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WO2019164176A1 - Procédé de production d'un copolymère greffé à base d'abs et procédé de production d'une composition de résine thermoplastique - Google Patents

Procédé de production d'un copolymère greffé à base d'abs et procédé de production d'une composition de résine thermoplastique Download PDF

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Publication number
WO2019164176A1
WO2019164176A1 PCT/KR2019/001793 KR2019001793W WO2019164176A1 WO 2019164176 A1 WO2019164176 A1 WO 2019164176A1 KR 2019001793 W KR2019001793 W KR 2019001793W WO 2019164176 A1 WO2019164176 A1 WO 2019164176A1
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Prior art keywords
weight
graft copolymer
latex
rubber latex
producing
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PCT/KR2019/001793
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English (en)
Korean (ko)
Inventor
전희정
김건수
김창회
김형준
채민수
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180167193A external-priority patent/KR102282816B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US16/630,830 priority Critical patent/US11820849B2/en
Priority to CN201980003592.3A priority patent/CN110914319B/zh
Priority to EP19757280.3A priority patent/EP3626754B1/fr
Publication of WO2019164176A1 publication Critical patent/WO2019164176A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a method for producing an ABS-based graft copolymer and a method for producing a thermoplastic resin composition comprising the same, and more specifically, a vinyl aromatic compound and a vinyl cyan compound are partially grafted to a small-diameter rubber latex in advance.
  • the polymer coagulant is added to a specific content range to enlarge the method for producing an ABS-based graft copolymer and the like to provide an advantage of improved stability and excellent productivity while impact resistance.
  • ABS-based copolymers represented by acrylonitrile-butadiene-styrene are widely used in various fields such as electric parts, electronic parts, office equipment, automobile parts, etc. due to their good physical properties such as impact resistance, mechanical strength, moldability, and glossiness. have.
  • ABS-based copolymers are usually prepared by preparing butadiene rubber latex and then grafting styrene and acrylonitrile.
  • physical properties such as impact resistance, mechanical strength, glossiness, etc. of the graft copolymer are greatly affected by the average particle diameter, particle size distribution, dispersion state, coagulant content, and the like of the rubber polymer latex.
  • the core technology of the high impact ABS copolymer is the average particle diameter of the polybutadiene rubber latex (PBL) of the core (core), the required particle diameter of the rubber latex is about 3,000 to 3,500 ⁇ .
  • PBL is prepared by emulsion polymerization, which is advantageous for particle size control, and such a large-diameter PBL may be prepared by, for example, preparing a small diameter (about 1,000 to 1,500 kPa) PBL by emulsion polymerization, and then enlarging it. It may also be possible to prepare directly via polymerization.
  • the large-diameter PBL manufactured directly through emulsion polymerization has an advantageous advantage in terms of impact resistance due to its narrow particle size distribution and low content of coagulant, but the average particle diameter of rubber latex is closely related to the emulsion polymerization time, in order to obtain large-diameter PBL.
  • the reaction was required for more than 30 hours, there was a problem of low process efficiency.
  • the method of making the small-diameter PBL by enlarging it can shorten the reaction time by about half, which is advantageous in terms of productivity, but usually uses an acid as a coagulant (particle enlargement agent). This is difficult, pH control is required and there was a problem that a large amount of coagulum is produced.
  • Patent Documents Korean Registered Patent 10-1225559 B1
  • an object of the present invention is to provide a ABS-based graft copolymer manufacturing method having a high productivity and improved impact resistance while ensuring the stability of the latex using a polymer flocculant.
  • the present invention is to provide a method for producing a thermoplastic resin composition comprising an ABS-based graft copolymer according to the above production method.
