WO2019004333A1 - Polymère contenant un composant polymère aromatique vinyle, et procédé de fabrication de celui-ci - Google Patents

Polymère contenant un composant polymère aromatique vinyle, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2019004333A1
WO2019004333A1 PCT/JP2018/024503 JP2018024503W WO2019004333A1 WO 2019004333 A1 WO2019004333 A1 WO 2019004333A1 JP 2018024503 W JP2018024503 W JP 2018024503W WO 2019004333 A1 WO2019004333 A1 WO 2019004333A1
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polymer
vinyl aromatic
mass
less
polymer component
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PCT/JP2018/024503
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Japanese (ja)
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隆直 松本
高柳　健二郎
中川　淳
川上　公徳
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Ｍｃｐｐイノベーション合同会社
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Publication of WO2019004333A1 publication Critical patent/WO2019004333A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances

Definitions

  • the present invention relates to a polymer comprising a vinyl aromatic polymer component, and a process for the preparation thereof.
  • Vinyl aromatic polymers and copolymers such as styrene-isobutylene copolymers are usually produced by cationic polymerization.
  • cationic polymerization a compound having a chlorine atom bonded is used as a polymerization initiator or a catalyst.
  • the resulting polymer contains chlorine derived from a polymerization initiator and / or a catalyst.
  • the polymer contains chlorine, hydrogen chloride or the like is generated when heating at the time of processing of the polymer, or when performing hydrogenation treatment, etc., causing corrosion in the processing device or reactor.
  • hydrotalcite which is a solid base is added to the polymer to neutralize generated hydrochloric acid (Patent Document 1), or dioctyltin mercaptide is used as a hydrochloric acid trapping agent. (Patent Document 2).
  • hydrotalcite containing a metal element and a tin compound are added to the polymer, metal residues at the time of burning the polymer become a problem.
  • the addition of hydrotalcite or tin compound causes problems in the coloration and odor of the polymer.
  • problems such as a decrease in hydrogenation catalyst activity and a deterioration in filterability of the catalyst occur.
  • the present invention aims to solve the above-mentioned problems.
  • the present invention can suppress corrosion of processing equipment and reactors during heating, hydrogenation treatment, etc. during processing of polymers, and color residue of metals during combustion, coloring of polymers, odor, and also heavy It is an object of the present invention to provide a polymer containing a vinyl aromatic polymer component free from problems such as a decrease in catalytic activity and deterioration in filterability at the time of hydrogenation of a united substance.
  • the inventor has obtained the following findings through detailed studies.
  • a basic substance such as hydrotalcite which becomes an ignition residue in an ashing test is removed from a polymer containing a vinyl aromatic polymer component
  • Cl is used to hydrogenate an aromatic ring contained in the polymer. Hydrogenolysis of the radicals takes place and the eliminated hydrogen chloride causes corrosion of the equipment. If the basic substance is still contained in the polymer, the risk of corrosion of the device can be reduced, but a large amount of ignition residue will be generated, and when the polymer is to be hydrogenated, the catalyst It poisons and reduces the catalyst activity and deteriorates the filterability of the catalyst.
  • the inventor of the present invention can solve the above-mentioned problems by controlling the content of chlorine contained in the vinyl aromatic polymer and the amount of the ignition residue in the incineration test to a specific range. Found out.
  • the present invention provides the following.
  • Polymer containing a vinyl aromatic polymer component according to any one of [1] to [3], wherein the content of the vinyl aromatic polymer component in the polymer is 10% by mass or more and 95% by mass or less .
  • step (1) A method for producing a polymer containing a vinyl aromatic polymer component according to any one of [1] to [6], which comprises chlorine and a base from a polymer solution containing the vinyl aromatic polymer component
  • the polymer containing the vinyl aromatic polymer component of the present invention has a small amount of chlorine, and the ignition residue in the incineration test is reduced. Therefore, the polymer containing the vinyl aromatic polymer component of the present invention has less metal residue when the polymer is burned, and the problems of coloration and odor are improved.
  • the polymer containing the vinyl aromatic polymer component of the present invention can be suitably used, for example, in medical applications.
  • the polymer containing the vinyl aromatic polymer component of the present invention has a low chlorine content, it can suppress corrosion of equipment used for processing, etc. when processing it in a secondary manner, and it is possible to use Since the content of a certain basic substance is also small, it is possible to suppress problems such as a decrease in catalytic activity in the hydrogenation of a polymer and the like and a deterioration in filterability of the catalyst.
  • the polymer containing the vinyl aromatic polymer component of the present invention (hereinafter sometimes referred to as "the polymer of the present invention") is not particularly limited as long as it contains the vinyl aromatic polymer component.
  • the vinyl aromatic polymer component is a component constituting a vinyl aromatic polymer, and a monomer constituting a vinyl aromatic polymer described later (hereinafter sometimes referred to as "vinyl aromatic monomer"). Are polymerized.
  • vinyl aromatic monomer what the vinyl group was couple
  • the vinyl group bonded to the aromatic ring may be one or more.
  • the aromatic ring may have a substituent other than a vinyl group bonded thereto.
  • vinyl aromatic monomer examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-Butyl-2-methylstyrene, 4-monochlorostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, 4-t-butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, vinyl Examples thereof include naphthalene, vinyl anthracene and divinyl benzene, and styrene, ⁇ -methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-chloromethylstyrene and vinylnaphthalene are preferably used, and further styrene,
  • the polymer of the present invention includes components other than vinyl aromatic polymer components such as units derived from the above-mentioned vinyl aromatic monomer (hereinafter sometimes referred to as "components other than vinyl aromatic polymer”). It may be. As components other than a vinyl aromatic polymer which the polymer of this invention may contain, it originates in the monomer (Hereafter, it may be called "other monomers") shown below. And polymers composed of the unit and the monomer.
  • the other monomer examples include aliphatic olefins, conjugated dienes, vinyl ethers, ⁇ -pinenes and the like, and specific examples include ethylene, propylene, butadiene, isobutylene and the like.
  • the other monomer is preferably butadiene or isobutylene, most preferably isobutylene.
  • components other than these vinyl aromatic polymers only 1 type may be contained and 2 or more types may be contained.
  • the polymer of the present invention contains a component other than a vinyl aromatic polymer, it tends to be possible to obtain a polymer excellent in a well-balanced manner in gas barrier properties and non-adsorption of chemical solution.
  • the vinyl aromatic polymer component and the component other than the vinyl aromatic polymer may form a copolymer.
