyclic hydrocarbon polymer capable of reducing the amount of residual volatile components and reducing the molecular weight reduction, and a vuyl alicyclic hydrocarbon polymer obtained by this method. That is.

Another object of the present invention is to provide a molded article comprising such a bullet alicyclic hydrocarbon polymer and having high strength without molding failure.

The present inventor obtains a polymer by recovering a polymer by evaporating and removing a volatile component such as a solvent or an unreacted monomer from a reaction solution containing a vinyl alicyclic hydrocarbon polymer by a specific method. Residual volatile components can be efficiently reduced while suppressing a decrease in the molecular weight of the polymer.As a result, not only a decrease in the strength of a molded article molded using the obtained polymer, but also molding defects such as silver streaks are caused. We found that it could be prevented. That is, in the method for producing a bele cycloaliphatic hydrocarbon polymer according to the present invention, a reaction solution containing a vinyl alicyclic hydrocarbon polymer is heated at normal pressure or lower to vaporize and remove volatile components. And recovering the polymer.

If the polymer concentration of the reaction solution when heated at normal pressure or lower is less than 80%, a part of the volatile components contained in the reaction solution before heating the reaction solution at normal pressure or lower. It is preferable that the reaction solution is pre-concentrated so as to obtain a polymer concentration of 80% or more by removing water.

The specific means of heating the reaction solution at normal pressure or lower is preferably performed using a decompressible solvent removing device equipped with a heat exchanger, more preferably without a thin film stirrer and with a heat exchanger. A solvent removal device capable of reducing pressure is used.

The lower limit of the heating temperature when the reaction solution is heated at normal pressure or lower is the glass transition temperature (T g) of the polymer contained in the reaction solution + 50 ° C, and the upper limit is 320 ° C. C is preferred.

The operating pressure at the time of heating the reaction solution at normal pressure or lower may be normal pressure or lower, and is preferably as low as possible, more preferably 15 kPa or lower. The time (residence time in the apparatus) from the start of heating the reaction solution at normal pressure or lower to the recovery of the polymer is preferably 2 hours or less.

The vinyl alicyclic hydrocarbon polymer according to the present invention is obtained by any one of the above production methods.

A molded article according to the present invention is characterized by comprising a butyl alicyclic hydrocarbon polymer obtained by any one of the above production methods.

Bull alicyclic hydrocarbon polymers have a very large decrease in molecular weight due to prolonged high-temperature heating compared to metathesis ring-opening polymers, etc. When a molded article is molded using the polymer recovered by removing the components, the mechanical strength of the resulting molded article decreases. On the other hand, the complete removal of volatile components without any heating would take a long time, causing industrial productivity to suffer. In addition, when the operation time for removing volatile components is shortened without heating, many volatile components remain in the polymer, and when a molded article is molded using the polymer thus obtained, During the molding process, molding defects such as silver streaks may occur.

In the present invention, the reaction solution containing the butyl alicyclic hydrocarbon polymer is heated at normal pressure or lower to evaporate and remove volatile components to recover the polymer.

In particular, the reaction solution containing the butyl alicyclic hydrocarbon polymer is concentrated to a high concentration of 80% or more, and then heated at normal pressure or lower to evaporate and remove volatile components, thereby recovering the weight recovered. It is possible to efficiently reduce the residual volatile components contained in the polymer while suppressing the decrease in the molecular weight of the coalescence.

In addition, the reaction solution containing the alicyclic cycloaliphatic polymer is placed under optimum conditions, for example, under an operating pressure of 15 kPa or less, and the lower limit of the temperature of the polymer contained in the reaction solution is reduced. Transition temperature (Tg) + 50 ° C, heating at a temperature within the upper limit of 320 ° C to evaporate and remove volatile components, and to keep the residence time in the equipment for 2 hours or less As a result, it is possible to efficiently reduce the residual volatile components contained in the polymer while suppressing the decrease in the molecular weight of the polymer to be recovered, and to optimize the industrial productivity Will be balanced.

As described above, according to the method of the present invention, the amount of residual volatile components and the decrease in molecular weight are small. Since a bullet alicyclic hydrocarbon polymer is obtained, a molded article molded using the same has no molding failure and high strength.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the hydrogenated alicyclic hydrocarbon polymer according to the present invention include a hydride of an aromatic ring portion of an aromatic vinyl polymer, an alicyclic vinyl polymer, and a hydride of an alicyclic vinyl polymer. Can be

The method for producing a vinyl alicyclic hydrocarbon polymer according to the present invention comprises: a step of polymerizing an aromatic butyl compound and a phenyl or alicyclic butyl compound in the presence of a polymerization catalyst; The method includes a step of hydrogenating the polymer obtained in the step in the presence of a hydrogenation catalyst, and a step of removing volatile components of the reaction solution obtained in the polymerization step or the hydrogenation step.

Polymerization process

The aromatic butyl compound used in the polymerization step is not particularly limited as long as it is a compound having an aromatic ring and a polymerizable butyl group. Examples of the aromatic vinyl compound include, for example, styrene, α-methylstyrene, aethylstyrene, α-propynolestyrene, α-isopropynolestyrene, a-t-butynolestyrene,

2-Methylstyrene, 3-Methynolestyrene, 4-Methynolestyrene, 2,4-Dimethylstyrene, 2,4-Diisopropynolestyrene, 4-t-Butylstyrene, 5-t-Ptinole-1-Methylstyrene Examples include styrene, monochlorostyrene, dichlorostyrene, and monofluorostyrene. Among them, styrene, α-methylstyrene and the like are particularly preferable.

Examples of the alicyclic biel compound used in the polymerization step include a cycloalkene compound and a cycloalkane biel compound.