  • the present invention comprises a first graft polymerization step of grafting 4 to 15% by weight of the vinyl monomer to 20 to 70% by weight of the conjugated diene rubber latex; Latex agglomeration step of enlarging the rubber latex by introducing a polymer flocculant after the first graft polymerization; And a second graft polymerization step of grafting 25 to 75 wt% of the vinyl monomer to the enlarged rubber latex after the latex flocculation step, wherein the polymer flocculant comprises the conjugated diene rubber latex and vinyl base.
  • the vinyl monomers include a vinyl aromatic compound and a vinyl cyan compound
  • the enlarged rubber latex is ABS-based graphene, characterized in that the average particle size is 2800 ⁇ 5000 ⁇ It provides a process for preparing a copolymer.
  • the present invention comprises the steps of grafting 6 to 25 parts by weight of the vinyl compound to 100 parts by weight (based on solids) of the conjugated diene rubber latex; And adding 1 to 4 parts by weight of a polymer flocculant to enlarge the rubber latex; wherein the vinyl-based compound includes a vinyl aromatic compound and a vinyl cyan compound, and the enlarged rubber latex has an average particle diameter of 2800 to 5000 mm 3. It provides a method for producing a large diameter rubber latex, characterized in that the coagulant content is 0.05% by weight or less.
  • the present invention is a method for producing a thermoplastic resin composition comprising kneading and extruding 20 to 80% by weight of the ABS-based graft copolymer and 20 to 80% by weight of the non-graft resin according to the production method to provide.
  • the vinyl aromatic compound and the vinyl cyan compound are partially introduced to induce grafting, and then the polymer latex is added to a specific content range to enlarge the rubber latex.
  • the process efficiency is superior to the latex agglomeration process using a conventional polymer coagulant, and thus the physical properties may be improved while contributing to the productivity improvement.
  • according to the present invention provides an effect that the impact resistance is greatly improved without lowering the physical properties of the ABS-based graft copolymer.
  • thermoplastic resin composition prepared by using the ABS-based graft copolymer prepared according to the present invention provides an advantage that the impact strength is significantly improved while maintaining high glossiness.
  • 1 is a graph showing a change in impact strength according to the content of the vinyl monomer grafted to the rubber polymer in advance before the polymer flocculant is added.
  • the present inventors grafted some of the vinyl aromatic compound and vinyl cyan compound before grafting the flocculant into the small-diameter conjugated diene-based rubber latex, and after grafting the polymer flocculant into a specific content range to enlarge the remaining vinyl aromatic compound
  • the cohesive efficiency and productivity compared to the conventional coagulation process, while confirming that the impact strength is improved and completed the present invention based on this.
  • ABS-based graft copolymer production method of the present invention comprises a first graft polymerization step of grafting 4 to 15% by weight of the vinyl monomer to 20 to 70% by weight of the conjugated diene rubber latex as an example; Latex agglomeration step of enlarging the rubber latex by introducing a polymer flocculant after the first graft polymerization; And a second graft polymerization step of grafting 25 to 75 wt% of the vinyl monomer to the enlarged rubber latex after the latex flocculation step, wherein the polymer flocculant comprises the conjugated diene rubber latex and vinyl base.
  • the vinyl monomer includes a vinyl aromatic compound and a vinyl cyan compound
  • the enlarged rubber latex has an average particle diameter of 2800 to 5000 mm, in this case It provides the advantage of improving the cohesive efficiency and productivity while improving impact resistance.
  • the ABS-based graft copolymer manufacturing method may include a latex stabilization step of stabilizing an enlarged latex by adding a pH adjusting agent between the latex aggregation step and the second graft polymerization step.
  • ABS-based graft copolymer manufacturing method of the present disclosure will be described in detail for each step.
  • the first graft polymerization step of the present disclosure is a step of grafting some of the vinyl monomers grafted to the rubber polymer before adding the polymer flocculant.
  • the first graft polymerization step may be performed in an amount of 20 to 70 wt% of the conjugated diene rubber latex based on 100 wt% of the total conjugated diene rubber latex and the vinyl monomers used to prepare the ABS-based graft copolymer.