  • the copolymer may be a block copolymer.
  • the block copolymer has at least one segment A (vinyl aromatic polymer component) and at least one segment B (components other than vinyl aromatic polymer), and the combination can achieve the effects of the present invention If it is a range, it will not specifically limit.
  • segment A vinyl aromatic polymer component
  • segment B components other than vinyl aromatic polymer
  • AB, A- (BA) n , (AB) m , BA- (BA) n -B where n is an integer of 1 or more, m is 2 or more
  • a structure such as representing an integer of
  • the combination of components other than the vinyl aromatic polymer component and the vinyl aromatic polymer is not particularly limited as long as the effects of the present invention can be obtained.
  • the combination of styrene and isobutylene, the combination of styrene and ethylene, the combination of styrene and butadiene, the combination of styrene and 2-butene, etc. provide good weatherability, heat resistance, flexibility and strength of the resulting polymer. Preferred because it tends to.
  • the polymer of the present invention is more preferably a styrene-isobutylene copolymer.
  • the styrene-isobutylene copolymer include styrene-isobutylene-styrene block copolymer, styrene-isobutylene block copolymer, styrene-isobutylene alternating copolymer, etc.
  • styrene-isobutylene-styrene block copolymer Is particularly preferred.
  • the ratio of the above combination is also not particularly limited.
  • the content ratio of the vinyl aromatic polymer component in the polymer of the present invention (the ratio of styrene in the case of a styrene-isobutylene copolymer) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably Is 15% by mass or more.
  • the content of the vinyl aromatic polymer component in the polymer of the present invention is preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, particularly preferably 40% by mass or less .
  • the proportion of the vinyl aromatic polymer component in the polymer of the present invention When the proportion of the vinyl aromatic polymer component in the polymer of the present invention is not more than the above upper limit value, the polymer of the present invention tends to be excellent in flexibility and elasticity and excellent in impact resistance. When the proportion of the vinyl aromatic polymer component in the polymer of the present invention is at least the above lower limit value, the polymer of the present invention tends to have good heat resistance.
  • the molecular structure of the polymer of the present invention may be linear, branched, radial or any combination thereof.
  • the polymer of the present invention preferably has a weight-average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably 30,000 or more, and further preferably Is 50000 or more, preferably 200000 or less, more preferably 150,000 or less, and still more preferably 130000 or less.
  • Mw weight-average molecular weight
  • GPC gel permeation chromatography
  • the chlorine content of the polymer of the present invention is usually 350 mass ppm or less, preferably 200 mass ppm or less, more preferably 100 mass ppm or less, particularly preferably 50 mass ppm or less.
  • the smaller the chlorine content the more the corrosion of the processing apparatus or reactor during processing or hydrotreating can be suppressed.
  • the polymer of the present invention is hydrogenated as the chlorine content is smaller, the decrease in the reaction rate of hydrogenation tends to be suppressed because the acidity in the hydrogenation system does not decrease too much.
  • the polymers of the present invention also include those which are below the detection limit when the chlorine content is analyzed, within the range in which the effects of the present invention can be obtained.
  • the measuring method of the chlorine content of a polymer is not specifically limited, For example, the ion chromatograph measurement after wet decomposition, XRF measurement, etc. are mentioned. Specifically, the chlorine content of the polymer is measured by the method described in the section of Examples described later.
  • the polymer of the present invention has an ignition residue (hereinafter sometimes simply referred to as "ignition residue") when subjected to an ashing test, usually at most 0.1% by mass, preferably 0. The content is at most 05% by mass, more preferably at most 0.01% by mass. As the ignition residue is smaller, the residue can be reduced when the combustion treatment is performed.
  • ignition residue hereinafter sometimes simply referred to as "ignition residue”
  • a styrene-isobutylene-styrene copolymer having an ignition residue of 0.5% by mass in order to make the ignition residue 0.1% by mass or less, at least 5 times It is necessary to dilute with other polymers which do not contain ignition residues.
  • a styrene-isobutylene-styrene copolymer is diluted and used in medical applications, it is difficult to sufficiently exhibit the physical properties of the styrene-isobutylene-styrene copolymer, such as high gas barrier properties. Therefore, as in the present invention, a polymer having a small content of ignition residue is required.
  • the above-mentioned ashing test is the first edition of the Japanese Pharmacopoeia General Test Method 7.02 plastic drug container test made of plastic.
  • the ignition residue is 0.1 mass% or less, which is an essential item in using the polymer for medical use.
  • the polymer of the present invention in which the ignition residue is 0.1% by mass or less, as described above, there are merits such as widening of application to plastic medicine containers and the like.
  • the lower limit of the ignition residue of the polymer of the present invention is not particularly limited, and the ignition residue is preferably as small as possible.
  • the lower limit of the ignition residue of the polymer of the present invention is usually 0.0001% by mass or more, preferably 0.001% by mass or more. Within this range, the effect of reducing the ignition residue can be sufficiently obtained, for example, it can be used by mixing with other polymers containing the ignition residue.
  • the structure of the polymer of the present invention is not particularly limited, but in terms of polymer stability, it is desirable that the polymer end be saturated hydrocarbon.
  • the polymer end has a structure derived from a polymerization initiator at the time of polymer synthesis, and depending on the polymerization initiator, it may have a chlorinated hydrocarbon structure.
  • the polymer terminal can be made into a saturated hydrocarbon by performing dechlorination by hydrogenolysis or the like described later.
  • the terminal in the case of a polymer in which 1,4-bis ( ⁇ -chloro-isopropyl) benzene or the like is used as a polymerization initiator, the terminal can be an isopropyl group.
  • the proportion of the saturated hydrocarbon structure such as isopropyl group among the terminal structures is not particularly limited, but it is usually 40% or more, preferably 50% or more, more preferably 70% or more, still more preferably 90% of the terminal structure. The above, most preferably 95% or more. Although the upper limit of this ratio is not particularly limited, it is 99.9% or less.
  • the chlorine content of the polymer containing the vinyl aromatic polymer component in the polymer solution to be treated is 350 mass ppm or less, preferably 200 mass ppm or less, more preferably 100 mass ppm or less, particularly preferably Of the polymer solution to be 50 mass ppm or less, and the ignition residue being 0.1 mass% or less, preferably 0.05 mass% or less, more preferably 0.01 mass% or less Removing the chlorine and basic substances.
  • the basic substance is not particularly limited as long as it can suppress the corrosion of the reactor. Specifically, it has the property of neutralizing an acid.