The cycloalkene compound is not particularly limited as long as it has an aliphatic ring having 5 to 8 carbon atoms having a double bond and has a polymerizable bur group. The aliphatic ring can have an alkyl group having 1 to 4 carbon atoms or a halogen atom group as a substituent. Examples of cycloalkene bur compounds include, for example, 2-Biel cyclopentene, 2-Methinolay 4-vinylinolepentene, 3-Bielcyclopentene,

3-t ~ petite 4-cyclopentenebininole compound such as bininolepentene; 4- Biercyclohexene, 4-Isopropenylbiercyclohexene, 1-Methyl-14-Bursik mouth hexene, 1-Methyl-14-isopropidinylvinylsixene, Hexene, 2-Methinole-1-vinylinolecyclohexene, 2-Methinole 4 Cyclohexene biel compounds such as 1-isopropyl-rubiercyclohexene; 2-1-bulcic-heptene, 3-biercycloheptene, 4--bulcycloheptene, 3-methyl-1-hexinol-heptene, 4-ethynolehc-heptene, 4-ethynole-6 Cycloheptene vinyl compounds such as vienorcycloheptene, 3-t-butyl-1-5-bulcycloheptene; 2-bienolecyclootaten, 3-vinylcyclooctene, 4-bienolecyclooctene, 2-methinole 1-bulcinoleca otene, 4-ethynolee 6-vininole cyclo octene, 3 — Cyclooctenevinyl compounds such as t-butyl-7-butylcyclootatene. Among these, a cyclopentene compound and a cyclohexene vinyl compound are preferred, and a cyclohexene compound is particularly preferred.

The cycloalkane vinyl compound is not particularly limited as long as it is a compound having a saturated aliphatic ring having 5 to 8 carbon atoms 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 the compound having a lip of vinyl alcohol include cyclopentane vinyl chloride such as 2-vinylcyclopentane, 2-methylinole-4-vinylinolepentane, 3-butynolecyclopentane, and 3-t-butylinolene 4-vinylinolepentane. Norayi conjugate; 4-vinylinolecyclohexane, 4-isopropinolenobinoresin hex, 1-methinole 41-vinylinolexine hexane, 1-methyl-4-isoprozinylbininoresic mouth hexane, 2-methinole 14 -Cyclohexane vinyl compounds, such as -hexanolic hexane, 2-methinolyl 4-isopropinolenovinylic hexane; 2-vinyl ^ / cycloheptane, 3-bienolecycloheptane, 4-biercycloheptane, 3- Methynoreh 6-Biercyclohe butane, 4-Echinorhe 6-Bulurcycloheptane, 3-t-Buty L-5-Hyper-heptane vinylinole conjugates such as Bier cycloheptane; 2-Vinyl cyclo-octane, 3-Vinylcyclooctane, 4-Butylcyclooctane, 2-Methyl-5-vinylinolecyclooctane, 41- And cyclooctane biel compounds such as 6-vinylincyclooctane and 3-t-butyl-vinylcyclooctane. Of these, cyclopentane vinylide conjugates and cyclohexane vinyl compounds are preferred, and hexahexane vinyl compounds are particularly preferred.

Among these compounds, an aromatic bur compound, a pentopentyl compound and a cyclohexene vinylinoleic compound are preferred, and an aromatic bil compound and a hexene vinyl compound are more preferred. These compounds can be used alone or in combination of two or more.

A monomer copolymerizable therewith may be added in addition to the aromatic 'compound and the aromatic or alicyclic compound. Such a monomer is not particularly limited as long as it can be copolymerized by a polymerization method such as radical polymerization, anion polymerization, or cationic polymerization. Examples thereof include ethylene, propylene, isobutene, and 2-methyl-1- Α-olefin-based monomers such as butene, 2-methinolene 1-pentene, 4-methinolene 1-pentene; cyclopentadiene, 1-methyinclopentadiene, 2-methinole cyclopentadiene, 2-ethynolethic pentadiene, 5 -Cyclopentadiene-based monomers such as methinoresic pentagen and 5,5-dimethylcyclopentadiene; cyclic olefinic monomers such as cycloptene, cyclopentene, cyclohexene and dicyclopentadiene; butadiene, isoprene, 1 , 3_pentagen, furan, chofen, 1,3-hexa Conjugated diene monomers such as styrene; ditrinole monomers such as atari lonitrile, methacrylonitrile, and α-chloroacrylonitrile; methyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methallylate, and atalylic acid Acrylic ester monomers such as methyl, ethyl acrylate, propyl acrylate, and butyl acrylate; unsaturated fatty acid monomers such as atrial acid, methacrylic acid, and maleic anhydride; phenyl maleimide; ethylene oxide , Propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexenoxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and other cyclic ether monomers; methyl vinyl ether, vinyl vinyl azo And heterocyclic ring-containing vinyl compound monomers such as vinyl and vinyl 2-pyrrolidone. These copolymerizable monomers can be used alone or in combination of two or more. When copolymerizable monomers are added, the amount of repeating units in the polymer will be 50% by weight or less. What is necessary is just to add in the range.

When the aromatic vinyl compound and the Z or alicyclic vinyl compound are copolymerized with the copolymerizable monomer, the obtained copolymer may be a random copolymer or a pseudo-random copolymer. And graft copolymers and block copolymers. In the case of a block copolymer, it may be a diblock, triblock or higher multiblock, a block copolymer having a star-like or other branched structure, or a block copolymer having an inclined block. .

The mode of the polymerization reaction may be any of known methods such as radical polymerization, anion polymerization, and cationic polymerization, and may be any of suspension polymerization, solution polymerization, and bulk polymerization. When radical polymerization is performed, a radical initiator such as azobisisobutyronitrile and benzoyl peroxide can be used as a polymerization catalyst.