  • 4 to 15% by weight of the vinyl monomer may be characterized in that the grafting, there is an advantage that the impact resistance is improved while maintaining the cohesive efficiency or productivity of the latex within this range.
  • the first graft polymerization step may be characterized in that the grafting comprising 30 to 67% by weight of the conjugated diene rubber latex and 4 to 10% by weight of the vinyl monomer, in this case the gloss of the final product While excellent physical properties such as islands, there is an effect that the impact resistance is greatly improved.
  • the first graft polymerization step may include grafting including 47 to 65% by weight of the conjugated diene rubber latex and 4 to 8% by weight of the vinyl monomer, within this range. While the physical properties such as glossiness and formability of the final product are maintained high, the impact resistance is greatly improved.
  • the vinyl monomers of the present disclosure include vinyl aromatic compounds and vinyl cyan compounds, and examples thereof include 40 to 90 wt% of vinyl aromatic compounds and 10 to 60 wt% of vinyl cyan compounds; Or 60 to 80% by weight of a vinyl aromatic compound and 20 to 40% by weight of a vinyl cyan compound; and within this range, an excellent balance of physical properties such as impact resistance, surface properties, thermal stability, and moldability of the final product may be obtained. have.
  • the vinyl aromatic compound includes, for example, styrene, ⁇ -methyl styrene, vinyltoluene, chlorostyrene, and preferably styrene.
  • the vinyl cyan compound includes, for example, acrylonitrile, methacrylonitrile, and preferably acrylonitrile.
  • the conjugated diene-based rubber latex is used as a seed for preparing the graft copolymer, and an average particle diameter thereof may be, for example, 800 to 1500 kPa or 800 to 1300 kPa, and graft polymerization within this range.
  • an average particle diameter thereof may be, for example, 800 to 1500 kPa or 800 to 1300 kPa, and graft polymerization within this range.
  • the conjugated diene-based rubber latex may have an average particle diameter of 900 to 1200 mm, in which case the graft ratio and productivity are more excellent.
  • the average particle diameter of the latex in this description is measured by the dynamic laser light skating method using a Nicomp 370HPL instrument, unless otherwise specified.
  • the conjugated diene rubber latex of the present disclosure is a rubber polymer dispersed in water in the form of particles, and the rubber polymer is a polymer of a conjugated diene compound.
  • the conjugated diene-based compound may be at least one selected from, for example, 1,3-butadiene, isoprene, chloroprene, and piperylene, and may be preferably 1,3-butadiene. In this case, the impact resistance of the final product is excellent.
  • the first graft polymerization step of the present disclosure may be carried out including an initiator commonly used in the art, preferably cumene hydroperoxide, diisopropylbenzene hydroperoxide, tertiary butyl hydroperoxide It may be one or more fat-soluble peroxide initiator selected from, paramethane hydroperoxide, benzoyl peroxide.
  • an initiator commonly used in the art, preferably cumene hydroperoxide, diisopropylbenzene hydroperoxide, tertiary butyl hydroperoxide
  • It may be one or more fat-soluble peroxide initiator selected from, paramethane hydroperoxide, benzoyl peroxide.
  • the graft polymerization step may be carried out by optionally further comprising an oxidation-reduction polymerization initiator, the oxidation-reduction polymerization initiator is for example iron (II), iron (III), cobalt (II ) And at least one metal salt selected from cerium (IV); And at least one reducing agent selected from dextrose, glucose, fructose, dihydroxyacetone and polyamine.
  • an oxidation-reduction polymerization initiator is for example iron (II), iron (III), cobalt (II ) And at least one metal salt selected from cerium (IV); And at least one reducing agent selected from dextrose, glucose, fructose, dihydroxyacetone and polyamine.
  • a latex is added to the reaction system to enlarge the rubber latex.
  • a polymer coagulant is used in terms of reducing coagulant content and improving productivity.
