WO2018084407A1 - Procédé de préparation d'un latex de caoutchouc à base de diène, procédé de préparation d'un copolymère greffé à base d'abs le contenant, et procédé de fabrication d'un produit moulé par injection à base d'abs - Google Patents

Procédé de préparation d'un latex de caoutchouc à base de diène, procédé de préparation d'un copolymère greffé à base d'abs le contenant, et procédé de fabrication d'un produit moulé par injection à base d'abs Download PDF

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WO2018084407A1
WO2018084407A1 PCT/KR2017/008283 KR2017008283W WO2018084407A1 WO 2018084407 A1 WO2018084407 A1 WO 2018084407A1 KR 2017008283 W KR2017008283 W KR 2017008283W WO 2018084407 A1 WO2018084407 A1 WO 2018084407A1
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Prior art keywords
weight
emulsifier
rubber latex
abs
polymerization
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PCT/KR2017/008283
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English (en)
Korean (ko)
Inventor
이진형
김영민
한수정
김유빈
정영환
정선행
석재민
허재원
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(주) 엘지화학
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Priority claimed from KR1020170088827A external-priority patent/KR102013184B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to EP17867447.9A priority Critical patent/EP3363819B1/fr
Priority to US15/780,222 priority patent/US10988604B2/en
Priority to CN201780004325.9A priority patent/CN108368189B/zh
Priority to JP2018528783A priority patent/JP6602478B2/ja
Publication of WO2018084407A1 publication Critical patent/WO2018084407A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—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
    • C08F236/04—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
    • C08F236/06—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
    • 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
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a method for producing a diene rubber latex, a method for producing an ABS-based graft copolymer comprising the same, and a method for producing an ABS-based injection molded article, and more particularly, to include a multimeric acid of an unsaturated fatty acid or a metal salt thereof.
  • a bimodal rubber latex is prepared by dividing an emulsifying agent, a crosslinking agent having a long linear chain end, and a molecular weight modifier according to the polymerization conversion ratio, thereby producing a bimodal rubber latex, and an ABS-based graft copolymer and an ABS-based injection molded article having improved mechanical properties and surface properties It relates to a method of manufacturing.
  • Thermoplastic resins have relatively good physical properties such as impact resistance, mechanical strength, moldability, glossiness, and are widely used in electric parts, electronic parts, office equipment, automobile parts, and the like.
  • ABS resins as thermoplastic resins contain, as a main component, a rubber polymer represented by polybutadiene having excellent rubber properties as an impact modifier.
  • the rubber polymer is generally prepared by emulsion polymerization of a conjugated diene monomer, an aromatic vinyl monomer and a vinyl cyan monomer are mixed with the rubber polymer, and the monomer is grafted by an emulsion polymerization method to prepare an ABS graft copolymer. can do.
  • the ABS copolymer resin prepared by the emulsion polymerization method has excellent balance between physical properties and physical properties compared to that prepared by the bulk polymerization method, and the ABS copolymer resin is mainly manufactured by the emulsion polymerization method.
  • ABS-based graft copolymer prepared as described above with a styrene-acrylonitrile copolymer (SAN), it can be produced in a variety of products through a thermoforming process.
  • SAN styrene-acrylonitrile copolymer
  • the particle diameter of the polymer is closely related to the polymerization time, and the particle diameter of the polymer has a significant influence on the mechanical properties and surface properties of the finally produced ABS resin.
  • the impact resistance of the resin is greatly influenced by the particle size and size distribution of the dispersed rubber polymer, and in order to sufficiently secure the impact resistance of the resin, the rubber polymer should have a large particle diameter.
  • thermoplastic ABS resin using a graft copolymer comprising a rubber polymer having a large particle size prepared according to the conventional method has a disadvantage in that the low temperature impact strength is severely lowered, and the emulsifier, which remains after the ABS graft polymerization, Reaction monomers, oligomers, and the like were vaporized at the surface of the resin during the high temperature thermoforming process, resulting in poor surface roughness, thereby limiting the surface properties of the resin.
  • the present invention uses a novel emulsifier that is not easily vaporized in a high temperature thermoforming process in the polymerization of rubber latex including a conjugated diene monomer, a crosslinking agent, an emulsifier and a molecular weight regulator. And controlling the content, the timing and the type of the reactants to polymerize to form a large diameter rubber polymer and a small diameter rubber polymer in a desired ratio at a specific time during the manufacture of the large diameter rubber polymer, and manufacture an ABS-based graft copolymer and an injection molded article. It is an object of the present invention to provide a method for producing a diene-based rubber latex that can provide improved mechanical and surface properties.
  • the present invention by mixing the rubber latex prepared by the method for producing the diene rubber latex with an aromatic beanie monomer and vinyl cyan monomer, graft polymerization using the novel emulsifier to improve the mechanical properties and surface properties further ABS
  • An object of the present invention is to provide a method for producing a graft copolymer.
  • the present invention includes the step of injecting a resin composition comprising an ABS-based graft copolymer and an aromatic vinyl monomer-vinyl cyan monomer according to the production method, the amount of gas generated during injection (Total Volatile Organic Compounds, TVOC) is
  • a resin composition comprising an ABS-based graft copolymer and an aromatic vinyl monomer-vinyl cyan monomer according to the production method, the amount of gas generated during injection (Total Volatile Organic Compounds, TVOC) is An object of the present invention is to provide a method for manufacturing an ABS injection molded article that can provide reduced and improved gloss and clarity.
