WO2025206228A1 - Copolymère de diène conjugué, son procédé de production et composition de résine de styrène résistante aux chocs - Google Patents

Copolymère de diène conjugué, son procédé de production et composition de résine de styrène résistante aux chocs

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Publication number
WO2025206228A1
WO2025206228A1 PCT/JP2025/012592 JP2025012592W WO2025206228A1 WO 2025206228 A1 WO2025206228 A1 WO 2025206228A1 JP 2025012592 W JP2025012592 W JP 2025012592W WO 2025206228 A1 WO2025206228 A1 WO 2025206228A1
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WIPO (PCT)
Prior art keywords
conjugated diene
diene polymer
polymerization
impact
less
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PCT/JP2025/012592
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English (en)
Japanese (ja)
Inventor
美紀 京
栄治 笹谷
忠大 杉本
大祐 早田
知宏 近藤
英樹 山崎
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Publication of WO2025206228A1 publication Critical patent/WO2025206228A1/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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • 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
    • C08F6/00—Post-polymerisation treatments

Definitions

  • the present invention relates to a conjugated diene polymer, a method for producing the same, and an impact-resistant styrene resin composition.
  • Styrenic resins have excellent rigidity, transparency, and processability, and are widely used in a variety of products, from everyday items to industrial goods.
  • styrene resins have the drawback of being hard but brittle and having poor impact strength.
  • unvulcanized rubber is used as a toughening agent and graft-copolymerized with styrene monomer through bulk polymerization, solution polymerization, or bulk suspension polymerization, rubber particles are dispersed in a polystyrene matrix, and the dispersed rubber absorbs impact, resulting in an impact-resistant styrene resin composition that improves on the impact strength drawback of styrene resins.
  • Impact-resistant styrene resin compositions have an excellent balance of impact strength and rigidity and are used in a variety of packaging materials and containers, primarily for home appliances and food containers.
  • gloss and impact strength are important physical properties of impact-resistant styrene-based resin compositions, and there is still a strong demand for an improved balance between these two contradictory physical properties.
  • One way to improve the balance between gloss and impact strength is to reduce the gel content of the conjugated diene polymer used as rubber particles. This is because the gel content that does not participate in graft polymerization is reduced, and all of the added conjugated diene polymer participates in graft polymerization.
  • Patent Document 1 proposes suppressing gel formation in rubber particles by blending a specific sulfur-containing phenolic stabilizer with a specific low cis-conjugated diene polymer obtained by a continuous polymerization method.
  • Patent Document 2 proposes a conjugated diene polymer with good appearance in which gel generation is reduced by lowering the temperature when monomers are fed into a polymerization reactor in a continuous polymerization method.
  • an object of the present invention is to provide a conjugated diene-based polymer capable of providing an impact-resistant styrene-based resin composition having an excellent balance between appearance, gloss, and impact strength, a method for producing the conjugated diene-based polymer, and an impact-resistant styrene-based resin composition containing the conjugated diene-based polymer.
  • the present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, the present invention is as follows.
  • a conjugated diene polymer having an integrated luminescence intensity of weak luminescence due to a chemical reaction of 150 ⁇ 10 5 cps or less, and a ⁇ b value of 4.0 or less before and after heating at 160° C. for 2 hours.
  • SV styrene solution viscosity
  • ⁇ 6> The conjugated diene polymer according to any one of ⁇ 1> to ⁇ 5>, wherein the integrated light emission amount is 40 ⁇ 10 5 cps or less.
  • ⁇ 7> ⁇ 6> The conjugated diene polymer according to any one of ⁇ 1> to ⁇ 6>, wherein the conjugated diene polymer has a molecular weight distribution (Mw/Mn) of 1.5 or more and 2.5 or less as measured by GPC (gel permeation chromatography).
  • Mw/Mn molecular weight distribution
  • ⁇ 8> The conjugated diene polymer according to any one of ⁇ 1> to ⁇ 7>, wherein the conjugated diene polymer is polybutadiene.
  • a method for producing a conjugated diene polymer comprising: a polymerization step of continuously supplying 1,3-butadiene or 1,3-butadiene and an aromatic vinyl compound, and an inert solvent to a polymerization reactor, and continuously polymerizing the mixture using an organolithium compound as an initiator to obtain an active end-containing conjugated diene polymer; and the following steps (1) to (3): (1) a deactivator addition step of adding a deactivator that deactivates the active polymerization terminal of the active terminal-containing conjugated diene polymer; (2) a neutralizer addition step of adding a neutralizer that neutralizes lithium hydroxide; and (3) a stabilizer addition step ⁇ 11> of adding a stabilizer.