  • the polymer coagulant is 1 to 4 parts by weight based on a total of 100 parts by weight of the conjugated diene rubber latex (based on solids) and vinyl monomers used in the reaction. , 2 to 4 parts by weight, 2 to 3 parts by weight may be added, and within this range, aggregation may be facilitated within a short time without increasing the coagulant content.
  • the content of the polymer coagulant introduced in the coagulation step is less than the above range, there is a problem in that the coagulation effect is insufficient and cannot be enlarged to a desired size, and ultimately, there is a lack of an effect of improving physical properties such as impact strength.
  • the coagulant content may increase due to excessive agglomeration, and the excess polymer coagulant may remain in the latex to decrease the impact strength, thereby completing the graft polymerization.
  • There is a problem such as increasing the waste water content by using excess water to wash the flocculant.
  • the polymer coagulant of the present disclosure may be, for example, a copolymer polymerized including an unsaturated acid compound, and specifically, may be a polymer copolymerized including an unsaturated acid compound and a monomer copolymerizable therewith.
  • the unsaturated acid compound chemically interacts with the rubber polymer dispersed in the latex stabilized with an emulsifier to reduce the stability of the latex, thereby acting to enlarge the rubber polymer.
  • the unsaturated acid compound is, for example, (meth) acrylic acid [(meth) acrylic acid], itaconic acid (itaconic acid), itaconic anhydride, crotonic acid, crotonic acid, crotonic anhydride, fumaric acid (fumaric acid), maleic acid (maleic acid), maleic anhydride (maleic anhydride), citraconic acid (citraconic acid), may include one or more selected from citraconic anhydride (citraconic anhydride).
  • the unsaturated acid compound comprises (meth) acrylic acid, more preferably methacrylic acid (methacrylic acid).
  • the coagulation effect is excellent while the formation of coagulum is reduced, thereby contributing to productivity improvement.
  • the monomer copolymerizable with the unsaturated acid compound may be at least one selected from a (meth) acrylic acid alkyl ester, an aromatic vinyl compound, and a vinyl cyan compound, and the (meth) acrylic acid alkyl ester in terms of aggregation stability and reduction of coagulant content. May be more preferred.
  • the (meth) acrylic acid alkyl ester may be preferably an alkyl having 1 to 20 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, and ethyl acrylate and n-butyl acrylate are particularly preferred.
  • Examples of the aromatic vinyl compound include styrene, ⁇ -methyl styrene, vinyltoluene, and chlorostyrene.
  • Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile.
  • the polymer coagulant may be, for example, a copolymer of a core-shell structure containing an unsaturated acid compound, in which case the coagulant content may be further reduced to contribute to productivity improvement.
  • the core-shell copolymer may include, for example, 30 to 55 wt% of the core and 45 to 70 wt% of the shell; Or 40 to 55% by weight of the core and 45 to 60% by weight of the shell; in this case, the aggregation efficiency is better and the effect of reducing the coagulant content is reduced.
  • the shell comprises an unsaturated acid compound, and as described above, the agglomeration is carried out in such a way that the unsaturated acid compound breaks the dispersion stability of the latex so that the copolymer of the core-shell structure is included in the shell.
  • the shell may further comprise a (meth) acrylic acid alkyl ester.
  • the shell may include 10-20 wt% of an unsaturated acid compound and 80-90 wt% of (meth) acrylic acid alkyl ester; Or 12-20 wt% of unsaturated acid compounds and 80-88 wt% of (meth) acrylic acid alkyl esters; Or 15 to 20% by weight of an unsaturated acid compound and 80 to 85% by weight of (meth) acrylic acid alkyl ester; in this case, the aggregation efficiency is more excellent.
  • the core comprises a meth (acrylic acid) alkyl ester and optionally further comprises an unsaturated acid compound.