  • the present invention includes a step of polymerization including a conjugated diene monomer, a crosslinking agent, an emulsifier and a molecular weight adjusting agent, wherein the crosslinking agent
  • R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • R 3 is an alkylene group having 1 to 10 carbon atoms
  • R 4 is 1 to 10 carbon atoms.
  • Alkyl group l is an integer of 0 to 2
  • n is an integer of 4 to 20
  • m is an integer of 2 to 4
  • m + l 4
  • the emulsifier includes a multimer acid or a metal salt thereof of an unsaturated fatty acid, which is added at a polymerization conversion rate of 30% or less or 50 to 85%. It provides a method for producing a diene rubber latex characterized in that.
  • the present invention is a diene rubber latex according to the production method 40 to 70% by weight (based on solids), an aromatic vinyl monomer 20 to 50% by weight and 100 parts by weight of the monomer mixture containing 10 to 40% by weight vinyl cyan monomer, It provides a method for producing an ABS-based graft copolymer comprising the step of graft polymerization by adding 0.05 to 3 parts by weight of an emulsifier and 0.01 to 1 part by weight of an initiator.
  • the present invention is ABS injection molding comprising the step of injecting a resin composition comprising 5 to 70% by weight of the ABS-based graft copolymer and 30 to 95% by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer according to the production method It provides a method for producing a molded article.
  • the bimodal rubber latex may include an ABS resin having improved mechanical properties such as impact resistance and surface properties such as surface glossiness and sharpness.
  • the large-diameter rubber polymer and the small-diameter rubber polymer may be formed in a desired ratio without the cumbersome process of separately preparing and mixing the large-diameter rubber polymer and the small-diameter polymer, thereby contributing to the productivity increase of the latex, as well as By using the ABS resin, there is an advantage that the mechanical properties and surface properties can be improved at the same time.
  • the present inventors use a multimeric acid of an unsaturated fatty acid or a metal salt thereof as an emulsifier when performing a polymerization reaction including a conjugated diene-based monomer, a crosslinking agent, an emulsifier and a molecular weight modifier, which is not easily vaporized under high temperature thermoforming process conditions.
  • a polymerization reaction including a conjugated diene-based monomer, a crosslinking agent, an emulsifier and a molecular weight modifier, which is not easily vaporized under high temperature thermoforming process conditions.
  • the diene-based rubber latex manufacturing method of the present invention includes a step of polymerization including a conjugated diene-based monomer, a crosslinking agent, an emulsifier and a molecular weight adjusting agent, wherein the crosslinking agent is a compound represented by the following Formula 1, before the polymerization reaction is initiated or the polymerization conversion rate
  • the emulsifier may include a multimer acid of a unsaturated fatty acid or a metal salt thereof, and may be added at a polymerization conversion rate of 30% or less or 50 to 85%. have.
  • R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • R 3 is an alkylene group having 1 to 10 carbon atoms
  • R 4 is 1 to 10 carbon atoms.
  • Alkyl groups l is an integer from 0 to 2
  • n is an integer from 4 to 20
  • m is an integer from 2 to 4
  • m + l 4.
  • the conjugated diene-based monomer may be dividedly added according to the polymerization conversion rate, and may be separately added to the polymerization start step, the polymerization conversion rate of 30 to 40%, and the polymerization conversion rate of 50 to 85%, respectively.
  • the conjugated diene monomer in accordance with the polymerization conversion time point, it is possible to easily form a diene rubber polymer having a desired particle size.
  • the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, piperi It may be at least one selected from the group containing lene and the like.
  • Another example of the present invention may further include a vinyl cyan monomer, an aromatic vinyl monomer, or both of these monomers, optionally in the conjugated diene monomer.
  • the vinyl cyan monomer may be at least one selected from the group consisting of acrylonitrile, methyl acrylonitrile, ethyl acrylonitrile, isopropyl acrylonitrile, and the like.
  • the aromatic vinyl monomer may be at least one selected from the group consisting of styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, and the like.
  • the conjugated diene monomer may be, for example, 55 to 99.8 wt%, 55 to 95 wt%, or 100% by weight of the total monomers used.
  • the aromatic vinyl monomer may be included, for example 0.1 to 40% by weight, 1.5 to 22.5% by weight, or 5 to 20% by weight
  • the vinyl cyan monomer is 0.1 to 40 It may be included in the weight%, 2.5 to 22.5% by weight, or 5 to 20% by weight, the polymerization stability, mechanical properties, gloss properties are excellent within this range.
  • the emulsifier in the present invention may be characterized in that it comprises a multimeric acid or a metal salt thereof of an unsaturated fatty acid, the multimer acid or metal salt thereof of the unsaturated fatty acid has a high molecular weight and is not easily vaporized on the resin surface during the high temperature thermoforming process. As a result, the roughness of the surface of the resin may be improved, thereby improving surface characteristics such as glossiness and sharpness.
  • the multimeric acid of the unsaturated fatty acid is a polyvalent carboxylic acid obtained by polymerizing two or more unsaturated fatty acids, and the unsaturated fatty acid is a linear, branched, cyclic, or multicyclic unsaturated fatty acid. It is assumed to include derivatives thereof.