  • the basic substance is not particularly limited, but, for example, alkali metal compounds such as carbonates, bicarbonates and hydroxides of alkali metals; alkali earths such as carbonates, bicarbonates and hydroxides of alkaline earth metals Ammonium metal compounds; ammonia water; tertiary amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine and n-trioctylamine; secondary amines such as diethylamine and diisopropylamine; primary amines such as ethylenediamine; etc., etc.
  • Examples include sites, metal oxides such as magnesium oxide, and the like.
  • the basic substance may be two or more of these. Among them, at least one selected from the group consisting of hydrotalcites and metal oxides such as magnesium oxide is preferred, and hydrotalcites are more preferred.
  • these basic substances are usually derived from the process of producing a polymer containing a vinyl aromatic polymer component, and it is preferable to use a polymer containing a vinyl aromatic polymer component in a reactor or the like.
  • the content is usually about 0.01 to 5% by mass to prevent corrosion.
  • hydrotalcites are solid bases containing magnesium and aluminum, and hydrotalcites including natural mineral hydrotalcite and hydrotalcite artificially produced. Some are surface-modified with an organic compound or the like. Specific examples of hydrotalcites include DHT-4A, DHT-4C, DHT-6 (manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.
  • the hydrotalcites may be contained as a Mg content of about 25 mass ppm to about 1.2 mass% in a polymer containing a vinyl aromatic polymer component.
  • the step (1) may be performed through separate steps of a step of removing chlorine from the polymer solution to be treated and a step of removing a basic substance from the polymer solution to be treated, The above steps may be performed simultaneously. If the chlorine content or the content of the ignition residue of the obtained polymer satisfies the above range, a step of removing chlorine from the polymer solution to be treated, a basic substance is removed from the polymer solution to be treated Only one of the steps may be performed.
  • a method of reducing the chlorine content of polymers by hydrogenolysis Method of reducing chlorine content by heating a polymer.
  • Method to reduce the chlorine content by adding a base Method to reduce the chlorine content by adding a base.
  • the method of performing hydrogenolysis is most preferable, and it is preferable to perform hydrogenolysis to remove chlorine and the basic substance in one step.
  • a basic substance can be separated and removed together with the catalyst in a filtration process for separating the catalyst after the hydrocracking reaction.
  • the basic substance can be separated and removed in the process of precipitating the polymer from the polymer solution to be treated after the hydrogenolysis reaction.
  • Chlorine is usually contained as it is derived from a polymerization initiator or catalyst at the time of synthesis of a polymer containing a vinyl aromatic polymer component.
  • a polymerization initiator or catalyst for example, 1,4-bis ( ⁇ -chloro-isopropyl) benzene or the like is used as a polymerization initiator, but chlorine may be directly incorporated into the produced polymer skeleton. In this case, especially chlorine will be contained in the polymer containing the vinyl aromatic polymer component.
  • chlorine content contained in the polymer containing a vinyl aromatic polymer component before removing chlorine in a process (1) there is no restriction
  • chlorine is contained in the step of producing the polymer as described above, it is usually 5000 ppm by mass or less, preferably 1000 ppm by mass or less.
  • the lower limit of the chlorine content before the step (1) is not particularly limited, and the chlorine content may be equal to or less than the detection limit.
  • the chlorine content before the step (1) is, for example, 400 mass ppm or more as an amount contained in the raw material.
  • the polymer solution to be treated refers to a state in which the polymer containing the above-mentioned vinyl aromatic polymer component is completely dissolved or dispersed in a solvent, a partially dissolved or dispersed state, or a vinyl aromatic polymer component The polymer containing the above is in a state of being melted above the melting point.
  • a solvent may be used, or a polymer containing a vinyl aromatic polymer component may be melted as it is. It is preferred to use a solvent when carrying out the hydrogenolysis of chlorine.
  • the solvent is not particularly limited.
  • the solvent for example, alcohols such as methanol, ethanol, 1,4 butanediol, 2,3-butanediol, 1,2-butanediol, 1,3-butenediol, etc .; tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol Ethers such as dimethyl ether; Hydrocarbons such as hexane, cyclohexane and decalin; and the like.
  • THF tetrahydrofuran
  • cyclohexane from the viewpoint of the solubility of the polymer containing the vinyl aromatic polymer component.
  • the concentration of the polymer containing a vinyl aromatic polymer component in the polymer solution to be treated is not particularly limited, but preferably 5% by mass or more, more preferably 10% by mass The content is more preferably 15% by mass or more.
  • the concentration of the polymer containing the vinyl aromatic polymer component in the solution to be treated is preferably 70% by mass or less, more preferably 50% by mass or less.
  • Examples of the hydrogenolysis in the present invention include the following.
  • the basic substance is previously separated from the polymer solution by filtration or the like. Subsequently, catalytic hydrogenolysis is carried out in an acid-resistant container, chlorine is desorbed as hydrogen chloride during the reaction, and separated from the polymer solution as hydrogen chloride gas.
  • the catalyst which has subsequently been hydrocracked is not separated, said catalyst being contained in the polymer (but only in the case of catalytic amounts such that the ignition residue is within the scope of the present invention).
  • a catalyst in particular, a metal catalyst
  • the catalyst may be separated by filtration or the like, if necessary.
  • separating the catalyst it is also possible to separate simultaneously the basic substance which is trapping chlorine from the polymer solution.
  • (i) does not need to use an acid-resistant reaction vessel to trap generated hydrogen chloride with a basic substance, and it is used in “chlorinated basic substance” and “hydrocracking”
  • the catalyst is preferred because it can be separated simultaneously from the polymer solution by filtration or the like.
  • Metal catalyst The hydrogenolysis may be carried out in the coexistence of a metal catalyst.
  • the metal component of the metal catalyst is not particularly limited as long as it can promote hydrogenolysis and reduce the chlorine content of the polymer.
  • Examples of the metal catalyst include an alloy catalyst, and a supported metal catalyst in which a catalytically active metal is supported on a carrier.
  • the metal component of the metal catalyst is not particularly limited as long as it can hydrocrack hydrogen contained in the polymer.
  • metals such as ruthenium, nickel, copper, palladium, gold, platinum, iron, osmium, cobalt, rhodium and iridium can be used.
  • Rhodium, nickel, palladium or platinum is preferred, and ruthenium, nickel or palladium is particularly preferred in view of the high ability for hydrogenolysis of halogen atoms.
  • the metal catalyst used in the hydrogenolysis may use one metal or two or more metals.