  • Preferred examples of the polymer flocculant include 30 to 55 wt% of the polymerized core including 90 to 100 wt% of the (meth) acrylic acid alkyl ester and 0 to 10 wt% of the unsaturated acid compound; And 45 to 70 wt% of the polymerized shell surrounding the core, including 80 to 90 wt% of (meth) acrylic acid alkyl ester and 10 to 20 wt% of an unsaturated acid compound.
  • the coagulation effect is more excellent, but the coagulation content is less, there is an advantage of excellent productivity.
  • the polymer coagulant may be characterized in that the average particle diameter is 800 to 1500 ⁇ or 800 to 1300 ⁇ , in which case it is possible to enlarge the latex uniformly without significantly increasing the coagulant content.
  • Latex enlarged in the latex agglomeration step of the present substrate may be an average particle diameter of 2800 to 5000 ⁇ , 3000 to 4000 ⁇ or 3000 to 3500 ⁇ , and within this range to provide the effect of excellent appearance properties and impact resistance, such as gloss of the final product do.
  • the enlarged latex is in a state in which the dispersion stability is broken due to the addition of the polymer flocculant. After the enlargement is made to the desired size, it may be preferable to stabilize the latex and then perform the remaining graft polymerization.
  • Latex stabilization step of the present substrate may be characterized by stabilizing by adding a pH adjusting agent to the enlarged latex, for example, the pH adjusting agent may be preferably added 30 minutes after the polymer flocculant is added, in this case, The enlargement proceeds sufficiently to obtain a latex of the desired size.
  • the pH adjusting agent may be potassium hydroxide or sodium hydroxide, and these pH adjusting agents may be more advantageous in terms of securing stability of the latex to an aqueous solution of 1 to 10% by weight.
  • the pH adjusting agent is added in an amount of 0.01 to 1 part by weight or 0.1 to 0.5 part by weight based on 100 parts by weight of a total of 100 parts by weight of the conjugated diene-based rubber latex (based on solids) and the vinyl monomer, and the enlarged latex is It can be stably dispersed to facilitate subsequent processes, to reduce coagulation, and ultimately to provide a narrow particle size distribution, which provides excellent physical properties such as impact resistance.
  • the second graft polymerization step of the present disclosure is a step of grafting the remaining vinyl monomer to the enlarged rubber latex by grafting the remaining vinyl monomer to the enlarged latex.
  • the vinyl monomer to be added in the second graft polymerization step may be, for example, 25 to 75% by weight based on 100% by weight of the total conjugated diene rubber latex and vinyl monomer to be used to prepare the ABS-based graft copolymer. %, 25 to 60% by weight or 27 to 45% by weight, within this range can provide an advantage of excellent reaction efficiency and impact resistance of the final product.
  • the vinyl monomer of the second graft polymerization step is the same as the vinyl monomer of the first graft polymerization step, and description thereof will be omitted.
  • the ABS-based graft copolymer latex may be aggregated, dehydrated, and dried in a conventional manner to obtain an ABS-based graft copolymer powder.
  • the ABS-based graft copolymer latex may be aggregated with a metal salt flocculant and then aged, washed, dehydrated and dried to obtain a powder, but is not limited thereto.
  • metal salt flocculant examples include magnesium sulfate, aluminum sulfate, calcium chloride, calcium acetate, and the like.
  • additives or reaction conditions such as a reaction medium, an emulsifier, a catalyst, and the like are not particularly limited as long as they are known in the art to which the present invention pertains. It can select and implement suitably within the range.
  • ABS graft copolymer prepared according to the present disclosure may be provided as a thermoplastic resin composition by mixing with a matrix resin, and may be provided as a molded article through a molding process.
  • thermoplastic resin composition and the molded article manufacturing method of the present disclosure will be described.
  • the method for preparing a thermoplastic resin composition of the present disclosure may include, for example, kneading and extruding 20 to 80 wt% of the ABS-based graft copolymer and 20 to 80 wt% of the non-graft resin according to the preparation method.
