Classifications

• • 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
  • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
  • C08L27/22—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 a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—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 a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • 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
  • C08L51/04—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 rubbers
• • 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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/40—Redox systems

Definitions

• the present invention relates to a core-shell copolymer, and more particularly, to a core-shell copolymer used as an impact modifier for a thermoplastic resin composition, a method for manufacturing the same, and a thermoplastic resin composition comprising the same.
• Vinyl chloride resin is a general-purpose resin that is widely used in various fields due to its excellent physical and chemical properties.
• the vinyl chloride resin has a narrow temperature range that can be molded because the processing temperature is close to the thermal decomposition temperature.
• the melt viscosity is high and the fluidity is low, so that it adheres to the surface of the processing equipment during processing to form carbides, thereby lowering the quality of the final product.
• the vinyl chloride resin has a chlorine content of 56% to 57%
• the chlorinated vinyl chloride resin (CPVC) has a high chlorine content of 66% to 69%, so the chlorinated vinyl chloride resin has a mechanical strength compared to the vinyl chloride resin. It has the advantage of increasing, and high heat distortion temperature.
• the chlorinated vinyl chloride resin has an advantage of higher tensile strength and heat deformation temperature due to an increase in the chlorine content than the vinyl chloride resin, but there is a problem that impact strength and workability are deteriorated.
• the chlorinated vinyl chloride resin has been used by appropriately selecting additives such as impact modifiers, processing aids, stabilizers, and fillers.
• additives such as impact modifiers, processing aids, stabilizers, and fillers.
• butadiene-based impact modifiers and silicone-based impact modifiers are generally used as impact modifiers for chlorinated vinyl chloride resins, and in particular, butadiene-based impact modifiers are mainly used.
• the problem to be solved in the present invention is to apply the core-shell copolymer as an impact modifier for chlorinated vinyl chloride resin, in order to solve the problems mentioned in the technology that is the background of the invention, produced by including these It is to improve thermal stability, impact strength and tensile strength of molded products.
• the present invention is a core-shell copolymer, which is an impact modifier capable of improving the thermal stability, impact strength and tensile strength of a molded article, when manufacturing a molded article from a thermoplastic resin composition comprising a chlorinated vinyl chloride resin and an impact modifier It is an object to provide a method and a thermoplastic resin composition comprising the same.
• the present invention is a core-shell copolymer comprising a core and a shell surrounding the core, wherein the core is a repeating unit derived from a conjugated diene monomer and the following formula A crosslinking unit derived from a phosphate-based crosslinking agent represented by 1, wherein the shell is a repeating unit derived from a first alkyl (meth) acrylate monomer, a repeating unit derived from a second alkyl (meth) acrylate monomer, and sulfonate represented by the following formula (2) It contains a repeating unit derived from the ionic monomer, based on the total weight of the core-shell copolymer, the core is 68 parts by weight to 92 parts by weight, the shell is 8 parts by weight to 32 parts by weight, The swell index is 2.7 to 10.9, and the shell contains 1% to 16% by weight of repeat units derived from sulfonate-based ionic
• R 1 and R 2 are each independently an alkylene group having 1 to 30 carbon atoms, and R 3 and R 4 are each independently hydrogen or a methyl group.
• R 5 is a single bond or an alkylene group having 1 to 30 carbon atoms
• R 6 is each independently hydrogen or a methyl group
• M is potassium (K), sodium (Na) or hydrogen
• n is 0 or It is 1.
• the present invention is to prepare a core by polymerizing a core-forming mixture comprising a conjugated diene-based monomer and a phosphate-based crosslinking agent represented by Formula 1; And a repeating unit derived from a first alkyl (meth) acrylate monomer, a repeating unit derived from a second alkyl (meth) acrylate monomer, and a sulfonate-based ionic monomer represented by Formula 2 in the presence of the core prepared in the above step.
• the core is 68 parts by weight to 92 parts by weight
• the shell is 8 parts by weight to 32 parts by weight
• the swell index of the core is 2.7 to 10.9
• the shell comprises 1 to 16% by weight of the repeating unit derived from the sulfonate-based ionic monomer
• the shell It provides a method for preparing a core-shell copolymer having a weight average molecular weight of 105,000 g / mol to 645,000 g / mol.
• the present invention includes the core-shell copolymer and a chlorinated vinyl chloride resin, and the thermoplastic resin composition comprising 5 parts by weight to 10 parts by weight of the core-shell copolymer with respect to 100 parts by weight of the chlorinated vinyl chloride resin Gives
• the present invention has an effect of improving thermal stability, impact strength and tensile strength of a molded article molded from a thermoplastic resin composition comprising the same.