  • the derivative means a compound in which one or two or more of hydrogens of the original compound are substituted with an alkyl group, a halogen group or a hydroxy group.
  • the composite ring means that at least two or more saturated or unsaturated cycloalkyl groups having 5 to 15 carbon atoms are included.
  • the emulsifier includes 30 to 100% by weight, 40 to 100% by weight or 50 to 100% by weight of the multimer acid or metal salt thereof of the unsaturated fatty acid based on 100% by weight of the emulsifier.
  • Gas generation amount (TVOC) by the emulsifier remaining after the latex production within the range is reduced to improve the surface properties of the final ABS resin.
  • the emulsifier may be added at 30% or less, or 50 to 85% of the polymerization conversion rate, for example, and may be more preferably added separately at 30% or less and 50 to 85% of the polymerization conversion rate.
  • a rubber polymer having a desired particle size can be formed, a large diameter polymer and a small diameter polymer can be formed at a desired ratio, and ABS is reduced by reducing the content of coagulum in the rubber latex.
  • the productivity of the system resin can be further improved.
  • the emulsifier may include a multimeric acid or a metal salt thereof of a linear, branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms, and the amount of gas generated by the emulsifier remaining in a high temperature thermoforming process by including the same. (TVOC) can be reduced to improve the surface properties of the ABS resin.
  • TVOC gas generated by the emulsifier remaining in a high temperature thermoforming process by including the same.
  • the emulsifier may include a dimer acid of an unsaturated fatty acid or a metal salt thereof, thereby improving the surface properties of the resin by reducing the amount of gas generated on the surface of the resin in a high temperature thermoforming process. Can be.
  • the emulsifier may include one or more dimer acids or metal salts thereof selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 7, which are generated on the surface of the resin in a high temperature thermoforming process Reduction of the amount of generated gas (TVOC) can improve the surface properties of the resin.
  • one or more dimer acids or metal salts thereof selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 7, which are generated on the surface of the resin in a high temperature thermoforming process Reduction of the amount of generated gas (TVOC) can improve the surface properties of the resin.
  • the emulsifier is tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, which is a mixture of 3-octenic acid, 10- undecenoic acid, oleic acid, linoleic acid, ellidinic acid, palmitoleic acid, lenolenic acid, or unsaturated carboxylic acid, It may include a dimer acid or a metal salt thereof derived from a compound selected from the group consisting of tallow fatty acid, lard fatty acid, blotting fatty acid, rice bran oil fatty acid, flaxseed oil fatty acid, but this is only an example and the scope of the present invention is limited thereto. It is not intended to be.
  • the emulsifier may include an alkali metal salt or an alkaline earth metal salt of an unsaturated fatty acid multimer acid.
  • the alkali metal salt may be, for example, a sodium salt or a potassium salt
  • the alkaline earth metal salt may be, for example, a magnesium salt or a calcium salt. It may be, but not limited to.
  • the emulsifier is an alkali metal salt of an unsaturated fatty acid multimer acid prepared by adding a hydroxide of an alkali metal such as NaOH or KOH to the multimer acid of the unsaturated fatty acid to be substituted with an alkali metal. May be).
  • the emulsifier may be a compound prepared by adding a metal salt, such as calcium salt or magnesium salt, to an alkali metal salt of the unsaturated fatty acid or the unsaturated fatty acid multimer acid, but is not limited thereto. Specify it.
  • the emulsifier in the present invention specifies that it may be possible to use a mixture of two or more of the above-described multimer acid of the unsaturated fatty acid or a metal salt thereof.
  • a crosslinking agent may be added at the time of the polymerization reaction before starting, the polymerization conversion rate of 30% or less, the polymerization conversion rate less than or equal to 20% or less or a polymerization conversion rate of 15%, in formula (I)
  • R 1 is hydrogen or C 1 -C 3 alkyl groups
  • R 2 is an alkylene group having 1 to 4 carbon atoms
  • R 3 is an alkylene group having 1 to 3 carbon atoms
  • R 4 is an alkyl group having 1 to 3 carbon atoms
  • l is an integer of 0 to 2
  • m is an integer of 2 to 4
  • m + l 4
  • the product of m and n is 8 to 60 is preferable because it can provide improved surface properties and mechanical properties.
  • R 1 is H or CH 3
  • R 2 is C 2 H 4 or C 3 H 6
  • R 3 is CH 2
  • R 4 is C 2 H 5
  • l is It is an integer of 0 to 2
  • n is an integer of 4 to 10
  • m is an integer of 3 or 4
  • m + l 4 multiplied by m and n is 12 to 40 excellent surface properties and mechanical properties It is preferable because it can provide.
  • the crosslinking agent may be added at 0.05 to 0.5 parts by weight, 0.05 to 0.35 parts by weight, or 0.1 to 0.25 parts by weight based on 100 parts by weight of the total monomers used for polymerization before the start of the polymerization or at the time of 30% or less.
  • the surface glossiness, sharpness and mechanical properties of the resin may be excellent within the above range.
  • the stability of the latex within the above range can be improved the impact strength of the resin.
  • the molecular weight modifier of the present invention is, for example, n-octylmercaptan, sec-octylmercaptan, n-nonylmercaptan, n-decylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and n-octadecylmer It may be at least one selected from the group consisting of captans, which may facilitate the formation of a rubber polymer having a desired particle size without lowering the reaction rate.