  • the present invention provides a conjugated diene polymer that can provide an impact-resistant styrene-based resin composition that exhibits excellent appearance and a good balance between gloss and impact strength, as well as a method for producing the conjugated diene polymer and an impact-resistant styrene-based resin composition that contains the conjugated diene polymer.
  • the conjugated diene polymer of this embodiment has an integrated luminescence intensity of weak luminescence due to a chemical reaction of 150 ⁇ 10 5 cps or less, and a ⁇ b value of 4.0 or less before and after heating at 160° C. for 2 hours.
  • examples of the conjugated diene polymer of this embodiment include polybutadiene, and further include polybutadiene for impact-resistant styrene polymer compositions.
  • the cumulative luminescence amount of weak luminescence due to the chemical reaction of the conjugated diene polymer of this embodiment is 150 x 10 5 cps or less, preferably 75 x 10 5 cps, and more preferably 40 x 10 5 cps or less.
  • “cumulative luminescence amount of weak luminescence due to the chemical reaction of the conjugated diene polymer” means the total amount of luminescence due to the detected oxidation reaction of the conjugated diene polymer.
  • the cumulative luminescence amount can be measured, for example, by the following means.
  • the integrated light emission was measured using an ultraweak luminescence detection spectroscopy system (CLA-FS4, manufactured by Tohoku Electronics Industries Co., Ltd.) and a temperature-raising sample chamber (CLS-SH1, manufactured by Tohoku Electronics Industries Co., Ltd.).
  • CLA-FS4 manufactured by Tohoku Electronics Industries Co., Ltd.
  • CLS-SH1 manufactured by Tohoku Electronics Industries Co., Ltd.
  • the temperature was raised from the measurement starting temperature of 50°C to 200°C at a temperature-raising rate of 20°C/min in an oxygen atmosphere of 50 ml/min, and then maintained at 200°C for 10 minutes after the start of the temperature rise.
  • the total amount of light emitted during the 10 minutes after the start of the temperature rise was taken as the integrated light emission. This detects light emission due to an oxidation reaction that occurs when a conjugated diene polymer is heated in air or oxygen.
  • the phosphorus-based stabilizer is not particularly limited, and examples thereof include tris(nonylphenyl)phosphite, tris-(2,4-di-tert-butylphenyl)phosphite, and cyclic neopentanetetraylbis(octadecylphosphite).
  • the amounts of the phenolic stabilizer and the phosphorus-based stabilizer added are each preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, even more preferably 0.25 to 1.0 parts by mass, and even more preferably 0.45 to 0.8 parts by mass, relative to 100 parts by mass of the conjugated diene polymer.
  • the amount of the phenolic stabilizer and the phosphorus-based stabilizer added is preferably 0.01 parts by mass or more, and from the viewpoint of production costs, 5.0 parts by mass or less.
  • the hydrogenation rate of the butadiene moiety in the conjugated diene-based polymer is preferably 3% or more and 70% or less, more preferably 5% or more and 65% or less, and even more preferably 10% or more and 60% or less.
  • the conjugated diene polymer contains a monomer unit based on an aromatic vinyl compound
  • the hydrogenation rate of the aromatic double bonds based on the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less.
  • known hydrogenation catalysts described in JP-B Nos. 42-8704, 43-6636, 63-4841, 1-37970, 1-53851, 2-9041, and JP-A No. 8-109219 can be used as the hydrogenation catalyst.
  • Preferred hydrogenation catalysts include reaction mixtures of titanocene compounds and reducing organometallic compounds.
  • the content of the organic fatty acid is preferably 0.01 parts by mass or more and 0.5 parts by mass or less in total per 100 parts by mass of the conjugated diene polymer, from the viewpoint of ensuring the releasability of the rubber in the extruder while not inhibiting the radical polymerization during the production of the impact-resistant styrene-based resin composition.
  • conjugated diene polymer of the present embodiment When the conjugated diene polymer of the present embodiment is used for modifying a styrene resin, such as an impact-resistant polystyrene polymer composition, the conjugated diene polymer of the present embodiment may be used alone or may be blended with a linear butadiene polymer or a styrene-butadiene copolymer.