When performing cationic polymerization, BF _3, BF _e like it can be used as a polymerization catalyst. When performing anion polymerization, an organic metal can be used as a polymerization catalyst. When the hydrogenation reaction is carried out continuously after the polymerization reaction, solution polymerization in which the polymerization is carried out in an organic solvent is convenient for continuously carrying out the steps. Aion polymerization is preferable in order to obtain a polymer having a smaller molecular weight distribution, which is preferable as a polymer having a smaller birefringence.

The organic solvent is preferably a hydrocarbon solvent and is not particularly limited as long as it does not harm the polymerization catalyst. Examples thereof include η-butane, η-pentane, isopentane, η-hexane, η-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 to be used is such that the monomer concentration is usually 1 to 40% by weight, preferably 10 to 30% by weight.

The organic alkali metals used in the Ayuon polymerization include η-butyllithium, sec-butyllithium, t-butyl ^^ lithium, and hexinolelithium. Funinorerichiu Mono-organic lithium compounds such as lithium and stilbene lithium; polyfunctional organic lithium compounds such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithi-2-ethycyclohexane, 1,3,5-trilithiobenzene; sodium naphtha And potassium naphthalene. Of these, organolithium compounds are preferred, and monoorganic lithium is particularly preferred. These organic alkali metals can be used alone or in combination of two or more. The amount of the organic metal used is usually from 0.05 to 100 mmol, preferably from 0.1 to 50 mmol, per 100 parts by weight of the monomer.

In anion polymerization, a Lewis base can be added to the polymerization catalyst, if desired, to obtain a polymer having a narrow molecular weight distribution.

Examples of Lewis bases include, for example, ethenolei conjugates such as getyl ether, dibutyl ether, methyl oleno ethenoate, dibenzino oleateno and tetrahydrofuran: tetramethylethylene diamine, triethylamine, pyridine and the like Tertiary amine compounds; alkyl metal alkoxide compounds such as potassium tertiary hydroxide and potassium tertiary butyl oxide; phosphine compounds such as triphenylphenylphosphine; Of these, ether compounds are particularly preferred because they form polymers having a narrow molecular weight distribution. These Lewis base compounds can be used alone or in combination of two or more. The amount of the Lewis base compound used is usually 0.01 to 10.0 mmol, preferably 0.01 to 5.0 mmol, based on the organic alkali metal.

The polymerization reaction is usually carried out at 170 to 150 ° C, preferably at 150 to 120 ° C. The polymerization time is usually from 0.01 to 20 hours, preferably from 0.1 to 10 hours.

The polymerization reaction is stopped when the polymerization addition rate is increased and the monomer is almost eliminated, but a deactivator for the polymerization catalyst may be added for the purpose of preventing the reaction solution from gelling after the polymerization reaction. Examples of the deactivator of the polymerization catalyst include water; alcohols such as methanol, ethanol, isopropyl alcohol, 1,2-butanediol, and glycerin; carboxylic acids such as formic acid, acetic acid, citric acid, and phthalic acid; And phenols such as tarezol.

The molecular weight of the polymer obtained in the polymerization step is appropriately selected according to the purpose of use, From the viewpoint of balance between mechanical strength and moldability, gel permeation of tetrahydrofuran solution. Weight average molecular weight (Mw) in terms of polystyrene measured by chromatography, preferably 100000 or more, more preferably Is from 3,000 to 280,000, more preferably from 50,000 to 2,500,000. If the molecular weight is too large, not only does the moldability deteriorate, but also the progress of the hydrogenation reaction slows down in the case of performing the hydrogenation described later, and the hydrogenation rate decreases. If the molecular weight is too small, the mechanical strength of the polymer will be low.

The molecular weight distribution (Mw / Mn) of the polymer obtained in the polymerization step is preferably 1.25 or less, more preferably 1.20 or less, and further preferably 1.15 or less. When the molecular weight distribution is in the above range, a molded article molded using the polymer has excellent mechanical strength, and a decrease in the molecular weight in the volatile component removing step is reduced.

The glass transition temperature (Tg) of the polymer obtained in the polymerization step is preferably 50 to 250 ° C, more preferably 70 to 220 ° C, and still more preferably 80 to 200 ° C. C.

The polymer obtained by the polymerization step does not have a carbon-carbon unsaturated bond (a non-conjugated unsaturated bond and a di- or aromatic unsaturated bond, etc. in the side chain). When the hydrogenation step is not performed, it is preferable to include a step of removing the polymerization catalyst from the reaction solution after the polymerization step. In addition, even when the hydrogenation step is performed, a polymerization catalyst removing step may be included after the polymerization step. As a method for removing the polymerization catalyst in the case of solution polymerization, an adsorbent such as activated alumina is added to the polymerization reaction solution, and the mixture is stirred while being heated, and the polymerization catalyst is adsorbed on the adsorbent and filtered. And a method of adding a small amount of isopropyl alcohol or the like to a polymerization reaction solution to precipitate a polymerization catalyst and removing the polymerization catalyst by filtration. The residual amount of the catalyst in the reaction solution after removal of the catalyst is usually 10 ppm or less, preferably 1 ppm or less, by weight of the metal element (catalyst) with respect to the polymer in the reaction solution.

Hydrogenation process

In the present invention, when the polymer obtained by the above polymerization step has a carbon-carbon unsaturated bond in a side chain ring, it is preferable to partially or entirely hydrogenate the unsaturated group. By hydrogenating the unsaturated group, the heat resistance and transparency of the polymer can be improved. The hydrogenation reaction is carried out by contacting the polymer with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

The hydrogenation catalyst contains, for example, at least one element selected from nickel, nickel, iron, titanium, rhodium, palladium, platinum, ruthenium and rhenium. Among them, nickel catalysts are preferred because they give a hydride having a narrow molecular weight distribution of the polymer, that is, a weight average molecular weight Z number average molecular weight ratio Mw / 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.