  • the combination is not particularly limited, and even if each metal has catalytic activity (co-catalyst), it is one that improves the catalytic activity of one or more metals (co-catalyst) May be Of these, cocatalysts are preferred.
  • the alloy catalyst is not particularly limited, but an alloy of metals such as ruthenium, nickel, copper, palladium, gold and platinum is used. Specifically, commonly known Raney catalysts, copper-chromium catalysts and the like can be mentioned.
  • the metal catalyst may be a supported metal catalyst in which active metal species are supported on various carriers described later, or may be a homogeneous complex catalyst. It is preferable to use a supported metal catalyst from the viewpoint of easy separation from the reaction solution and easy reuse of the catalyst.
  • the carrier is not particularly limited, and examples thereof include carbon-based carriers such as activated carbon, carbon black and silicon carbide; and metal oxide carriers such as alumina, silica, zirconia, niobia, titania, ceria, diatomaceous earth and zeolite. Among them, it is preferable to use at least one selected from the group consisting of activated carbon, silica and alumina as a carrier in terms of activity expression and activity stabilization of the catalyst. It is desirable to use silica and alumina which can maintain relatively high support strength in the separation step after using the catalyst.
  • the content of the metal in the supported metal catalyst is not particularly limited.
  • the content of metal in the supported metal catalyst is, in terms of mass percentage converted to metal, usually 0.5% by mass or more, preferably 1% by mass or more, and usually 50% by mass or less based on the total mass of the support and the metal. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less.
  • the value described as% by mass indicates the metal content relative to the total mass of the carrier and metal of the catalyst.
  • the surface area of the support used for the metal catalyst is not particularly limited, but is usually 1 m 2 / g or more, preferably 10 m 2 / g or more, more preferably 50 m 2 / g or more, preferably 2000 m 2 / g or less, more preferably Is 1500 m 2 / g or less, more preferably 1000 m 2 / g or less.
  • a support having a surface area of the above lower limit or more it is possible to support the metal on the support with a high degree of dispersion, which is preferable in order to obtain sufficient catalytic activity. It is preferable to use a support having a surface area equal to or less than the above upper limit, because the pores possessed by the support can be effectively used.
  • the average pore diameter of the support used for the supported metal catalyst is not particularly limited, but is usually 200 ⁇ or more, preferably 250 ⁇ or more, preferably 500 ⁇ or less, more preferably 400 ⁇ or less.
  • the average pore size is at least the above lower limit, the polymer containing the vinyl aromatic polymer component is sufficiently incorporated, and the processing efficiency tends to be maintained.
  • a carrier having an average pore diameter larger than the above range can also be used, the above upper limit is preferable from the viewpoint of effectively using the carrier surface.
  • the method for producing a metal catalyst used in hydrogenolysis is not particularly limited as long as the active component functions as a catalyst in the metal state.
  • the metal catalyst can be obtained, for example, by reduction treatment of a metal, a metal compound or the like.
  • the method for producing the supported metal catalyst is not particularly limited, and can be produced by appropriately combining general methods.
  • a metal compound to be a metal source is supported on a carrier, subjected to treatments such as drying, washing, and calcination, and then converted to a metal state by reduction treatment.
  • the method for supporting the metal compound on the carrier is not particularly limited, and for example, known methods commonly used for preparation of a supported metal catalyst such as an impregnation method, an ion exchange method, a spray method and a coprecipitation method can be used.
  • a supported metal catalyst such as an impregnation method, an ion exchange method, a spray method and a coprecipitation method.
  • the reduction treatment can be carried out either in the liquid phase or in the gas phase, but a gas phase reduction in which a reducing gas such as hydrogen is used for reduction, a liquid phase reduction in which an alcohol, formic acid, sodium formate or the like is used preferable.
  • a gas phase reduction in which a reducing gas such as hydrogen is used for reduction a liquid phase reduction in which an alcohol, formic acid, sodium formate or the like is used preferable.
  • the reduction temperature in the reduction treatment is not particularly limited, but is usually 20 ° C. or more, preferably 100 ° C. or more, more preferably 250 ° C. or more, and usually 600 ° C. or less, preferably 500 ° C. or less.
  • the shape of the metal catalyst used in the hydrogenolysis is not particularly limited, and can be appropriately selected and used according to the type of reaction performed using the metal catalyst.
  • Specific examples of the shape of the metal catalyst include, for example, shapes such as powder, particles, and pellets. Among them, powder is preferable because the influence of diffusion in pores is small.
  • the particle size and the like of the metal catalyst used in the hydrogenolysis are not particularly limited.
  • the metal catalyst can be appropriately selected and used depending on the type of reaction to be used, but a catalyst having an average particle diameter of 30 ⁇ m or more and 20 mm or less is usually used.
  • the amount of the metal catalyst used in the hydrocracking is not particularly limited as long as it can be dechlorinated within an appropriate time by the hydrocracking.
  • the amount of the metal catalyst used is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, based on the weight of the polymer containing the vinyl aromatic polymer component. Preferably it is 50 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.
  • the temperature in the hydrogenolysis is not particularly limited, but is usually 20 ° C. or more, preferably 50 ° C. or more, more preferably 70 ° C. or more, and still more preferably 150 ° C. or more, 190 ° C. or more, 200 ° C. or more. Even more preferable in the order of 210 ° C. or higher.
  • the temperature in the hydrogenolysis is preferably 350 ° C. or less, more preferably 300 ° C. or less, still more preferably 280 ° C. or less. When the reaction temperature is in the above range, chlorine tends to be efficiently hydrocracked and removed while suppressing the decomposition reaction of the polymer containing the vinyl aromatic polymer component.
  • the hydrogenolysis time is not particularly limited as long as the chlorine content of the polymer containing the vinyl aromatic polymer component is equal to or less than the above upper limit.
  • the hydrogenolysis time is preferably 30 minutes or more, more preferably 1 hour or more, preferably 24 hours or less, more preferably 12 hours or less.
  • the hydrogen source in the hydrogenolysis is not particularly limited, but it is desirable to use gaseous hydrogen which does not require separation and purification after completion of the reaction.
  • the hydrogen gas pressure is not particularly limited, it is usually performed under hydrogen gas pressure.
  • the pressure of the hydrocracking reaction is not particularly limited, it is usually 0.1 MPa or more, preferably 1 MPa or more, more preferably 2 MPa or more, preferably 30 MPa or less, more preferably 20 MPa or less, further preferably 15 MPa or less.