  • the molecular weight modifier may be added at 0.01 to 0.25 parts by weight, 0.05 to 0.25 parts by weight or 0.1 to 0.2 parts by weight at 40 to 75%, 45 to 65% or 50 to 60% of the polymerization conversion rate, within the above range It is possible to easily prepare a rubber polymer having a desired particle size without lowering the reaction rate.
  • the molecular weight control agent may be optionally added in 0.1 to 1 parts by weight or 0.1 to 0.5 parts by weight before the start of the polymerization reaction, the molecular weight control agent is added before the start of the polymerization reaction, for example n-decylmercaptan, n-dodecylmer It may be at least one selected from the group consisting of captan, t-dodecyl mercaptan, and n-octadecyl mercaptan.
  • the chain length of the molecular weight regulator to be added before the polymerization reaction described above and the molecular weight regulator to be added at the polymerization conversion rate of 40 to 75% is the same, the materials in the preceding order of the order of tert, iso, and normal are added before starting the polymerization. It is preferable to add the remaining material at a polymerization conversion rate of 40% to 75% after the reaction rate and the polymerization stability effect.
  • the preferred molecular weight modifier for the addition of 40 to 75% of the polymerization conversion rate is t-dodecyl mercaptan, n-dodecyl mercaptan, or n-decyl mercaptan. Can be used.
  • the diene-based rubber latex production method of the present invention may be carried out more specifically including one or more or all of the following steps:
  • the conjugated diene monomer may be preferably added to 60 to 75 parts by weight, 62 to 72 parts by weight or 65 to 70 parts by weight, for example, within the above-described range of the reaction pressure and reaction temperature It does not cause excessive rise, thereby improving the stability of the reactants to facilitate the preparation of rubber polymers having the desired particle diameter.
  • the emulsifier in the polymerization initiation step may be included, for example, 0.05 to 3 parts by weight, 0.5 to 3 parts by weight or 1 to 3 parts by weight, and excellent in the stability of the polymerization within this range, rubber latex having a desired particle size Can be prepared.
  • the emulsifier of the polymerization initiation step may be used alone of a polycarboxylic acid or a metal salt thereof, or sodium lauryl sulfate, sulfonated alkyl ester, sodium alkylbenzene sulfonate, sodium dodecyl allyl sulfosuccinate, Sodium acrylamido stearate, polyoxyethylene alkyl ether sulfate ammonium salt, alkenyl succinate dipotassium salt with 16 to 18 carbon atoms, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylphenyl ether ammonium sulfate, rosin acid metal salt, fatty acid It may be possible to use in admixture with at least one auxiliary emulsifier selected from the group consisting of metal salts, metal oleic acid salts.
  • the content thereof may be preferably less than 30 wt% or 20 wt% or less with respect to the total 100 wt% of the emulsifier, and stability of the emulsion polymerization within this range.
  • the surface characteristics and mechanical properties of the resin are improved by reducing the amount of gas generated (TVOC) generated on the surface of the resin during the high temperature thermoforming process.
  • TVOC gas generated
  • the polymerization initiation step may preferably include 0.01 to 1 parts by weight, 0.1 to 0.7 parts by weight or 0.2 to 0.4 parts by weight based on 100 parts by weight of the total monomers used in the polymerization reaction, and efficiently within this range.
  • Emulsion polymerization can be carried out.
  • Initiators include, for example, potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, diisopropylbenzenehydroperoxide, azobisisobutyronitrile, tertiary butylhydroperoxide, paramethane hydroperoxide and It may be at least one selected from the group consisting of benzoyl peroxide.
  • the polymerization initiation step may optionally include at least one redox system selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate, sodium sulfite, and the like.
  • a catalyst may be further included, and by including the catalyst, a more efficient polymerization reaction may be possible.
  • the polymerization initiation step may optionally further include an electrolyte in an amount of 0.01 to 3 parts by weight or 0.2 to 3 parts by weight based on 100 parts by weight of the total monomers used in the polymerization, and improve the stability of the latex within the above range, and A polymer having a particle diameter can be prepared.
  • the electrolyte is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , It may be at least one selected from the group consisting of Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4 .
  • the polymerization initiation step may be initiated at a temperature of 60 to 75 °C, 65 to 75 °C or 65 to 70 °C, in this case, the degree of polymerization of the conjugated diene monomer can be improved without causing overreaction.
  • the auxiliary emulsifier input step may be carried out by adding 10 to 25 parts by weight of the conjugated diene monomer and 0.1 to 1.0 parts by weight of the auxiliary emulsifier at 30 to 40% of the polymerization conversion rate, and at the time of 30 to 40% polymerization conversion rate.
  • a conjugated diene-based monomer as described above, it is possible to easily form a polymer having a desired particle size, the stability of the polymerization can be improved by the addition of the auxiliary emulsifier.
  • the step of adding the auxiliary emulsifier may be carried out by adding 15 to 20 parts by weight of the conjugated diene monomer and 0.1 to 0.8 parts by weight of the auxiliary emulsifier at 30 to 40% of the polymerization conversion rate, the desired particle size within this range It is possible to easily form a polymer having, and to improve the stability of the polymerization reaction, it is possible to further reduce the gas generation (TVOC) generated during the thermoforming process.