Examples of the carrier include activated carbon, diatomaceous earth, magnesia, silica, alumina, silica-magnesia, silica-zirconia, diatomaceous earth-zirconia, and alumina-zirconia. The amount of the metal supported on the carrier is usually from 0.01 to 80% by weight.

As a homogeneous catalyst, for example, a catalyst in which a metal compound such as nickel, cobalt, titanium, or iron is combined 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 metal compound, for example, an acetylacetone salt, a naphthenate, a cyclopentagenenyl compound, a cyclopentadienyl dichloro compound, etc. of each metal are used. Examples of the organoaluminum include alkyl aluminum such as triethylaluminum and triisobutylaluminum; alkylaluminum alkylaluminum such as dimethylaluminum chloride and ethylaluminum dichloride; and alkylaluminum hydride such as diisobutylaluminum hydride. Is used. Examples of the organometallic complex include a “y-dichloro-π-benzene complex”, a dichlorotris (triphenyl-norethosphine) complex, and a hydride-chlorotris (triphenylphosphine) complex of the above metals.

These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst to be used is generally 0.03 to 50 parts by weight, preferably 0.16 to 33 parts by weight, per 100 parts by weight of the polymer. Examples of the organic solvent used in the hydrogenation step include alcohols in addition to the solvent used in the solution polymerization described above. 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 concentration of the polymer in the reaction solution is usually 1 to 50% by weight, preferably 3 to 40% by weight. The hydrogenation reaction of the polymer is carried out by introducing hydrogen into the hydrogenation reaction solution. For example, a method of bringing the introduced hydrogen into sufficient contact with the polymer while stirring the organic solvent solution of the polymer is known. preferable.

The temperature of the hydrogenation reaction is usually 10 to 250 ° C, preferably 50 to 200 ° C. The hydrogen pressure is usually 1 to 30 MPa, preferably 0.5 to 25 MPa.

After the hydrogenation, it is preferable to add a filter aid to the reaction solution, to separate the hydrogenation catalyst and the filter aid by filtration, and to reuse them in the next hydrogenation step.

Filter aids are chemically inert, porous particles that are used to reduce the likelihood of the filtered material from clogging the filter media. Examples of the filter aid include inert, solvent-insoluble powders such as diatomaceous earth, silica, synthetic zeolite, perlite, and radiolite. The filter aid is used in a body feed method in which a filter aid is added to the suspension to be filtered in advance, or a pre-coat method in which a filter aid is formed after a filter aid bed is formed and then filtered. The method is preferred. The amount of the filter aid used is preferably about the same as that of the hydrogenation catalyst. Next batch for polymer

In the (batch) hydrogenation reaction, it is preferable to use the recovered hydrogenation catalyst as a hydrogenation catalyst in a state in which a filter aid is mixed, since this saves the amount of catalyst used. If necessary, a new hydrogenation catalyst or a filter aid may be supplemented in addition to the recovered hydrogenation catalyst. Although the cause is not clear, the reduction of the hydrogenation rate can be prevented by keeping the filter aid mixed.

The molecular weight of the polymer obtained in the hydrogenation step is appropriately selected depending on the purpose of use, but the genole permeation of a tetrahydrofuran (THF) solution 'weight average molecular weight (Mw) in terms of polystyrene measured by chromatography. Preferably, it is 10 000 or more, more preferably 30,000 to 280,000, further preferably 50 000 to 250,000.

The molecular weight distribution MwZMn of the polymer obtained in the hydrogenation step is preferably 2.0 or less. Below, more preferably 1.7 or less, still more preferably 1.5 or less.

The glass transition temperature (T g) of the polymer obtained in the hydrogenation step is preferably 50 to 250 ° C., more preferably 70 to 220 ° C., and still more preferably 80 to 200 ° C. ° C.

The present invention preferably includes a step of removing the hydrogenation catalyst from the reaction solution after the hydrogenation step. Note that both the polymerization catalyst and the hydrogenation catalyst may be removed at once after the hydrogenation step without performing the polymerization catalyst removal step. The removal method and the residual amount of the catalyst after the removal may be the same as those in the polymerization catalyst removal step.

Volatile component removal process

Next, the reaction solution after the above-described polymerization step or hydrogenation step is supplied to a closed system in which foreign substances do not enter from the external environment, and volatile components mainly including an organic solvent are removed from the reaction solution to obtain a heavy solution. Collect the coalesced. It is also preferable that the solvent removed by evaporation is collected by condensing in a condensing device and reused.

To remove volatile components in the present invention, a direct drying method is used in which the reaction solution is heated at normal pressure or lower to evaporate and remove solvents and other volatile components.

Solvent removal equipment that can be directly dried and can be decompressed include vented screw extrusion dryers and thin film dryers, but considering the decrease in the amount of polymer molecules caused by mechanical stress, the It is preferable to use a thin film dryer that has a small shear stress applied to the polymer of the present invention. And the like) are particularly preferable because no shear stress is applied to the polymer in the solution. Examples of such a solvent removing device that does not include a thin film stirrer and includes a heat exchanger and that can be decompressed include a hibiscus evaporator (manufactured by Mitsui Engineering & Shipbuilding Co., Ltd.).

The heating temperature for the reaction solution is preferably such that the lower limit is the glass transition temperature (T g) of the polymer contained in the reaction solution + 50 ° C, and the upper limit is 320 ° C, more preferably It is 240 ° C or more and 280 ° C or less. If the heating temperature of the reaction solution is too low, the evaporation efficiency becomes poor, causing problems such as a decrease in productivity and thermal degradation of the polymer. If the heating temperature is too high, the polymer to be recovered will be thermally degraded, causing a decrease in molecular weight. There is it.