  • reaction pressure promotes hydrogen supply to the metal catalyst and improves the hydrogenolysis reaction rate.
  • equipment such as a reactor having a particularly high pressure resistance is required, and a high reaction pressure condition may cause a decomposition reaction of the polymer.
  • hydrogenation of the aromatic ring may also proceed, and it is difficult to selectively carry out only dechlorination if hydrogenation of the aromatic ring is not desired.
  • the hydrogen concentration of hydrogen gas under a hydrogen atmosphere is not particularly limited, but is usually 70% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, and the upper limit is usually 100% by volume, preferably 95% % Or less.
  • the reactor used in the hydrogenolysis is not particularly limited, but usually an autoclave capable of high pressure reaction is used. A loop reactor may be used. The use of continuous reactors is also possible.
  • the catalyst may be charged into a reactor, and the reaction may be carried out by passing the solution to be treated and hydrogen. In the case of a continuous reactor, the catalyst separation step is not necessary, so in the case of mass production, the continuous reactor is preferable.
  • SUS is generally used as the material of the reaction apparatus
  • acid resistant SUS such as hastelloy
  • Glass-lined containers, Teflon-coated containers, etc. can also be used to cope with the generated acid.
  • the metal catalyst may be separated from the reaction solution.
  • the specific method for separating the catalyst is not particularly limited, filtration with a filter or the like, decantation, centrifugation and the like can be mentioned. By performing the separation operation of the metal catalyst, it is usually possible to remove the basic substance as well.
  • the progress rate of nuclear hydrogenation of the polymer containing the vinyl aromatic polymer component in the hydrogenolysis step is not particularly limited, but usually 50 moles of the aromatic rings contained in the polymer containing the vinyl aromatic polymer component %, Preferably 30 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, particularly preferably 1 mol% or less.
  • the lower limit of the rate of progress of nuclear hydrogenation is not particularly limited. When the nuclear hydrogenation progress rate is less than the above upper limit, the mechanical strength of the polymer tends to increase.
  • reaction temperature In order to carry out efficient dechlorination by hydrogenolysis after preventing nuclear hydrogenation of a polymer containing a vinyl aromatic polymer component with a nuclear hydrogenation progressing rate below the above upper limit, reaction temperature, reaction It is preferable to adjust the pressure, reaction time and amount of catalyst appropriately. If necessary, the amount of basic substance to be poisoned may be adjusted for the catalyst for hydrocracking.
  • the rate of progress of nuclear hydrogenation may be calculated, for example, by 1 H-NMR from the integrated value of an aliphatic-derived peak at around 0.5 to 2.5 ppm and an aromatic-derived peak at around 6.0 to 8.0 ppm. Can.
  • dechlorination is performed by heating a polymer containing a vinyl aromatic polymer component.
  • Dechlorinated chlorine is adsorbed to the basic substance, and when the basic substance is separated by filtration or the like, chlorine can be removed at the same time. Therefore, as described later, it is preferable to adjust the amount of the basic substance before the step (1).
  • the dechlorination temperature by heating of the polymer containing the vinyl aromatic polymer component is not particularly limited, but is usually 100 ° C. or more, preferably 150 ° C. or more, more preferably 200 ° C. or more, still more preferably 250 ° C. or more Is 400 ° C. or less, more preferably 350 ° C. or less, and still more preferably 300 ° C. or less. It exists in the tendency which can achieve efficient dechlorination, suppressing the decomposition reaction of a polymer because reaction temperature is the said range.
  • the gas atmosphere at the time of dechlorination by heating is not particularly limited, but usually nitrogen, argon, helium, oxygen or the like is used.
  • Inert gases such as nitrogen, argon and helium are preferably used since oxidative decomposition of the polymer may proceed if under oxygen.
  • the inert gas concentration is usually 70% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, and the upper limit is usually 100% by volume, preferably 95% by volume or less.
  • the treatment time in the case of dechlorination by heating is not particularly limited as long as the chlorine content of the polymer containing the vinyl aromatic polymer component is equal to or less than the above-mentioned upper limit value.
  • the heat treatment time is preferably 30 minutes or more, more preferably 1 hour or more, preferably 24 hours or less, more preferably 12 hours or less.
  • the amount of basic substance Prior to the above-mentioned step of removing chlorine, the amount of basic substance may be adjusted, if necessary. Specifically, by adjusting the amount of the basic substance to leave some basic substance or adding the basic substance, the eliminated chlorine is likely to be trapped by the basic substance. Adjust the amount of basic substance to
  • a styrene-isobutylene-styrene copolymer usually contains chlorine, and as described above, hydrogen chloride or the like is generated when it is heated when the polymer is molded while the chlorine is contained.
  • the reaction equipment may be corroded. Therefore, it may be necessary to add a basic substance such as hydrotalcite in order to neutralize chlorine.
  • a basic substance such as hydrotalcite
  • the ignition residue tends to increase when a basic substance is added, it is necessary to adjust the addition amount of the basic substance, the reaction conditions in the step of removing chlorine, and the like.
  • the amount of addition or residual amount in the case of adding or leaving a basic substance in the step of removing chlorine is such an amount that can neutralize the acid derived from the eliminated chlorine when dechlorinating in the step of removing chlorine. It is not particularly limited as long as The addition amount or residual amount of the basic substance is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 10% by mass or less based on the mass of the polymer containing the vinyl aromatic polymer component to be used Preferably it is 5 mass% or less, More preferably, it is 1 mass% or less.
  • the addition amount or residual amount of the basic substance is preferably 0.8 equivalent or more, more preferably 1 equivalent or more, still more preferably with respect to the chlorine content molar amount in the polymer containing the vinyl aromatic polymer component to be used. It is 1.1 equivalents or more, preferably 3 equivalents or less, more preferably 2.5 equivalents or less, further preferably 2 equivalents or less.
  • the basic substance may be added to the polymer containing the vinyl aromatic polymer component in advance within the above range. Therefore, when the step of removing chlorine is carried out, the basic substance is added in the above range, thereby hydrogenolysis of hydrogen, thermal decomposition reaction of chlorine while trapping hydrogen chloride generated by hydrogenolysis, heating, etc. There is a tendency to be able to do etc.
  • the method of removing the polymer of the present invention as a solid is not particularly limited, a steam coagulation method of removing the solvent by steam stripping, a direct desolvation method of removing the solvent under heating under reduced pressure, methanol, ethanol, isopropyl alcohol, water, A known method such as coagulation method of pouring a solution into a poor solvent of a polymer containing a vinyl aromatic polymer component such as acetone, methyl ethyl ketone and ethyl acetate to precipitate and coagulate a polymer containing a vinyl aromatic polymer component Can be adopted.