  • the impact-resistant styrene polymer composition can be produced using the conjugated diene polymer of this embodiment, for example, by bulk polymerization. Specifically, styrene and the conjugated diene polymer of this embodiment are added to a reactor equipped with a stirrer, and if necessary, a stabilizer, chain transfer agent, etc. are added, and the mixture is stirred to dissolve and prepare a pre-polymerization solution. If necessary, a catalyst such as di-tert-butyl peroxide is added to this, and the mixture is heated to polymerize, thereby obtaining the impact-resistant styrene polymer composition.
  • a catalyst such as di-tert-butyl peroxide
  • the method for producing the impact-resistant styrene-based resin composition is not particularly limited as long as consideration is given to satisfying the constituent requirements of this embodiment, and any known method can be used.
  • a preferred method is to dissolve the conjugated diene polymer (1) and the random copolymer (2) in an aromatic vinyl monomer or a mixture of a monomer copolymerizable with the aromatic vinyl monomer to obtain a rubber solution, and then carry out a polymerization step such as bulk polymerization, bulk suspension polymerization, or solution polymerization while stirring the rubber solution so as to apply a shearing stress to the rubber solution, thereby graft-polymerizing the rubber solution and obtaining an impact-resistant styrene resin composition in which rubber particles are dispersed in a matrix of an aromatic vinyl monomer or a copolymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
  • Aromatic vinyl monomers used in the manufacturing method of impact-resistant styrene resin compositions include, for example, ⁇ -alkyl-substituted styrenes such as styrene, vinylnaphthalene, ⁇ -methylstyrene, ⁇ -ethylstyrene, and ⁇ -methyl-p-methylstyrene; nuclear-alkyl-substituted styrenes such as m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylvinylbenzene, and p-tert-butylstyrene; halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene; p-hydroxystyrene, o-methoxystyrene, and the like. These may be used
  • Copolymerizable monomers other than aromatic vinyl monomers include those selected from unsaturated nitrile monomers, (meth)acrylic acid esters, and other copolymerizable monomers.
  • Examples of unsaturated nitrile monomers include, but are not limited to, acrylonitrile and methacrylonitrile. These may be used alone or in combination. Acrylonitrile is particularly preferred.
  • Examples of (meth)acrylic acid esters include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, and cyclohexyl methacrylate.
  • Methyl methacrylate is particularly preferred.
  • Other copolymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, N-methylmaleimide, and N-phenylmaleimide.
  • an inert solvent may be added to a mixed solution of the aromatic vinyl monomer or a monomer copolymerizable with the aromatic vinyl monomer to carry out polymerization.
  • inert solvents include, but are not limited to, ethylbenzene and toluene.
  • one or more polar solvents such as methyl ethyl ketone and cyclohexanone may be used.
  • the amount of these inert solvents is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, per 100 parts by mass of the aromatic vinyl monomer mixture liquid in which the conjugated diene polymer (1) and the random copolymer (2) are dissolved.
  • the polymerization when radically polymerizing an aromatic vinyl monomer dissolving a conjugated diene-based polymer (1) or a random copolymer (2), or a mixed solution of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, the polymerization may be carried out in the presence of an organic peroxide or an azo compound.
  • organic peroxides include, but are not limited to, peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane and 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane; dialkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide; diacyl peroxides such as benzoyl peroxide, m-toluoyl peroxide and lauroyl peroxide; dimyristyl peroxide; peroxydicarbonates such as diisopropyl peroxycarbonate and diisopropyl peroxydicarbonate; peroxyesters such as t-butylperoxyisopropylcarbonate, t-butylperoxyacetate, di-t-butyldiperoxyisophthalate, and t-butyl
  • azo compound examples include, but are not limited to, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and the like. These may be used alone or in combination of two or more.
  • the amount of the organic peroxide or azo compound used is preferably in the range of 10 to 1,000 ppm in the above-mentioned aromatic vinyl monomer or the mixed solution of the aromatic vinyl monomer and a monomer copolymerizable therewith.
  • chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, ⁇ -methylstyrene dimer, 1-phenylbutene-2-fluorene, dipentene, and chloroform, terpenes, and halogen compounds.
  • the impact-resistant styrene resin composition may contain known antioxidants and ultraviolet stabilizers.
  • antioxidants include, but are not limited to, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), 2,4-bis[(octylthio)methyl]-o-cresol, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], tris(dinonylphenyl)phosphite, and tris-(2,4-di-t-butylphenyl)phosphite.