The operating pressure at the time of heating the reaction solution, that is, the pressure in the vessel, is preferably such that the effect of removing volatile components increases as the pressure decreases, more preferably 15 kPa or less, and further preferably 5 kPa or less. is there. If the operating pressure is too high, the evaporation efficiency of the solution will be poor and the content of volatile components in the polymer after drying will be high.

After the reaction solution is started to be heated at normal pressure or lower (specifically, after being introduced into the solvent removing device capable of reducing the life), until the polymer is recovered (specifically, for example, the solvent The time (remaining time in the device) after being taken out of the removing device and cooled and solidified and then pelletized is preferably 2 hours or less, more preferably 1 hour or less. If the residence time in the apparatus is too long, the polymer to be recovered may be thermally degraded and cause a decrease in molecular weight.

In the direct drying in the present invention, two or more solvent removing devices capable of reducing the pressure may be used, and in this case, the operating pressure and the heating temperature may be different for each device.

When the polymer concentration of the reaction solution supplied to the volatile component removal step and heated at normal pressure or lower is less than 80%, a part of the volatile component contained in the reaction solution is removed. It is preferred that the method further comprises a step of pre-concentration (pre-concentration step) so that the polymer concentration becomes 80% or more, preferably 85% or more. The preconcentration method is not particularly limited, and is a method in which the reaction solution is concentrated only at normal pressure; a method in which the reaction solution is heated and concentrated under normal pressure (heating concentration method); A method in which the pressurized reaction solution is released into a system under normal pressure, and only the volatile components are scattered and separated by the pressure difference to concentrate the reaction solution (flash concentration method). The flash concentration method is preferred from the viewpoint of good productivity, and the heat flash concentration method combining the heat concentration method and the flash concentration method is particularly preferred. Examples of the apparatus used for the flash concentration method include a flash box and a flash separator (manufactured by Mitsui Engineering & Shipbuilding Co., Ltd.).

In addition, even when performing pre-concentration, the method may further include a step of pre-heating the reaction solution before pre-concentration (pre-heating step). By preheating the reaction solution before the preconcentration, the concentration efficiency of the polymer is improved. Preheating method The method includes heating the storage container for the reaction solution before concentration and the transfer pipe from the storage container or Z to the solvent removal device with a jacket-type heating device, or using a multi-tube heat exchanger or plate-fin heat exchanger. Method using a known heat exchanger such as a heat exchanger. The temperature of the solution at the time of preheating is usually 50 to 400 ° C, preferably 70 to 350 ° C.

In the present invention, it is preferable that the above-mentioned removal of volatile components is performed in a low oxygen concentration atmosphere. By performing the treatment in a low oxygen concentration atmosphere, the coloring of the polymer finally recovered can be effectively prevented. The low oxygen concentration atmosphere, preferably oxygen concentration of 1 0 Capacity ° / ₀ or less, more preferably adjusted 8 vol ° / ₀ following atmosphere so as. By setting the working atmosphere to have a lower oxygen concentration, oxidation of the polymer is prevented, and coloring of the obtained molded body is prevented. As a specific means for creating a low oxygen concentration atmosphere, there is a method of setting the inside of an apparatus used for removing volatile components to an atmosphere of an inert gas such as nitrogen or helium.

Through the above volatile component removal step, the volatile component content in the recovered polymer can be reduced to preferably 1000 ppm or less, more preferably 500 ppm or less. . By setting the content of the volatile component in the polymer to be recovered to 100 000 ppm or less, there is little possibility that molding failure such as sylper streak void occurs in the molded product.

Various compounding agents

Various binders can be added to the bullet alicyclic hydrocarbon polymer obtained by the method of the present invention, if necessary. The various compounding agents are not particularly limited as long as they are generally used in the resin industry. For example, antioxidants such as phenol-based, phosphite-based, and thioether-based compounds; and ultraviolet rays such as hindered phenol-based compounds Absorbents; mold release agents such as aliphatic alcohols, aliphatic esters, aromatic esters, triglycerides, fluorinated surfactants and higher fatty acid metal salts; other lubricants, anti-fog agents, plasticizers, pigments, near red External absorbents, antistatic agents and the like. These combinations may be used alone or in combination of two or more. The amount of the compounding agent is appropriately selected within a range that does not impair the scope of the present invention. Bull alicyclic hydrocarbon polymers to which various compounding agents are added may be used alone or in combination of two or more. It is.

Molding

The bullet alicyclic hydrocarbon polymer obtained by the method of the present invention can be kneaded in a molten state using a twin-screw extruder or the like after production, and used as pellets. Then, molding is performed by a known method, for example, injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, rolling molding, cutting molding, or the like. be able to.

Use

The bullet alicyclic hydrocarbon polymer obtained by the method of the present invention is useful in a wide range of fields as various molded articles including optical materials.

For example, optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films; liquid chemical containers, ampoules, and vials , Prefilled syringes, infusion bags, sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, etc. for liquid, powder or solid medicine containers, food containers, blood test sampling test tubes, medicine containers Caps, blood collection tubes, sampling containers such as sample containers, medical instruments such as syringes, sterile containers such as scalpels, forceps, gauze, contact lenses, etc., beakers, petri dishes, flasks, flasks, test tubes, centrifuge tubes, etc. '' Medical optical components such as analytical instruments, plastic lenses for medical inspection, Ryoyo infusion Chi Interview one flop, pipes, fittings, piping materials such as pulp, denture, medical equipment, such as artificial hearts, artificial tooth root of any artificial organs or parts thereof;