  • a solution is poured into a poor solvent of a polymer containing a vinyl aromatic polymer component to adopt a coagulation method in which a polymer containing a vinyl aromatic polymer component is precipitated and solidified.
  • the basic substance can be removed by eluting or washing out the basic substance in the solvent.
  • a step of removing a basic substance can be provided simultaneously with the above-described step of removing chlorine or as a separate step from the above-described step of removing chlorine.
  • the step of removing chlorine at the same time as separating the catalyst used in the step, the basic substance can also be separated and removed.
  • the form added to the polymer containing a vinyl aromatic polymer component is mentioned.
  • a polymer containing a vinyl aromatic polymer component is dissolved in a solvent, if the basic substance is insoluble in the solvent, it becomes dispersed in the solvent.
  • the type and content of the basic substance contained in the polymer containing the vinyl aromatic polymer component are as described above.
  • the effect of the improvement of the catalyst activity and the improvement of the catalyst separation filterability used in the case of hydrogenating the polymer of the present invention tends to be favorably obtained. It is preferable to remove talcites.
  • the method for removing the basic substance from the polymer solution to be treated is not particularly limited.
  • the following method may be mentioned.
  • a method of precipitating and removing as a salt with an acid a method of removing by solvent extraction and the like can be mentioned. From the viewpoint of efficiency, insoluble basic substances are preferably removed by filtration.
  • auxiliary agent may be used when removing the basic substance.
  • the auxiliary agent is not particularly limited as long as it does not adversely affect the removal of the basic substance, but includes one that directly adsorbs the basic substance, and one that improves the filtration rate when filtering the basic substance.
  • activated carbon silica, alumina, activated clay, diatomaceous earth and the like.
  • activated carbon is preferable from the viewpoint of being able to remove organic low molecular weight substances and the like which affect the color of the polymer.
  • the amount of the auxiliary used is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass with respect to the mass of the polymer containing a vinyl aromatic polymer component. % Or more, preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.
  • the amount of the auxiliary used is in the above range, the effect of the auxiliary is sufficiently obtained, and the deterioration of the handling of the polymer solution containing the vinyl aromatic polymer component is suppressed, and the basic substance to the auxiliary is used. The adsorption and filtration rate tend to be sufficiently improved.
  • the content of the basic substance in the polymer of the present invention after removal of the basic substance is usually 0.05% by mass or less, preferably 0.005% by mass or less, based on the mass of the polymer of the present invention More preferably, it is 0.0005 mass% or less.
  • the lower limit of the basic substance content is not particularly limited, and is, for example, 0.0001% by mass or more based on the mass of the polymer of the present invention.
  • the content of the basic substance in the polymer containing the vinyl aromatic polymer component can be generally determined by neutralization titration with an acid.
  • the amount of elements derived from the basic substance can be analyzed and converted from the result.
  • the content can be determined by measuring the amount of Mg.
  • a resin composition (hereinafter sometimes referred to as "the resin composition of the present invention") may be blended with a resin component of the present invention other than the polymer of the present invention, various additives, etc., if necessary. It can be done.
  • the resin composition of the present invention contains a polymer containing the above-mentioned vinyl aromatic polymer component, has a chlorine content of 350 mass ppm or less, and has a high ignition residue when subjected to an incineration test. It is preferable that it is a resin composition which is 0.1 mass% or less.
  • the resin composition of the present invention may contain, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, Ethylene / ⁇ -olefin copolymer such as ethylene / methacrylic acid ester copolymer, polyolefin resin such as polyethylene, polypropylene, polybutene-1 resin, polyphenylene ether resin, polyamide resin such as nylon 6, nylon 66, aramid Resins, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polylactic acid, polybutylene succinate, aliphatic polyester resins such as polycaprolactone, polycarbonate resins, polyarylate resins, modified polyphenylene oxide Resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ketone resin,
  • vinyl aromatic vinyl polymers, hydrogenated vinyl aromatic block copolymers, cycloolefin polymers, cycloolefin co-polymers are excellent because of their excellent balance of transparency, heat resistance, gas barrier properties, and non-adsorption ability of chemical solutions.
  • Polymers and polyolefin resins are preferred, and in particular, hydrogenated vinyl aromatic polymers are preferred.
  • vinyl aromatics of the above-mentioned hydrogenated vinyl aromatic polymer and monomers constituting the hydrogenated vinyl aromatic block copolymer examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene And 4-phenylstyrene vinyl naphthalene and vinyl anthracene.
  • styrene, ⁇ -methylstyrene and 4-methylstyrene are preferably used.
  • One of these vinyl aromatics may be used alone, or two or more thereof may be used in combination.
  • Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, dispersing agents, coloring agents, Flame retardants, antistatic agents, conductivity imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight regulators, antifungal agents, fungicides, fluorescent brighteners, organic diffusing agents, inorganic diffusing agents, etc. And the like.
  • the resin composition of the present invention can be suitably used as a medical plastic, for example, as a material for an infusion bag, etc., taking advantage of its excellent gas barrier properties, heat resistance, and low adsorption properties.
  • the resin composition of the present invention can be produced, for example, by a method of mechanically melt-kneading the above-mentioned components.
  • the melt-kneader used here include a single-screw extruder, a twin-screw extruder, Brabender, Banbury mixer, kneader blender, roll mill and the like.
  • the lower limit of the kneading temperature is usually 100 ° C. or more, preferably 145 ° C. or more, more preferably 160 ° C. or more.
  • the upper limit of the kneading temperature is usually 350 ° C., preferably 300 ° C., more preferably 250 ° C.
  • a multi-stage split-kneading method may be used, in which each component is kneaded at once or an arbitrary component is kneaded and then the other remaining components are added and kneaded.
  • the molded article of the present invention is a molded article obtained by molding the resin composition of the present invention described above.
  • the resin composition of the present invention may be, for example, injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, It can be processed into various molded articles by molding methods such as a blow molding method, a hollow molding method, a compression molding method, and a calendar molding method.
  • the shape of the molded body is not particularly limited, and examples thereof include a sheet, a film, a plate, a particle, a lump, a fiber, a rod, a porous body, a foam and the like, preferably a sheet, a film or a plate.
  • the stretching method include a roll method, a tenter method, a tubular method and the like.