  • TVOC gas generation
  • the co-emulsifier may not be specific to CMC values, for example sodium lauryl sulfate, sulfonated alkylesters, sodium alkylbenzene sulfonates, sodium dodecyl allyl sulfosuccinate, sodium acrylamido stearate, polyoxy Ethylene alkylether sulfate ester ammonium salt, alkenyl succinate dipotassium salt with 16 to 18 carbon atoms, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylphenylether ammonium sulfate, rosin acid metal salt, fatty acid metal salt, oleic acid metal salt It may be one or more.
  • the addition step of the emulsifier may be added to 5 to 20 parts by weight of the conjugated diene monomer and 0.01 to 0.5 parts by weight of the emulsifier at 50 to 85%, 55 to 80% or 60 to 70% of the polymerization conversion rate, this range
  • the polymerization rate is improved in the productivity of the latex is improved, it is possible to form a large diameter polymer and a small diameter polymer in a desired ratio, and ultimately the mechanical properties and surface properties of the ABS resin is improved.
  • the addition step of the emulsifier is another example, 10 to 20 parts by weight of the conjugated diene monomer and 0.1 to 0.5 parts by weight of the emulsifier may be added at 50 to 85%, 55 to 80% or 60 to 70% of the polymerization conversion rate. Within this range, the polymerization rate is improved to improve the productivity of the latex, to form a large diameter polymer and a small diameter polymer at a desired ratio, and ultimately, the mechanical properties and surface properties of the resin are improved.
  • the emulsifier of the addition step of the emulsifier is a multimer acid or a metal salt thereof of an unsaturated fatty acid having a CMC greater than 150 mg / L, greater than 165 mg / L, greater than 175 mg / L, greater than 190 mg / L, or greater than 150 mg / L and less than 1,000 mg / L.
  • auxiliary emulsifier having a CMC of 150 mg / L or less, or a mixture of the emulsifier and the auxiliary emulsifier can be used, and excellent polymerization stability within this range to form a large diameter polymer and a small diameter polymer in a desired ratio There is an effect of improving the surface properties and impact resistance of the ABS resin.
  • the emulsifier of the additional charging step of the emulsifier comprises a secondary emulsifier of 150mg / L or less
  • the content thereof may be preferably less than 30% by weight or 20% by weight or less based on 100% by weight of the total emulsifier, this range
  • the large diameter polymer and the small diameter polymer are easily formed in a desired ratio to provide improved impact resistance, and the surface characteristics of the resin are improved by reducing the amount of gas generated (TVOC) generated on the surface of the resin during the high temperature thermoforming process. It works.
  • the co-emulsifier having a CMC of 150 mg / L or less may include a co-emulsifier having a CMC of 10 mg / L or less, a co-emulsifier having a CMC of more than 10 to 150 mg / L or less, or both of these co-emulsifiers.
  • a caliber rubber polymer can be formed at the desired ratio.
  • the auxiliary emulsifier having a CMC of 10 mg / L or less may be, for example, one or more selected from the group consisting of alkenyl succinate dipotassium salt of 16 to 18 carbon atoms, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylphenylether ammonium sulfate. .
  • the co-emulsifier having a CMC greater than 10 to 150 mg / L may be a fatty acid metal salt or an oleic acid metal salt.
  • the CMC is measured by a surface tension meter, and may be determined by measuring the surface tension while changing the concentration of an emulsifier in distilled water.
  • the polymerization may terminate the reaction at a polymerization conversion rate of 90 to 99%, 92 to 99%, or 95 to 99% to obtain a diene rubber latex.
  • a rubber latex having a high degree of polymerization and a low coagulant content may be obtained. It can be obtained in high yield.
  • the diene rubber latex prepared according to the present invention is, for example, a phosphorus including a large diameter rubber polymer having an average particle diameter of 2,600 to 5,000 mm 3 or 3,000 to 3,500 mm 3 and a small diameter rubber polymer having an average particle diameter of 200 to 800 mm 3 or 300 to 700 mm 3. It may be characterized in that the (in-situ) bimodal rubber latex, and when producing the ABS-based graft copolymer and ABS-based resin composition using the rubber latex under such conditions, the impact resistance while providing polymerization stability And surface properties can be improved.
  • In-situ bimodal rubber latex as used herein means rubber latex having a bimodal particle distribution in a single polymerization reaction, and is distinguished from physically mixing two rubber polymers having different average particle diameters.
  • the diene-based rubber latex prepared according to the present invention may have a weight ratio of the large-diameter rubber polymer and the small-diameter rubber polymer may be 98: 2 to 99.9: 0.1 or 98: 2 to 99: 1, the particle diameter within this range Eliminate the limitations and provide improved surface gloss, clarity and mechanical properties.
  • the present invention further improves the surface by reducing the amount of gas generated during the thermoforming process (TVOC) by producing a diene-based rubber latex using an emulsifier including a multimeric acid of an unsaturated fatty acid or a metal salt thereof. Gloss and clarity can be provided.
  • reaction conditions such as reaction pressure, reaction time, temperature, etc. are not particularly limited as long as they are within a range that is commonly practiced in the art to which the present invention pertains, and may be selected as appropriate.
  • the manufacturing method of the ABS-based graft copolymer according to the present invention includes, for example, 40 to 70% by weight of the diene rubber latex (based on solids), 20 to 50% by weight of aromatic vinyl monomer, and 10 to 40% by weight of vinyl cyan monomer.