Processing or transfer containers such as tanks, trays, carriers, cases, etc., protective materials such as carrier tapes, separation films, pipes, tubes, pulp, shipper flowmeters, piping such as filters and pumps, sampling containers, and bottles Equipment for processing electronic components such as liquid containers such as liquid and ampoule bags; covering materials for electric wires and cables; general-purpose insulation such as OA equipment such as industrial electronic equipment, copying machines, computers, and printers, and instruments Materials; Rigid printed circuit boards, flexible printed circuit boards, multilayer printed wiring boards, and other circuit boards, especially high-frequency circuit boards for satellite communications equipment that require high-frequency characteristics; liquid crystal substrates, optical memories, automobiles and aircraft Substrate of transparent conductive film such as surface heating element such as defroster, electric and conductor sealing materials such as transistors, ICs, LSIs, LEDs, etc.Sealing of electric and electronic parts such as components, motors, capacitors, switches, and sensors Electrical insulation materials such as sealing materials, body materials such as TVs and video cameras, parabolic antennas, flat antennas, structural members of radar dome; films such as packaging films and agricultural films; information such as magnetic flip-up disks and magnetic hard disks A recording substrate may be used. Above all, it is preferable to apply to an optical material which does not like coloring of a molded article.

The embodiments of the present invention have been described above. However, the present invention is not limited to these embodiments at all, and it is needless to say that the present invention can be implemented in various modes without departing from the gist of the present invention. .

Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples. In the following examples, parts by weight are based on weight unless otherwise specified.

In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation using a cyclohexane as a moving layer (chromatography-one in terms of polystyrene) unless otherwise specified. Hydrogenation rates were measured by — NMR.

Production example 1 (Production example of reaction solution)

Stirrer, equipped with a jacket for heating your Yopi cooling, internal volume 1. varus応器of 5 m ³ was replaced by nitrogen gas, styrene as monomer 200 kg, hexane and 600 kg in a solvent cyclohexane Then, 0.4 kg of dibutyl ether as a polymerization accelerator is supplied into the reactor, and 0.5 O kg of a 15% by weight n-hexane solution of n-butyllithium as a polymerization catalyst is added at 60 ° C. The polymerization reaction was performed for 2 hours. Thereafter, 0.2 kg of isopropanol was added as a polymerization terminator, and the polymerization step was completed to obtain a styrene polymer. The conversion of the styrene monomer into a styrene polymer in this polymerization reaction was 99.9%.

The resulting styrene polymer solution was transferred to a pressurizable reactor, and 20 kg of a nickel-silicone supported catalyst (E22U, manufactured by JGC Corporation) was added as a hydrogenation catalyst, and the hydrogen pressure in the reactor was reduced. 4. Perform hydrogenation reaction at 5MPa, temperature 160 ° C for 6 hours, A vinylcyclohexane polymer was obtained. The hydrogenation rate of the obtained bulcyclohexane polymer was 99.9%, and the glass transition temperature was 145 ° C.

Production Example 2 (Production example of reaction solution)

Stirrer, equipped with a jacket for heating your Yopi cooling, the varus応器having an inner volume of 1. 5 m ³ was replaced by nitrogen gas, hexane 600 kg to dehydration cycloalkyl, styrene 60 kg Oyopi Djibouti ether 0. 4 kg, and while stirring at 60 ° C, add 0.9 kg of II-butyllithium solution (15./. Containing hexane solution) to start the polymerization reaction, and carry out the polymerization reaction as it is for 1 hour. I got it. At this time, the polymerization conversion was 99% or more. Next, 80 kg of a mixed monomer composed of 40 kg of styrene and 40 kg of butadiene was added to the reaction solution, and the polymerization reaction was further performed for 1 hour. At this time, the polymerization conversion was 99% or more. Thereafter, 60 kg of styrene was further added to the reaction solution, and the polymerization reaction was further performed for 1 hour. Then, 0.4 kg of isopropinoleanololecol was added to the reaction solution to stop the reaction. The polymerization conversion was 99% or more.

The obtained styrene-styrene / ptadene-styrene block copolymer solution was transferred to a pressurizable reactor, and a nickel-silica supported catalyst (E22U: Nikki Chemical Co., Ltd.) was used as a hydrogenation catalyst. 18 kg The hydrogenation reaction was performed for 6 hours at a hydrogen pressure in the reactor of 4.5 MPa and a temperature of 170 ° C for 6 hours, and the hydrogenation-styrene polymer (viercyclohexane polymer) block, hydrogenated monostyrene A ternary block copolymer comprising a nobutadiene copolymer block and a hydrogenated monostyrene polymer block was obtained. The hydrogenation rate of the obtained block copolymer was 99.9 ° / ₀ , and the glass transition temperature was 140 ° C.

Example 1

Concentration process

After the hydrogenation catalyst in the vinyl-necked hexane reaction solution obtained in Production Example 1 was separated and removed by filtration, the reaction solution was subjected to ilganox 1010 (manufactured by CHIPAGIGI CORPORATION) as a phenolic acid inhibitor. kg was added.

After heating the above reaction solution (25% concentration) to 220 ° C, it is applied to a pressurizable cylindrical solution concentrator (550 mm ID, 500 mm height, manufactured by BUSS) at 40 k / h. Introduced in g. As an operation at the time of introduction, a part of the solvent in the reaction solution is flash-separated by creating a pressure difference by setting the introduction pressure of the reaction solution to 300 kPa and the exhaust pressure to 300 kPa. The reaction solution was preliminarily concentrated. The separated and evaporated solvent was transferred to the heat exchanger from the exhaust port and then recovered by condensation. The polymer concentration of the obtained reaction solution was 85%.