  • the moldability is excellent within this range, and the impact resistance is greatly improved while maintaining the surface characteristics of the final product.
  • thermoplastic resin composition manufacturing method may include kneading and extruding 20 to 40 wt% of the ABS-based graft copolymer and 60 to 80 wt% of the non-graft resin according to the preparation method. In this case, it provides an advantage that the impact resistance is greatly improved while forming and processing is easy.
  • ABS-based graft copolymer is manufactured according to the above-described ABS-based graft copolymer manufacturing method, and thus the description thereof will be omitted.
  • the non-graft resin may be, for example, a copolymer of a vinyl aromatic compound and a vinyl cyan compound.
  • the non-graft resin may include 10 to 90 wt% of a vinyl aromatic compound and 10 to 90 wt% of a vinyl cyan compound; Or 60 to 90% by weight of a vinyl aromatic compound and 10 to 40% by weight of a vinyl cyan compound; may be a polymerized copolymer, and within this range, the mechanical properties of the ABS-based graft copolymer are not degraded. It has the advantage of excellent processability and formability.
  • Examples of the vinyl aromatic compound include styrene, ⁇ -methyl styrene, vinyltoluene, and chlorostyrene.
  • Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile.
  • the non-graft resin may be a styrene-acrylonitrile copolymer, and in this case, there is an advantage of excellent mechanical properties and processability and formability of the composition.
  • the non-graft resin may be prepared by, for example, a method selected from emulsion polymerization and bulk polymerization, but is not limited thereto. In terms of manufacturing cost, the non-graft resin may be preferably prepared through continuous bulk polymerization.
  • the kneading and extrusion is for example 220 to 300 °C and 200 to 400rpm; Or it may be carried out under the conditions of 260 to 300 °C and 200 to 300rpm; but is not limited thereto and may be carried out by appropriately selected within the range commonly practiced in the art.
  • the kneading and extrusion may be carried out using, for example, a half-barley mixer, a single screw extruder, a twin screw extruder, a kneader reactor, and the like, and is not particularly limited.
  • additives such as colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids may be added as necessary.
  • the composition is that the impact strength (1/8 ", 23 °C) measured according to ASTM D256 is 30 kgcm / cm or more, 30 to 40 kgcm / cm, 30.5 to 40 kgcm / cm, 32 to 40 kgcm / cm It may be characterized, and thus may be more suitable for thin film products requiring high impact resistance.
  • thermoplastic resin composition prepared according to the present disclosure may be manufactured into molded articles of various fields through molding processes such as injection molding and blow molding.
  • the present invention provides a large-diameter rubber latex manufacturing method of the following method, the large-diameter rubber latex prepared as described above may be used as an impact modifier by copolymerizing with a monomer copolymerizable therewith.
  • the large-diameter rubber latex manufacturing method of the present disclosure is, for example, graft polymerization by adding 6 to 25 parts by weight of a vinyl compound to 100 parts by weight (based on solids) of the conjugated diene-based rubber latex; And enlarging the rubber latex by adding 1 to 4 parts by weight of a polymer flocculant after graft polymerization, wherein the vinyl compound includes a vinyl aromatic compound and a vinyl cyan compound, and the enlarged rubber latex has an average particle diameter. 2800 to 5000 ⁇ or 3000 to 4000 ⁇ , the coagulation content may be characterized in that less than 0.05% by weight or less than 0.03% by weight, in this case there is an excellent impact reinforcement characteristics.
  • the vinyl compound is added in an amount of 6 to 25 parts by weight, 6 to 20 parts by weight, and 6 to 15 parts by weight based on 100 parts by weight (based on solids) of the conjugated diene rubber latex, and more preferably 6 to 10 parts by weight.
  • the content of the coagulant in this range is lower, and the impact reinforcing property is provided.