• the term 'monomer-derived repeating unit' may refer to a component, a structure derived from a monomer, or a substance itself, and in a specific example, upon polymerization of a polymer, a monomer to be introduced participates in a polymerization reaction and is repeated in the polymer. It may mean a unit.
• crosslinking unit derived from a crosslinking agent' may refer to a component, a structure, or a substance itself resulting from a compound used as a crosslinking agent, and crosslinking in a polymer formed by a crosslinking agent and reacting or crosslinking between polymers It may mean a cross linking part that performs a role.
• the term 'core' may mean a polymer component or a copolymer component in which a monomer forming a core is polymerized to form a core or core layer of a core-shell copolymer
• the term 'shell (shell)' is a monomer forming a shell is grafted to the core of the core-shell copolymer, the shell represents the form surrounding the core, the shell or shell layer of the core-shell copolymer It may mean a polymer component or a copolymer component.
• the core-shell copolymer according to the present invention may include a core and a shell surrounding the core.
• the core serves to improve the thermal stability and impact strength of a molded article molded from a thermoplastic resin composition containing the core-shell copolymer containing the core as an impact modifier.
• the core may include a repeating unit derived from a conjugated diene-based monomer and a crosslinking portion derived from a phosphate-based crosslinking agent.
• the conjugated diene-based monomer is a main component constituting the core, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene or 2-phenyl- 1,3-butadiene.
• the content of the repeating unit derived from the conjugated diene-based monomer may be 89% to 99.9% by weight, 90% to 99.9% by weight, or 92% to 99.9% by weight based on the total weight of the core.
• the content of the repeating unit derived from the conjugated diene-based monomer may be 89% to 99.9% by weight, 90% to 99.9% by weight, or 92% to 99.9% by weight based on the total weight of the core.
• the crosslinking unit derived from the phosphate-based crosslinking agent may be a compound represented by the following Chemical Formula 1 as a component for controlling the degree of crosslinking of the core and improving thermal stability.
• R 1 and R 2 are each independently an alkylene group having 1 to 30 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 8 carbon atoms, and R 3 and R 4 are each independently Hydrogen or methyl group.
• the phosphate-based crosslinking agent may include one or more selected from compounds represented by the following Chemical Formulas 3 and 4.
• the swell index of the core by the phosphate-based crosslinking agent may be 2.7 to 10.9, 3 to 10, or 4 to 10. Within this range, an excellent effect of thermal stability and impact strength of a molded article molded using a thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier can be achieved.
• the swelling index of the core is low, the crosslinking degree of the core is too high, and the impact strength of the molded article may deteriorate due to the brittle characteristics of the rubbery core.
• the swelling index is high, the crosslinking degree of the core is too low to absorb external impact, and thus the impact strength may be lowered.
• the 'swell index' means that the polymer is not dissolved by a solvent due to crosslinking in the polymer formed by the crosslinking agent acting and reacting, or when the polymer is swelled without being dissolved by a solvent. It may mean a degree of swelling. On the other hand, the degree of swelling (swelling index) differs depending on the degree of crosslinking (crosslinking) of the polymer.
• the swelling index can be adjusted to the content of the phosphate-based crosslinking agent, through which the thermal stability and the impact strength of the molded article molded using the thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier can be achieved. Can be.
• the core-shell copolymer of the present invention can control the swelling index by controlling the content of the phosphate-based crosslinking agent when the phosphate-based crosslinking agent is used as the crosslinking agent of the core, and can not only improve the impact strength of the molded article, but also heat Stability can be imparted.
• the content of the crosslinking part derived from the phosphate crosslinking agent may be 0.01 wt% to 11 wt%, 0.01 wt% to 9 wt%, or 0.01 wt% to 8 wt% based on the total weight of the core.
• the content of the crosslinking part derived from the phosphate crosslinking agent may be 0.01 wt% to 11 wt%, 0.01 wt% to 9 wt%, or 0.01 wt% to 8 wt% based on the total weight of the core.
• the shell serves to improve the thermal stability and processability of a molded article molded from a thermoplastic resin composition containing the core-shell copolymer containing the shell as an impact modifier.
• the shell may include a repeating unit derived from a first alkyl (meth) acrylate monomer, a repeating unit derived from a second alkyl (meth) acrylate monomer, and a repeating unit derived from a sulfonate-based ionic monomer.
• the first alkyl (meth) acrylate monomer is a component for imparting the dispersibility of the matrix by having excellent compatibility with a thermoplastic resin (eg, chlorinated vinyl chloride resin), and the second alkyl (meth) acrylate monomer is the As a component for easily dispersing the matrix by copolymerizing with the first alkyl (meth) acrylate monomer, it may be an alkyl (meth) acrylate monomer containing an alkyl group having 1 to 8 carbon atoms.