Drying process

The reaction solution pre-concentrated by the above method was converted to a solvent equipped with a plate-fin heat exchanger (width 27 O mm, height 20 O mm, depth 255 mm, heat transfer area 4.3 m ² ). The gas was directly introduced into the removal device (manufactured by BUSS) from the outlet of the cylindrical concentrator through the inside of the double pipe through which the heating medium at 270 ° C passed, and the heating temperature was set at 270 ° C. At an operating pressure of 1 kPa in the apparatus, a process of removing volatile components such as solvents was performed by heating and decompression. The evaporated solvent (cyclohexane) was suctioned from the exhaust port by a vacuum pump and condensed by a heat exchanger and recovered. The vinylcyclohexane polymer in the molten state accumulated at the bottom of the equipment was continuously led out of the equipment by a gear pump, extruded into strands, cooled and solidified, and formed into pellets by a pelletizer. . In the above series of operations, the time from introduction of the concentrated solution into the device to pelletization (residence time in the device) was 1 hour.

The concentration of the volatile components remaining in the obtained pellet-shaped bush hex polymer was measured by gas chromatography and found to be 80 ppm.

The weight average molecular weight (Mw) of the bulcyclohexane polymer was determined in terms of polystyrene by gel permeation chromatography (GPC). After the treatment, it was 11.90000, and the reduction rate was 10%.

Example 2

In the drying step, the same procedure as in Example 1 was carried out except that the heating temperature was set at 220 ° C. and the residence time of the bulcyclohexane polymer in the apparatus was set at 2 hours. A coalescence was obtained. The volatile component concentration of the obtained bulcyclohexane polymer was 100 ppm, and Mw was 132 000 before the solvent removal treatment and 123 000 after the solvent removal treatment. Was 7%. Example 3

A pellet-like bicyclohexane polymer was obtained in the same manner as in Example 1 except that the internal pressure of the apparatus was changed to 15 kPa in the drying step. The volatile component concentration in the obtained Biercyclohexane polymer was 160 ppm, and Mw was 1320000 before the solvent removal treatment, and 1190 000 after the solvent removal treatment. The decrease was 10%.

Example 4

After separating and removing the hydrogenation catalyst from the bulcyclohexane reaction solution obtained in Production Example 1 by filtration, the reaction solution was added to a phenolic acid inhibitor, ilganox 100 (Chipagaigi Co., Ltd.). 0.5 kg).

The obtained vinylcyclohexane reaction solution (concentration: 25%) was introduced into the solvent removing apparatus used in Example 1 at 40 kg / h without passing through the concentration step, and was heated at a heating temperature of 270 ° C. At an internal pressure of 1 kPa, a solvent removal treatment was performed by heating under reduced pressure. The evaporated solvent was sucked from the exhaust port by a vacuum pump, and was condensed and recovered by a heat exchanger. The molten cyclohexane-based polymer collected at the bottom of the apparatus was continuously drawn out of the apparatus by a gear pump, solidified by cooling while extruding into a strand, and formed into a pellet by a pelletizer. The residence time of the bulcyclohexane polymer in the apparatus was 6 hours. The volatile component concentration in the obtained vinylcyclohexane polymer was 200 ppm, and Mw was 132,000 before the solvent removal treatment, and 112,000 after the solvent removal treatment, and decreased. The rate was 15%.

Example 5

A pellet-shaped vinyl hexane polymer was obtained in the same manner as in Example 1 except that the concentration step was not performed, and the residence time of the vinyl siloxane polymer in the drying step in the apparatus was set to 10 hours. The volatile component concentration in the obtained bursik-mouth hexane-based polymer was 100 ppm, and the Mw was 13200000 before the solvent removal treatment and 11000000 after the solvent removal treatment. 0, a decrease of 17%.

Example 6

A pellet-shaped vinylcyclohexane polymer was obtained in the same manner as in Example 1 except that the concentration step was not performed and the heating temperature in the drying step was 220 ° C. The volatile component concentration in the obtained bulcyclohexane polymer was 250 pm, and Mw was Before the solvent removal treatment, it was 132,000, and after the solvent removal treatment, it was 110,000, and the reduction rate was 13. /. Met.

Example 7

A pellet-shaped bulcyclohexane polymer was obtained in the same manner as in Example 1 except that the block copolymer solution obtained in Production Example 2 was used. The concentration of volatile components in the obtained polymer was 70 ppm, and Mw was 7500 before the solvent removal treatment and 7150 after the solvent removal treatment, and decreased. Rate is 5. /. Met.

Comparative Example 1

A bicyclohexane polymer was recovered from the Bielsik-mouth reaction solution obtained in Production Example 1 by a coagulation drying method. That is, after the hydrogenation catalyst hexane reaction solution to Byurushi black obtained in Preparation Example 1 was separated off by filtration and then to the reaction solution 1 part by weight to 1 0 m ³ of agitator with container, 3 weight A part of isopropanol was added, and the reaction solution was introduced at 40 kg / h under stirring of isopropanol to coagulate the hexane polymer at the mouth of the vininole resin to obtain a slurry of a bielcyclohexane polymer.

Next, the slurry of the bulcyclohexane polymer is sent to a filter to separate most volatile components such as isopropanol / cyclohexane, and the bulcyclohexane polymer is transferred to a hot air dryer, which is a known facility. The temperature of the hot air was 60 ° C, and the drying time was 2 hours.

The volatile component concentration in the obtained vinylcyclohexane polymer was 20000 p, and Mw was 13200000 before the solvent removal treatment, and 1320000 after the solvent removal treatment. Yes, the reduction rate was 0%.

Comparative Example 2

A dried block copolymer was obtained in the same manner as in Comparative Example 1, except that the block copolymer solution obtained in Production Example 2 was used. The volatile component concentration in the obtained block copolymer was 1,600 ppm, and Mw was 7,500,000 before the solvent removal treatment, and 7,500,000 after the solvent removal treatment. The decrease was 0%.