  • the amount of the antioxidant added is
  • ultraviolet stabilizers include, but are not limited to, triazole-based stabilizers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole and 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole; hindered amine-based stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate; and others such as p-t-butylphenyl salicylate and 2,2′-dihydroxy-4-methoxybenzophenone. Particularly preferred are triazole-based and hindered amine-based compounds, either singly or in combination.
  • the amount of these ultraviolet stabilizers added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the impact resistant styrene-based resin composition of this embodiment.
  • the impact-resistant styrene-based resin composition of the present embodiment may be blended with a flame retardant and a flame retardant aid as needed to impart flame retardancy.
  • a flame retardant a conventionally known flame retardant can be used, and halogen-based flame retardants, phosphorus-based flame retardants, etc. are effective.
  • the flame retardant include, but are not limited to, decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A oligomer, tris-(2,3-dibromopropyl-1)isocyanurate, ammonium phosphate, red phosphorus, and tricresyl phosphate.
  • the flame retardant aid examples include, but are not limited to, antimony trioxide, antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, zinc borate, barium metaborate, and zirconium oxide.
  • the blending amount of the flame retardant is preferably 5 to 40 parts by mass per 100 parts by mass of the impact resistant styrene-based resin composition of this embodiment, and the blending amount of the flame retardant aid is preferably 2 to 20 parts by mass per 100 parts by mass of the impact resistant styrene-based resin composition of this embodiment.
  • Mooney Viscosity The Mooney viscosity was measured using a Mooney viscometer (manufactured by Ueshima Seisakusho Co., Ltd., "VR1132") in accordance with JIS K6300 (ISO289-1). The measurement temperature was 100°C. First, the sample was preheated for 1 minute, and then the rotor was rotated at 2 rpm. The torque after 4 minutes was measured and used as the Mooney viscosity (ML 1+4 ).
  • the column used consisted of three columns connected in series: a guard column: TSKguardcolumn SuperMP(HZ)-H manufactured by Tosoh Corporation, and a column: TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation.
  • An RI detector (“HLC8320" manufactured by Tosoh Corporation) was used under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL/min. 10 mg of the sample to be measured was dissolved in 20 mL of THF to prepare a measurement solution, and 200 ⁇ L of the measurement solution was injected into a GPC measurement device and measured.
  • Example 1 An autoclave (a tank-type reactor equipped with a stirrer) having an internal volume of 11 L, an internal height-to-diameter ratio (L/D) of 4, an inlet at the bottom and an outlet at the top, and equipped with a stirrer and a jacket for temperature control was used as a polymerization reactor.
  • n-butyllithium as a polymerization initiator was fed to the bottom of the reactor at a rate of 0.243 mmol/min, and the polymerization reaction was continued so that the internal temperature at the reactor outlet became 114°C (polymerization step).
  • Water as a terminator was continuously added to the active end-containing conjugated diene polymer solution flowing out from the top of the reactor in an amount of 10 g per 100 g of butadiene polymer, and the mixture was mixed using a static mixer (terminator addition step).
  • Examples 2 to 5, Example 7, Comparative Example 2 The procedure was the same as in Example 1, and the conditions were as shown in Table 1. The analytical results of the obtained samples B to E, G, and I are shown in Table 1.
  • Example 6 Using the same polymerization reactor as in the polymerization step of Example 1, 1,3-butadiene, from which impurities such as moisture had been removed in advance, were mixed at 22.9 g/min, 1,2-butadiene at 0.014 g/min, and n-hexane at 95.8 g/min and continuously supplied to the bottom of the reactor. Furthermore, n-butyllithium as a polymerization initiator was supplied to the bottom of the first reactor at a rate of 0.228 mmol/min, and the polymerization reaction was continued so that the internal temperature at the reactor outlet became 90°C (polymerization step).
  • the temperature of the second reactor was maintained at 90°C, and the linear butadiene-based polymer solution flowing out from the top of the first reactor was continuously fed from the bottom. Furthermore, tetramethoxysilane, a coupling agent, was added from the bottom of the second reactor at a rate of 0.046 mmol/min to carry out a coupling reaction (coupling step). Water, as a terminating agent, was continuously added to the branched butadiene-based polymer solution flowing out from the top of the second reactor in an amount of 20 g per 100 g of butadiene-based polymer, and the mixture was mixed in a static mixer (terminating agent addition step).