  • the surface gloss and sharpness of the ABS copolymer within the above range It can provide an effect of improving physical properties, such as impact strength, low temperature impact strength.
  • the ABS-based graft copolymer manufacturing method of the present invention comprises 55 to 70% by weight of the diene rubber latex (based on solids), 20 to 35% by weight of aromatic vinyl monomer and 10 to 25% by weight of vinyl cyan monomer.
  • the step of graft polymerization by adding 0.5 to 2 parts by weight of the emulsifier and 0.05 to 0.5 parts by weight of the initiator, within the above range the surface gloss and sharpness of the ABS copolymer It can provide an effect of improving physical properties, such as impact strength, low temperature impact strength.
  • the emulsifier may be used alone of the multimeric acid of the unsaturated fatty acid or a metal salt thereof, an emulsifier for preparing a conventional ABS-based graft copolymer such as rosin acid salt, fatty acid metal salt, or a mixture of these emulsifiers. Can be.
  • the emulsifier may include a multimeric acid of an unsaturated fatty acid or a metal salt thereof in an amount of 30 to 100 wt%, 40 to 100 wt%, or 50 to 100 wt%, based on 100 wt% of the total emulsifier, within this range.
  • the stability of the graft polymerization may be improved, and the surface glossiness and sharpness may be further improved by reducing the amount of gas generated (TVOC) generated on the surface of the resin in a high temperature thermoforming process.
  • TVOC gas generated
  • the initiator may be used as an example, but not limited to tertiary butyl hydroperoxide, benzoyl peroxide, and the like.
  • the ABS-based graft copolymer manufacturing method may be performed by further including, for example, a molecular weight regulator or an oxidation-reduction catalyst.
  • the molecular weight modifier and the oxidation-reduction catalyst are not particularly limited as long as they are used in the manufacture of the ABS-based graft copolymer, and may be selected and used as necessary.
  • ABS-based graft copolymer according to the manufacturing method is made of a latex, which may be provided in powder form through a conventional process such as agglomeration, aging, dehydration, drying.
  • agglomeration, aging, dehydration, drying The process of flocculation, aging, dehydration, drying and the like is not particularly limited in the case of a method commonly performed in the art.
  • reaction conditions such as reaction time, reaction temperature, pressure, time of addition of reactants, etc. are not particularly limited in the range that is commonly used in the technical field to which the present invention belongs, and may be appropriately selected according to need. .
  • ABS-based graft copolymer powder according to the manufacturing method may be mixed with SAN resin, etc., extruded, and injected to produce an ABS injection molded product.
  • a method of manufacturing an ABS injection molded article according to the present invention is to inject a resin composition comprising 5 to 70% by weight of the ABS-based graft copolymer and 30 to 95% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer. It may include a step, the mechanical properties and surface properties are excellent in the above range.
  • the manufacturing method of the ABS injection molded article according to the present invention is injected into a resin composition comprising 20 to 40% by weight of the ABS-based graft copolymer and 60 to 80% by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer. It may include the step, the mechanical properties and surface properties within the above range has an excellent effect.
  • the extrusion may be carried out under the conditions of 200 to 240 °C and 140 to 190 rpm, or 200 to 220 °C and 150 to 180 rpm, for example, it may be possible to manufacture an ABS resin having the desired physical properties within this range. have.
  • the gas generation amount may be preferably 4,000 ppm or less, 3,500 ppm or less, 2,500 ppm or less, 2,000 ppm or less, or 100 to 4,000 ppm or less, and within this range, the surface gloss and sharpness of the injection molded product There is an effect to be improved.
  • the gas generation amount (TVOC) during the injection is a total amount of volatile organic compounds (VOCs) generated at 250 ° C. for 1 hour with respect to 1 g of the pellet extruded ABS-based graft copolymer using HS-GC / MSD. It is measured by analyzing.
  • the injection may be carried out under the conditions of 200 to 230 °C and 70 to 90 bar, or 200 to 220 °C and 70 to 80 bar, for example, the production of ABS-based injection molded article having the desired mechanical properties within this range It may be possible.
  • the ABS injection molded article manufactured according to the present invention can achieve high glossiness (45 °) of 95.5 or more, 96.5 or more, or 97 or more, and the reflection haze (sharpness) of 2.0 or less, 1.7 or less, or 1.5 or less. It can be characterized by having.
  • R 1 is H
  • R 2 is C 2 H 4
  • R 3 is CH 2
  • R 4 is C 2 H 5
  • l is 1
  • n is 5 and m is 3.
  • the average particle diameter of the prepared polymer was 3130mm 3
  • the gel content was 75%
  • the weight ratio of the large-diameter rubbery polymer and the small-diameter rubbery polymer was 98: 2.
  • the polymerization conversion rate was obtained by weighing 1.5 g of the prepared latex in a 150 ° C. hot air dryer for 15 minutes to obtain a total solid content (TSC), and was calculated using Equation 1 below.
  • the average particle size was measured using Nicomp 380HPL (US, PSS, Nicomp, Inc.) by mixing 1 g of latex with 100 g of distilled water, and then using a dynamic laser light scattering method.