Table 1 also shows the results of Examples 1 to 7 and Comparative Examples 1 and 2. table 1

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Concentration (%) (° C) (kPa) (h) Concentration (ppm) (%) Example 1 Production Example 1 85 270 1 1 80 10 Example 2 Production Example 1 85 220 1 2 100 7 Example 3 Production Example 1 85 270 15 1 160 10 Example 4 Production Example 1 No concentration 270 1 6 200 15 Example 5 Production Example 1 No concentration 270 1 10 100 17 Example 6 Production Example 1 No concentration 220 1 6 250 13 Example 7 Production Example 2 85 270 1 1 70 5 Comparative Example 1 Production Example 1 No concentration 2000 0 Comparative Example 2 Production Example 2 No concentration 1600 0

From the results shown in Table 1, if heating is not performed at normal pressure or lower as in Comparative Examples 1 and 2, the Mw reduction rate is 0%, but the residual volatile component concentration increases. In contrast, in Examples 1 to 7 in which heating was performed at normal pressure or lower, it was confirmed that the residual volatile component concentration could be reduced while suppressing the Mw reduction rate.

Further, in comparison between Examples 1 to 3 and 7 and Examples 4 to 6, the polymer contained in the reaction solution was subjected to pre-concentration before heating at normal pressure or lower, as in Examples 1 to 3 and 7, When the concentration was increased in advance, the residence time during heating and depressurization after heating was reduced by 1 compared to the case of Examples 4 to 6 in which heating was performed at normal pressure or lower without preconcentration. As a result, it was confirmed that the residual volatile component concentration could be reduced while suppressing the Mw reduction rate.

Claims

The scope of the claims

1. A bicyclic alicyclic hydrocarbon characterized in that a reaction solution containing a bicyclic alicyclic hydrocarbon polymer is heated at normal pressure or lower to evaporate and remove volatile components to recover the polymer. A method for producing a polymer.

2. The butyl alicyclic hydrocarbon polymer according to claim 1, comprising a hydride of an aromatic ring portion of an aromatic vinyl polymer, an alicyclic butyl polymer, or a hydride of an alicyclic vinyl polymer. A process for producing a bullet alicyclic hydrocarbon polymer.

3. A method comprising a step of polymerizing an aromatic vinyl compound and / or an alicyclic vinyl compound in the presence of a polymerization catalyst, and a step of hydrogenating the polymer obtained in the polymerization step in the presence of a hydrogenation catalyst. Item 3. The process for producing a bullet alicyclic hydrocarbon polymer according to item 1 or 2.

4. The vinyl alicyclic hydrocarbon polymer is a copolymer of an aromatic butyl compound and / or an alicyclic butyl compound and a monomer copolymerizable with the compound. A method for producing the butyl alicyclic hydrocarbon polymer according to any one of the above.

5. The molecular weight of the butyl alicyclic hydrocarbon polymer is 100,000 or more in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel 'permeation' chromatography. The process for producing a butyl alicyclic hydrocarbon polymer according to any one of the above.

6. The molecular weight distribution of the Bull alicyclic hydrocarbon polymer is determined by gel permeation 'chromatography.

The production of a butyl alicyclic hydrocarbon polymer according to any one of claims 1 to 5, wherein the ratio (Mw / Mn) of (Mw) to the number average molecular weight (Mn) is 2.0 or less. Method.

7. The production of a vinyl alicyclic hydrocarbon polymer according to any one of claims 1 to 6, wherein the vinyl alicyclic hydrocarbon polymer has a glass transition temperature (Tg) force of 50 to 250 ° C. Method.

8. The method for producing a butyl alicyclic hydrocarbon polymer according to any one of claims 1 to 7, wherein the reaction solution is concentrated before the reaction solution is heated at normal pressure or lower.

9. Concentrate the reaction solution so that the polymer concentration is 85% or more 9. A method for producing the bullet alicyclic hydrocarbon polymer according to claim 8.

10. The production of the butyl alicyclic hydrocarbon polymer according to claim 8 or 9, wherein after the reaction solution is pressurized to a normal pressure or higher, the reaction solution is concentrated by releasing the reaction solution into a normal pressure system. Method.

11. The method for producing a vinyl alicyclic hydrocarbon polymer according to any one of claims 8 to 10, wherein the reaction solution is heated before the reaction solution is concentrated.

12. The method for producing a bullet alicyclic hydrocarbon polymer according to claim 11, wherein the reaction solution is heated to 50 to 400 ° C.

13. The butyl alicyclic hydrocarbon according to any one of claims 1 to 12, wherein the reaction solution is heated at a normal pressure or lower using a solvent removal device capable of reducing pressure provided with a heat exchanger. A method for producing a polymer.

14. The lower limit of the heating temperature when heating the reaction solution at normal pressure or lower is the glass transition temperature (T g) of the polymer contained in the reaction solution + 50 ° C, and the upper limit of the heating temperature. The method for producing a vinyl alicyclic hydrocarbon polymer according to any one of claims 1 to 13, wherein the temperature is 320 ° C.

15. The method for producing a vinyl alicyclic hydrocarbon polymer according to any one of claims 1 to 13, wherein an operating pressure for heating the reaction solution at normal pressure or lower is 15 kPa or lower.

16. The butyl alicyclic hydrocarbon polymer according to any one of claims 1 to 13, wherein the time from starting heating the reaction solution at normal pressure or lower to recovering the polymer is 2 hours or shorter. Manufacturing method.

17. A vinyl alicyclic hydrocarbon polymer obtained by heating a reaction solution containing a butyl alicyclic hydrocarbon polymer under normal pressure to remove volatile components by evaporation, and recovering the reaction solution.

18. A molded article comprising the vinyl alicyclic hydrocarbon polymer according to claim 17.