  • surface treatment such as corona discharge treatment, flame treatment, plasma treatment, or ozone treatment that is usually used industrially can also be performed.
  • Wires, cords, covering materials such as wire harnesses, insulation sheets, displays and touch panels for office automation equipment, membrane switches, photographic covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, FDD collets , Floppy hubs, optical disk substrates in optical component fields, pickup lenses for optical disks, optical lenses, LCD substrates, PDP substrates, television screens for projection televisions, retardation films, fog lamp lenses, illumination switch lenses, sensor switch lenses, Fresnel lenses, Protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, LED reflectors, headlamp lenses in automobile parts, winkers Lens, tail lamp lens, plastic window glass, meter cover, skin, door handle, rear panel, wheel cap, visor, roof rail, sun roof, instrument panel, panels, control cable coating, air bag cover, mud guard, bumper, boots, Air hoses, lamp packings, gaskets,
  • the molded object of this invention is excellent in gas barrier property, heat resistance, and low adsorption property, it can be used suitably for a film, a sheet
  • the molded article of the present invention can be particularly suitably used as a medical plastic for an infusion bag and the like, taking advantage of its excellent gas barrier properties, heat resistance, and low adsorption properties.
  • the molded article of the present invention has the merits of being hard to adsorb molecules such as vitamins to the bag material, being excellent in heat resistance, and capable of high-temperature heat sterilization operation.
  • an adhesive composition or as a film / sheet field in which an adhesive is applied to a substrate to impart adhesiveness
  • Adhesive tapes for electric insulation, adhesive tapes for electrical insulation, adhesive tapes for electronic devices, patch films, adhesive tapes for medical and sanitary materials such as bansou base films, adhesive tapes for identification and decoration, display tapes, packaging tapes, surgical tapes, The adhesive tape for labels etc. are mentioned.
  • the use of the molded article of the present invention in the field of fiber and non-woven fabric is not particularly limited, but the following uses may be mentioned as an example.
  • canvas, tent material, hood, flexible container, leisure sheet, tarpaulin and the like by knitted fabric of these non-woven fabrics, monofilaments, flat yarns, slit tapes and the like and film / sheet laminates can be mentioned.
  • ignition residue (hereinafter sometimes simply referred to as “ignition residue”) when the above-mentioned ashing test is conducted is 0.1 mass% or less, it is evaluated as “o”, The thing exceeding 0.1 mass% was evaluated as "x”.
  • the nuclear hydrogenation progress rate was calculated by 1 H-NMR from the integrated value of an aliphatic-derived peak at around 0.5 to 2.5 ppm and an aromatic-derived peak at around 6.0 to 8.0 ppm.
  • the refractive index of the polymer containing a vinyl aromatic polymer component was measured by the following method.
  • Test specimen A 4-mm thick injection sheet cut and coated with a small amount of bromonaphthalene between the measurement surface and the sample surface.
  • Measuring device DR-M4 manufactured by Atago Co., Ltd. Measurement temperature: room temperature
  • ⁇ Catalyst preparation method> Silica (Fuji Silysia Chemical Carrier Q 30: carrier particle size 75 to 150 ⁇ m) 2.85 g of a carrier and 0.25 g of palladium chloride (Nippon Engelhard Co., Ltd.) as a palladium raw material were weighed in a 100 ml eggplant flask. 9 g of water and 6.6 ml of water were added and stirred (the amount of water added corresponds to 130% by mass of the water absorption of the silica carrier).
  • the silica support impregnated with the palladium source solution was filled in a glass tube (manufactured by Pyrex Co., Ltd.), dried under argon gas flow, cooled to room temperature, and then taken out.
  • a catalyst precursor this is referred to as a catalyst precursor.
  • the drying conditions are as follows. Gas flow rate: argon gas 83 ml / min Drying temperature: The temperature was raised from room temperature to 150 ° C. over 15 minutes, held at 150 ° C. for 1 hour, and allowed to cool to 50 ° C.
  • the catalyst precursor that had been subjected to the above-mentioned drying step was subjected to reduction treatment.
  • the reduction treatment the catalyst precursor is again charged in a glass tube (manufactured by Pyrex Corporation), and the temperature is raised from a reduction temperature of 50 ° C. to 300 ° C. over 30 minutes while flowing H 2 gas at 83 ml / min. It was carried out by holding for 2 hours at ° C. Thereafter, the flow gas was switched to argon, and allowed to cool to room temperature under a flow of 83 ml / min.
  • Example 1 Styrene-isobutylene-styrene copolymer (styrene content: 30% by mass, weight average molecular weight: 110,000, containing 820 mass ppm of Mg derived from hydrotalcite) in a 200 ml Erlenmeyer flask containing cyclohexane: "Copolymer A- It was made to melt
  • the 5% by mass Pd / SiO 2 catalyst (particle diameter 45 to 75 ⁇ m) and the to-be-treated polymer solution were used in an amount of 0.4% by mass with respect to the copolymer A-1 contained in the to-be-treated polymer solution
  • the mixture was placed in a Hastelloy autoclave equipped with a stirrer and mixed to obtain a raw material mixture a.
  • a solution was prepared by mixing 3 g of the copolymer A-1 treatment liquid 1 and 3 g of THF, and the solution was introduced into 30 g of methanol to precipitate a polymer.
  • the obtained polymer was dried under reduced pressure to remove the solvent in the solid. It was 44 mass ppm when Cl content in this solid polymer was measured. Moreover, when the ignition residue of this solid polymer was measured, it was 0.01 mass% or less. Moreover, the nuclear hydrogenation progress rate of this solid polymer was 2.2 mol%, and the refractive index of this solid polymer was 1.535. Moreover, the cyclohexane solution of this solid polymer was transparent.
  • Example 2 A copolymer A- was prepared in the same manner as in Example 1 except that the total pressure in the autoclave was set to 1.1 MPa while the treatment temperature by the autoclave was set to 70 ° C., and that the treatment time was set to 8 hours. The hydrogenolysis of 1 was carried out. The measurement results of the Cl content, the ignition residue and the nuclear hydrogenation progress rate of the obtained solid polymer and the evaluation results are shown in Table 1.
  • Example 3 The hydrogenolysis of the copolymer A-1 was performed in the same manner as in Example 1 except that the treatment temperature by the autoclave was 70 ° C. and the total pressure in the autoclave was 1.1 MPa. The measurement results of the Cl content, the ignition residue and the nuclear hydrogenation progress rate of the obtained solid polymer and the evaluation results are shown in Table 1.