  • the gel content was solidified by diluting the rubbery polymer with dilute acid or metal salt, washing, drying in a vacuum oven at 60 ° C. for 24 hours, then crushing the obtained rubber mass with scissors and putting 1 g of rubber sections in 100 g of toluene. After storing for a period of time in a dark room at room temperature, separated into sol and gel, the separated gel portion was calculated by using Equation 2 using the weight of the dried gel after drying for 6 hours in an 85 °C oven.
  • the average particle diameter and the ratio of the small diameter and the large diameter rubbery polymer were measured by counting analysis value by particle diameter in a TEM (JEM-1400, Jeol) analyzer.
  • 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.005 parts by weight of t-butyl hydroperoxide were collectively added to the reactor, and then the temperature was 80. The temperature was raised to 1 ° C. over 1 hour and then the reaction was terminated. At this time, the polymerization conversion rate of the obtained graft copolymer latex was 98.7%, the graft rate was 40%.
  • the graft rate was obtained by coagulating, washing and drying graft polymer latex to obtain a powder form, and 2 g of this powder was added to 300 ml of acetone and stirred for 24 hours.
  • the solution is separated with an ultracentrifuge and the separated solution is dropped in methanol to obtain an ungrafted portion, which is dried at 60 to 120 ° C. and weighed. It was calculated according to the equation (3) from the measured weights.
  • antioxidant IR1076 0.5 parts by weight was added to the graft copolymer latex, followed by dropping it with 2.0 parts by weight of H 2 SO 4 (10% aqueous solution) while maintaining the temperature of the aggregation tank at 85 ° C., followed by 97 ° C. After secondary aging at dehydrated and dried to obtain a powdery graft copolymer.
  • the graft copolymer of Example 1 was prepared in the same manner as in Example 1 except for using potassium rosinate instead of dimer acid potassium salt as an emulsifier. At this time, the polymerization conversion rate of the prepared graft copolymer latex was 98.4%, graft rate was 38%.
  • Example 2 The same method as in Example 1 except that the dimeric acid potassium salt and potassium oleate were mixed at 50: 50% by weight in the preparation of the rubbery polymer of Example 1 and the graft copolymer. Was carried out. At this time, the polymerization conversion rate of the prepared graft copolymer latex was 98.7%, the graft rate was 41%.
  • the preparation of the rubbery polymer was carried out in the same manner as in Example 1 except that the addition of the dimer acid potassium salt was omitted at the time of 61% conversion.
  • the resulting rubbery polymer latex had an average particle diameter of 3,204 mm 3, a gel content of 74%, no small diameter rubbery polymer, and only large diameter rubbery polymer.
  • the rubber polymer was prepared in the same manner as in Example 1, except that the dimeric acid potassium salt and the stearic acid potassium salt were mixed at 80: 20% by weight instead of the dimeric acid potassium salt.
  • the resulting rubbery polymer latex had an average particle diameter of 3,095 mm 3, a gel content of 76%, and a weight ratio of large-diameter rubbery polymer and small-diameter rubbery polymer (average particle diameter: 30-70 nm) was 98: 2.
  • Example 3 The same procedure as in Example 3 was carried out except that the dimeric acid potassium salt and potassium oleate were mixed at a ratio of 20: 80% by weight in the preparation of the rubbery polymer and the graft copolymer of Example 3.
  • the conversion ratio of the prepared rubber polymer was 93.5%
  • the average particle diameter was 3,070 mm 3
  • the gel content was 75%
  • the weight ratio of the large diameter rubber polymer and the small diameter rubber polymer (average particle diameter: 30-70 nm) was 97: 3.
  • the polymerization conversion rate of the prepared graft copolymer latex was 98.7% and the graft rate was 40%.
  • the resulting rubbery polymer latex had an average particle diameter of 2,795 mm 3, a gel content of 78%, and a weight ratio of large diameter rubber polymer to small diameter rubber polymer (average particle diameter: 30-70 nm) of 96: 4.
  • Izod impact strength was measured by the standard measurement method of ASTM D256 with a thickness of 1/4 ".
  • the impact strength was measured in accordance with ASTM D256 in a low temperature chamber equipped with an impact strength meter.
  • the glossiness of the specimen was measured according to the standard measurement ASTM D528 at an angle of 45 °.
  • the reflection haze was measured by adding gloss values between 17 and 19 ° and 21 to 23 ° according to standard measurement ASTM E430.
  • VOC volatile organic compounds
  • Example 1 in which an emulsifier including a dimer acid potassium salt was introduced during the production of diene rubber latex and the production of ABS graft copolymer, the gas generation amount (TVOC) during injection was considerably low, and the gloss and clarity were high. Was found to be the best.
  • TVOC gas generation amount
  • Example 4 Compared to the results of Example 1, Example 4 and Comparative Example 3 in Table 1, it was confirmed that the ratio of the large-diameter polymer and the small-diameter polymer in the latex is different depending on the timing of the emulsifier in the rubber latex production.
  • the ratio of the large diameter polymer to the small diameter polymer in latex affects the impact strength and the low temperature impact strength of the final ABS injection molded article, and Examples 1 to 3 and Examples including the large diameter polymer and the small diameter polymer in an appropriate ratio. 5 shows that not only appearance characteristics such as glossiness but also mechanical properties such as impact strength are excellent.
  • Example 1 and Comparative Example 3 in Tables 1 and 2, the ratio of the large-diameter polymer to the small-diameter polymer is different according to the addition time of the dibasic acid potassium salt in preparing the rubbery polymer, and the ratio of the small-diameter polymer is In the case of the high Comparative Example 3 it was confirmed that the impact strength and low temperature impact strength is very poor.