  • the large-diameter rubber latex manufacturing method may further comprise the step of stabilizing the enlarged latex by adding a pH adjuster after the step of enlarging the rubber latex, in this case, the particle size distribution is narrow and uniform size An enlarged rubber latex of can be obtained, which can contribute to the improvement of physical properties, and provides a good productivity due to the low content of coagulum.
  • 208 parts by weight of distilled water and 0.75 parts by weight of an emulsifier (dioctyl sulfosuccinate sodium, DOSS) were added to the reactor and stirred while heating at 80 ° C., followed by 0.2 part by weight of an initiator (potassium persulfate, KPS) and butyl acrylate (BA). ) 50 parts by weight is added and reacted for 90 minutes. Thereafter, 41 parts by weight of butyl acrylate and 9 parts by weight of methacrylic acid (MAA) were added and reacted.
  • the shell contained 41 parts by weight of BA and 9 parts by weight of MAA, and 18% by weight of the functional monomer contained in the shell).
  • ABS graft copolymer latex was aggregated with magnesium sulfate (MgSO 4 ), followed by washing, dehydration and drying to obtain ABS powder.
  • MgSO 4 magnesium sulfate
  • the mixture was added to the mixer so that the weight ratio of the ABS powder and the styrene-acrylonitrile (SAN) copolymer prepared as described above was 23:77, mixed, pelletized using an extruder, and the pellet was injected using an injection machine. To prepare a test piece for measuring the physical properties.
  • SAN styrene-acrylonitrile
  • Example 1 11.25 parts by weight of styrene and 3.75 parts by weight of acrylonitrile were added for a small amount of grafting before adding the polymer flocculant, and 6.25 parts by weight of acrylonitrile and 18.75 parts by weight of styrene were added to the enlarged large-diameter rubber latex.
  • 11.25 parts by weight of styrene and 3.75 parts by weight of acrylonitrile were added for a small amount of grafting before adding the polymer flocculant, and 6.25 parts by weight of acrylonitrile and 18.75 parts by weight of styrene were added to the enlarged large-diameter rubber latex.
  • the average particle diameter of the enlarged large diameter latex was found to be 3093 mm 3.
  • a specimen for measuring physical properties was prepared in the same manner as in Example 1 except for using the ABS graft copolymer prepared according to Example 2.
  • Example 1 Except that the amount of the polymer flocculant in Example 1 was changed from 2.2 parts by weight to 3.3 parts by weight was carried out in the same manner and conditions as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 3250 mm 3.
  • ABS graft copolymer prepared according to Example 3 was prepared in the same manner as in Example 1 for measuring the physical properties.
  • Example 1 Except for changing to 7.5 parts by weight of styrene and 2.5 parts by weight of acrylonitrile for a small amount of grafting before the polymer flocculant is added in Example 1, and to 7.5 parts by weight of acrylonitrile and 22.5 parts by weight of styrene in the enlarged large diameter rubber latex. Was carried out in the same manner and in the same manner as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 3091 mm 3.
  • ABS graft copolymer prepared according to Example 4 was prepared in the same manner as in Example 1 for measuring the physical properties.
  • ABS powder was obtained in the same manner as in Example 1.
  • a specimen for measuring physical properties was prepared in the same manner as in Example 1, except that the ABS graft copolymer prepared according to Comparative Example 1 was used.
  • Example 1 Except that the amount of the polymer flocculant in Example 1 was changed from 2.2 parts by weight to 0.5 parts by weight was carried out in the same manner and conditions as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 1950 mm 3.
  • a specimen for measuring physical properties was prepared in the same manner as in Example 1, except that the ABS graft copolymer prepared according to Comparative Example 2 was used.
  • Example 1 Except that the amount of the polymer flocculant in Example 1 was changed from 2.2 parts by weight to 4.4 parts by weight was carried out in the same manner and conditions as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 3310 ⁇ .
  • a specimen for measuring physical properties was prepared in the same manner as in Example 1 except for using the ABS graft copolymer prepared according to Comparative Example 3.