  • Example 8 Using the same polymerization reactor as in the polymerization step of Example 1, 1,3-butadiene, from which impurities such as moisture had been removed in advance, were mixed at 42.2 g/min, 1,2-butadiene at 0.008 g/min, and n-hexane at 198.8 g/min and continuously supplied to the bottom of the reactor. Furthermore, n-butyllithium as a polymerization initiator was supplied to the bottom of the first reactor at a rate of 1.20 mmol/min, and the polymerization reaction was continued so that the internal temperature at the reactor outlet became 100°C (polymerization step).
  • the temperature of the second reactor was maintained at 100°C, and the linear butadiene-based polymer solution flowing out from the top of the first reactor was continuously fed from the bottom. Furthermore, tetramethoxysilane, a coupling agent, was added from the bottom of the second reactor at a rate of 0.31 mmol/min, to carry out a coupling reaction (coupling step). Water, as a terminating agent, was continuously added to the branched butadiene-based polymer solution flowing out from the top of the second reactor in an amount of 20 g per 100 g of butadiene-based polymer, and the mixture was mixed in a static mixer (terminating agent addition step).
  • Example 9 The steps from the polymerization step to the stabilizer addition step were carried out in the same manner as in Example 1.
  • the resulting conjugated diene polymer solution was subjected to steam stripping to remove the solvent, and polyoxyethylene alkyl ether phosphate was added in an amount of 0.3 g per 100 g of the conjugated diene polymer, and the remaining water was removed using an open roll to obtain Sample M.
  • the time required to remove the remaining water using an open roll to a water content of 0.5% by mass was 40 minutes.
  • Example 1 Polymerization of an active end-containing conjugated diene polymer was carried out in the same manner as in Example 1. To the active end-containing butadiene polymer solution flowing out from the top of the reactor, without adding a neutralizing agent or a terminator, Stabilizer 1 and Stabilizer 2 were continuously added in amounts of 0.10 g and 0.10 g, respectively, per 100 g of the active end-containing conjugated diene polymer, and the mixture was mixed in a static mixer to terminate the polymerization reaction. The resulting conjugated diene polymer solution was desolvated by steam stripping, and the remaining water was evaporated using an open roll for 10 minutes to obtain Sample H. The analytical results of sample H are shown in Table 1.
  • Example 4 Polymerization of an active end-containing conjugated diene polymer was carried out in the same manner as in Example 1.
  • Stabilizer 1 and Stabilizer 2 were continuously added to the active end-containing butadiene polymer solution flowing out from the top of the reactor in amounts of 0.50 g and 0.15 g per 100 g of conjugated diene polymer, respectively, and mixed in a static mixer (stabilizer addition step).
  • water was continuously added as a terminator in an amount of 10.0 g per 100 g of active end-containing conjugated diene polymer, and mixed in a static mixer (terminator addition step).
  • An impact-resistant styrene resin composition was produced by the following bulk polymerization method. To a reactor equipped with a stirrer, 91.76 mass % of styrene and 7.97 mass % of sample A were added. Next, 0.23% by mass of n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate as a stabilizer and 0.02% by mass of t-dodecyl mercaptan as a chain transfer agent were added and dissolved with stirring to prepare a prepolymerization solution.
  • Samples A to G, L, and M produced impact-resistant styrene resin compositions with excellent appearance and a good balance of gloss and impact strength.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le copolymère de diène conjugué selon la présente invention est configuré de telle sorte que l'émission de lumière accumulée de lumière faible générée par réaction chimique n'est pas supérieure à 150 x 105 cps et la valeur Δb avant et après chauffage pendant 2 heures à 160°C n'est pas supérieure à 4,0.
PCT/JP2025/012592 2024-03-28 2025-03-27 Copolymère de diène conjugué, son procédé de production et composition de résine de styrène résistante aux chocs Pending WO2025206228A1 (fr)

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JPH09124728A (ja) * 1995-10-31 1997-05-13 Asahi Chem Ind Co Ltd ブロック共重合体を回収する方法
JPH09124727A (ja) * 1995-10-31 1997-05-13 Asahi Chem Ind Co Ltd ブロック共重合体の回収方法
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JP2014108978A (ja) * 2012-11-30 2014-06-12 Japan Elastomer Co Ltd スチレン系樹脂補強用ゴム組成物
JP2016011405A (ja) * 2014-06-30 2016-01-21 日本エラストマー株式会社 共役ジエン系重合体の製造方法
JP2021063170A (ja) * 2019-10-11 2021-04-22 日本エラストマー株式会社 耐衝撃性スチレン系樹脂組成物、及びその製造方法

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