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Abstract

La présente invention concerne un procédé de préparation d'un latex de caoutchouc à base de diène, un procédé de préparation d'un copolymère greffé à base d'ABS le contenant, et un procédé de fabrication d'un produit moulé par injection à base d'ABS et, plus spécifiquement, un procédé de fabrication d'un latex de caoutchouc bimodal in situ, comprenant un polymère de petit diamètre et un polymère de grand diamètre, qui sont formés dans un rapport recherché, par maîtrise de la teneur, du temps d'injection et du type de réactifs pendant la polymérisation d'un monomère à base de diène conjugué, d'un agent de réticulation à longue extrémité de chaîne linéaire, d'un émulsifiant comprenant un acide multimère d'acide gras insaturé ou un sel métallique de celui-ci, et d'un agent d'ajustement de poids moléculaire ; un procédé de préparation d'un copolymère greffé à base D'ABS le contenant ; et un procédé de fabrication d'un produit moulé par injection à base d'ABS. Selon la présente invention, la stabilité de polymérisation et la productivité d'un latex peuvent être améliorées, et quand le latex est incorporé dans la préparation d'une résine à base d'ABS, des propriétés mécaniques, un brillant et une finesse améliorés peuvent être obtenus.
PCT/KR2017/008283 2016-11-01 2017-08-01 Procédé de préparation d'un latex de caoutchouc à base de diène, procédé de préparation d'un copolymère greffé à base d'abs le contenant, et procédé de fabrication d'un produit moulé par injection à base d'abs WO2018084407A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP17867447.9A EP3363819B1 (fr) 2016-11-01 2017-08-01 Procédé de préparation d'un latex de caoutchouc à base de diène, procédé de préparation d'un copolymère greffé à base d'abs le contenant, et procédé de fabrication d'un produit moulé par injection à base d'abs
US15/780,222 US10988604B2 (en) 2016-11-01 2017-08-01 Method of preparing diene-based rubber latex, method of preparing ABS-based graft copolymer and method of manufacturing injection-molded article
CN201780004325.9A CN108368189B (zh) 2016-11-01 2017-08-01 二烯类橡胶胶乳的制备方法、abs类接枝共聚物的制备方法和注塑制品的制备方法
JP2018528783A JP6602478B2 (ja) 2016-11-01 2017-08-01 ジエン系ゴムラテックスの製造方法、それを含むａｂｓ系グラフト共重合体の製造方法及びａｂｓ系射出成形品の製造方法

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KR10-2016-0144441 2016-11-01
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KR1020170088827A KR102013184B1 (ko) 2016-11-01 2017-07-13 디엔계 고무 라텍스의 제조방법, 이를 포함하는 abs계 그라프트 공중합체의 제조방법 및 abs계 사출성형품의 제조방법
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100755592B1 (ko) * 2000-03-10 2007-09-06 란세스 도이치란트 게엠베하 미분된 폴리부타디엔 라텍스의 응집 방법
US20120034478A1 (en) * 2010-08-09 2012-02-09 Basf Se Thermoplastic moulding composition with improved adhesion of electroplated metal layer
KR20140045883A (ko) * 2012-10-09 2014-04-17 주식회사 엘지화학 모노모달 입도분포의 나노 사이즈 라텍스 입자를 포함하는 아크릴계 에멀젼 점착제 조성물 및 이의 제조방법
KR20140046755A (ko) * 2012-10-11 2014-04-21 주식회사 엘지화학 충격강도가 우수한 알킬아크릴레이트-비닐방향족 화합물-비닐시안 화합물 공중합체의 제조방법 및 이를 포함하는 열가소성 수지 조성물
CN104987775A (zh) * 2015-07-17 2015-10-21 苏州世名科技股份有限公司 使用反应型乳化剂制备原液着色用包覆颜料色浆的方法
KR20160078288A (ko) * 2014-12-24 2016-07-04 주식회사 엘지화학 디엔계 고무 라텍스의 제조방법 및 이를 포함하는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100755592B1 (ko) * 2000-03-10 2007-09-06 란세스 도이치란트 게엠베하 미분된 폴리부타디엔 라텍스의 응집 방법
US20120034478A1 (en) * 2010-08-09 2012-02-09 Basf Se Thermoplastic moulding composition with improved adhesion of electroplated metal layer
KR20140045883A (ko) * 2012-10-09 2014-04-17 주식회사 엘지화학 모노모달 입도분포의 나노 사이즈 라텍스 입자를 포함하는 아크릴계 에멀젼 점착제 조성물 및 이의 제조방법
KR20140046755A (ko) * 2012-10-11 2014-04-21 주식회사 엘지화학 충격강도가 우수한 알킬아크릴레이트-비닐방향족 화합물-비닐시안 화합물 공중합체의 제조방법 및 이를 포함하는 열가소성 수지 조성물
KR20160078288A (ko) * 2014-12-24 2016-07-04 주식회사 엘지화학 디엔계 고무 라텍스의 제조방법 및 이를 포함하는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체
CN104987775A (zh) * 2015-07-17 2015-10-21 苏州世名科技股份有限公司 使用反应型乳化剂制备原液着色用包覆颜料色浆的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3363819A4 *

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