  • Example 1 Except that the acetic acid in 1 to 2 parts by weight instead of the polymer flocculant in Example 1 was carried out in the same manner and conditions as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 3100 mm 3.
  • Example 1 Except that the addition of potassium hydroxide in Example 1 was carried out in the same manner and conditions as in Example 1.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 3556 ⁇ .
  • Example 2 The same process and conditions as in Example 1 were conducted except that a polymer flocculant having a weight ratio of 10:90 of the core and the shell was added.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 2879 mm 3.
  • Example 2 The same procedure and conditions as in Example 1 were carried out except that a polymer flocculant having a weight ratio of 60:40 of the core and the shell was added.
  • the average particle diameter of the enlarged large diameter latex was confirmed to be 2806 mm3.
  • FIG. 1 is a graph showing the impact strength change according to the content (B / M) of the vinyl monomer grafted to the rubber polymer in advance before the polymer flocculant is added
  • Figure 2 is the impact strength (IMP) according to the input amount to the polymer flocculation )
  • Izod impact strength (IMP): Izod impact strength for each 1/4 "(6.4mm) thick specimen and 1/8" (3.2mm) specimen was measured at room temperature (23 ° C) in accordance with ASTM D256.
  • Average particle diameter of latex The average particle diameter of rubber in latex was measured by the dynamic laser light scattering method using the Nicomp 370HPL instrument.
  • Content of coagulum in latex The content of coagulum produced in the latex is measured by weighing the enlarged large-diameter rubber latex using 60 mesh wire mesh, drying the unfiltered coagulum, and measuring the total solid content. Calculated as a percentage of the content.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de production d'un copolymère greffé à base d'ABS et un procédé de production d'une composition de résine thermoplastique le comprenant. Plus particulièrement, la présente invention concerne un procédé de production d'un copolymère greffé à base d'ABS et un procédé de production d'une composition de résine thermoplastique le comprenant, caractérisé en ce qu'une quantité prédéterminée d'un composé aromatique de vinyle et d'un composé de vinylcyan sont ajoutés et partiellement greffés avant d'agrandir un latex de caoutchouc de petit diamètre, puis un coagulant polymère est ajouté dans une plage de teneur spécifique pour agrandir le latex de caoutchouc. Selon la présente invention, la stabilité du latex peut permettre d'obtenir un copolymère greffé à base d'ABS et présente l'avantage d'améliorer la résistance aux chocs. [Figure représentative] FIG. 1
PCT/KR2019/001793 2018-02-26 2019-02-14 Procédé de production d'un copolymère greffé à base d'abs et procédé de production d'une composition de résine thermoplastique Ceased WO2019164176A1 (fr)

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US16/630,830 US11820849B2 (en) 2018-02-26 2019-02-14 Method of preparing abs graft copolymer and method of preparing thermoplastic resin composition
CN201980003592.3A CN110914319B (zh) 2018-02-26 2019-02-14 Abs接枝共聚物的制备方法和热塑性树脂组合物的制备方法
EP19757280.3A EP3626754B1 (fr) 2018-02-26 2019-02-14 Procédé de production d'un copolymère greffé à base d'abs et procédé de production d'une composition de résine thermoplastique

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KR10-2018-0023042 2018-02-26
KR20180023042 2018-02-26
KR10-2018-0167193 2018-12-21
KR1020180167193A KR102282816B1 (ko) 2018-02-26 2018-12-21 Abs계 그라프트 공중합체의 제조방법 및 열가소성 수지 조성물의 제조방법

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US20220411559A1 (en) * 2020-09-18 2022-12-29 Lg Chem, Ltd. Method of preparing graft copolymer and method of preparing thermoplastic resin composition including the same
US20230167218A1 (en) * 2020-11-27 2023-06-01 Lg Chem, Ltd. Method for preparing graft copolymer, graft copolymer, and resin composition comprising the same

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