  • Example 4 Example except using 5% by mass Pd / SiO 2 catalyst (particle size 75 to 150 ⁇ m) instead of 5% by mass Pd / SiO 2 catalyst (particle size 45 to 75 ⁇ m) and setting the processing time to 6 hours
  • the hydrogenolysis of copolymer A-1 was carried out in the same manner as in 1.
  • the measurement results of the Cl content, the ignition residue and the nuclear hydrogenation progress rate of the obtained solid polymer and the evaluation results are shown in Table 1.
  • Example 5 Instead of 5 wt% Pd / SiO 2 catalyst (particle size 45 ⁇ 75 [mu] m), using a 5 wt% Pd / SiO 2 catalyst (particle size 75 ⁇ 150 [mu] m), autoclave processing a treatment temperature in an autoclave as 230 ° C.
  • the hydrogenolysis of copolymer A-1 was carried out in the same manner as in Example 1 except that the total internal pressure was 3 MPa.
  • the measurement results of the Cl content, the ignition residue and the nuclear hydrogenation progress rate of the obtained solid polymer and the evaluation results are shown in Table 1.
  • Example 6 Do not use 5 mass% Pd / SiO 2 catalyst (particle size 45 to 75 ⁇ m), use nitrogen gas instead of hydrogen gas, set the autoclave processing temperature to 260 ° C, and set the total pressure inside the autoclave to 3 MPa during processing
  • the heat treatment of the copolymer A-1 was performed in the same manner as in Example 1 except for the difference.
  • the catalyst and insoluble residue were separated by a filter.
  • a white matter remained on the filter after filtration, and hydrotalcite as a basic substance was removed.
  • the Cl content of the obtained solid polymer was measured, it was 100 mass ppm.
  • the corrosion risk reduction ability of this solid polymer is evaluated as " ⁇ ".
  • Comparative Example 1 The Cl content of the untreated copolymer A-1 not subjected to the hydrogenolysis treatment was measured and found to be 550 mass ppm.
  • the ignition residue of copolymer A-1 was 0.5% by mass, and the refractive index was 1.539.
  • the cyclohexane solution of the copolymer A-1 had an insoluble component and was opaque. It can be seen that when the ignition residue is more than 0.1% by mass, it tends to be opaque.
  • Comparative Example 2 In a 200 ml Erlenmeyer flask containing cyclohexane, the copolymer A-1 was dissolved to 18% by mass to obtain a polymer solution to be treated. Activated carbon (Hakuto A made by Osaka Gas Chemical Co., Ltd.) and the polymer solution to be treated are placed in an eggplant flask in an amount of 0.4% by mass with respect to the copolymer A-1 contained in the polymer solution to be treated The mixture was mixed to obtain a raw material mixture b. The raw material mixture b was stirred at room temperature for 2 hours.
  • Activated carbon Haakuto A made by Osaka Gas Chemical Co., Ltd.
  • a solution was prepared by mixing 3 g of the copolymer A-1 treatment liquid 2 and 3 g of THF, and the solution was introduced into 30 g of methanol to precipitate a polymer.
  • the obtained polymer was dried under reduced pressure to remove the solvent in the solid. It was 400 mass ppm when Cl content in this solid polymer was measured. Moreover, when the ignition residue of this solid polymer was measured, it was 0.01 mass%. Further, the progress of nuclear hydrogenation of this solid polymer was 0 mol%. Moreover, the cyclohexane solution of this solid polymer was transparent.
  • the refractive index of the copolymer A-1 of Comparative Example 1 is 1.539
  • the refractive index of the solid polymer obtained by the hydrocracking treatment in Example 1 is 1.535
  • the two are equivalent. Indicated. From this, it can be seen that the polymer of the present invention is one in which the ignition residue and the Cl content are reduced without largely changing the refractive index of itself.

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Abstract

L'invention concerne un polymère contenant un composant polymère aromatique vinyle dont la teneur en chlore est inférieure ou égale à ３５０ｐｐｍ en masse, et qui présente un résidu d'incinération inférieur ou égal à 0,1% en masse lorsqu'un examen par incinération est effectué. En outre, l'invention concerne un procédé de fabrication de polymère contenant un composant polymère aromatique vinyle qui présente une étape au cours de laquelle le chlore et une substance basique sont retirées d'une solution polymère contenant un composant polymère aromatique vinyle.
PCT/JP2018/024503 2017-06-30 2018-06-28 Polymère contenant un composant polymère aromatique vinyle, et procédé de fabrication de celui-ci WO2019004333A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5536222A (en) * 1978-09-04 1980-03-13 Kuraray Co Ltd Hydrogenation of liquid olefin polymer
JPH04249501A (ja) * 1990-12-28 1992-09-04 Arakawa Chem Ind Co Ltd 高分子重合体の脱ハロゲン方法
JP3259476B2 (ja) * 1993-09-30 2002-02-25 日本ゼオン株式会社 シクロオレフィン系開環重合体水素添加物の製造方法
JP2002179728A (ja) * 2000-12-15 2002-06-26 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法
JP2004203922A (ja) * 2002-12-24 2004-07-22 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体及びその製造方法
JP2013216902A (ja) * 2011-09-29 2013-10-24 Mitsubishi Chemicals Corp 水素化ブロック共重合体及びその樹脂組成物、並びに該樹脂組成物を含むフィルム及び容器
WO2016017528A1 (fr) * 2014-07-28 2016-02-04 日本ゼオン株式会社 Corps moulé en résine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5536222A (en) * 1978-09-04 1980-03-13 Kuraray Co Ltd Hydrogenation of liquid olefin polymer
JPH04249501A (ja) * 1990-12-28 1992-09-04 Arakawa Chem Ind Co Ltd 高分子重合体の脱ハロゲン方法
JP3259476B2 (ja) * 1993-09-30 2002-02-25 日本ゼオン株式会社 シクロオレフィン系開環重合体水素添加物の製造方法
JP2002179728A (ja) * 2000-12-15 2002-06-26 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法
JP2004203922A (ja) * 2002-12-24 2004-07-22 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体及びその製造方法
JP2013216902A (ja) * 2011-09-29 2013-10-24 Mitsubishi Chemicals Corp 水素化ブロック共重合体及びその樹脂組成物、並びに該樹脂組成物を含むフィルム及び容器
WO2016017528A1 (fr) * 2014-07-28 2016-02-04 日本ゼオン株式会社 Corps moulé en résine

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