• the alkyl group having 1 to 8 carbon atoms may mean a linear alkyl group having 1 to 8 carbon atoms and a branched alkyl group having 3 to 8 carbon atoms.
• the alkyl (meth) acrylate monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate.
• first alkyl (meth) acrylate monomer and the second alkyl (meth) acrylate monomer may mean an alkyl acrylate or an alkyl methacrylate, and the first alkyl (meth) acrylate monomer and the second alkyl
• the (meth) acrylate monomers may be different from each other.
• the first alkyl (meth) acrylate monomer may mean an alkyl methacrylate
• the second alkyl (meth) acrylate monomer may mean an alkyl acrylate monomer
• the content of the repeating unit derived from the first alkyl (meth) acrylate monomer may be 76 wt% to 94.2 wt%, 79 wt% to 94 wt%, or 85 wt% to 93 wt% based on the total weight of the shell.
• the content of the repeating unit derived from the first alkyl (meth) acrylate monomer may be 76 wt% to 94.2 wt%, 79 wt% to 94 wt%, or 85 wt% to 93 wt% based on the total weight of the shell.
• the content of the repeating unit derived from the second alkyl (meth) acrylate monomer may be 4.8 wt% to 8 wt%, 5 wt% to 8 wt%, or 6 wt% to 8 wt% based on the total weight of the shell.
• the content of the repeating unit derived from the second alkyl (meth) acrylate monomer may be 4.8 wt% to 8 wt%, 5 wt% to 8 wt%, or 6 wt% to 8 wt% based on the total weight of the shell.
• the sulfonate-based ionic monomer is a component for controlling the molecular weight and glass transition temperature of the shell, and may be a compound represented by the following Chemical Formula 2.
• R 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 8 carbon atoms
• R 6 are each independently hydrogen or a methyl group
• M is Potassium (K), sodium (Na) or hydrogen
• n is 0 or 1.
• the sulfonate-based ionic monomer may include one or more selected from compounds represented by the following Chemical Formulas 5 to 8.
• the sulfonate-based ionic monomer may increase the glass transition temperature of the shell containing the sulfonate-based ionic monomer by ion bonding between the polymer sulfonate ion and the metal ion.
• the glass transition temperature of the shell may be 101 ° C to 135 ° C, 105 ° C to 130 ° C, or 108 ° C to 115 ° C. Within this range, the tensile strength and thermal stability of the molded article molded using the thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier have excellent effects.
• the content of the sulfonate-based ionic monomer may be 1% by weight to 16% by weight, 1% by weight to 13% by weight, or 1% by weight to 7% by weight based on the total weight of the shell.
• a thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier.
• the content of the sulfonate-based ionic monomer exceeds the above range, the ionic cluster is largely formed, thereby increasing the glass transition temperature of the shell, thereby causing the thermoplastic resin composition to include the core-shell copolymer as an impact modifier. Using it may cause a problem that the formability of the molded article is lowered.
• the weight average molecular weight of the shell may be 105,000 g / mol to 645,000 g / mol, 110,000 g / mol to 640,000 g / mol, or 120,000 g / mol to 500,000 g / mol.
• the mechanical strength for example, tensile strength, impact strength, etc.
• thermal stability for example, thermal stability, and processability of molded articles molded using a thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier have excellent effects. have.
• the weight-average molecular weight of the shell is less than 105,000 g / mol, mechanical strength and thermal stability may be deteriorated due to weak bonding strength between the shell-forming polymer and the matrix.
• the weight-average molecular weight of the shell exceeds 645,000 g / mol, processability may decrease due to an increase in processing viscosity.
• the weight average molecular weight of the shell can be controlled by the polymerization temperature, the content of the catalyst, and the content of the molecular weight modifier.
• the core-shell copolymer of the present invention comprising the core and the shell, the core-shell copolymer with respect to 100 parts by weight of the core, 68 parts by weight to 92 parts by weight, 69 parts by weight to 91 parts by weight, or 70 parts by weight Part to 90 parts by weight and 8 parts to 32 parts by weight of shell, 9 parts to 31 parts by weight, or 10 parts to 30 parts by weight may be included.
• 68 parts by weight to 92 parts by weight 69 parts by weight to 91 parts by weight, or 70 parts by weight Part to 90 parts by weight and 8 parts to 32 parts by weight of shell, 9 parts to 31 parts by weight, or 10 parts to 30 parts by weight
• an impact modifier there is an excellent effect of thermal stability, impact strength and tensile strength of a molded article molded using a thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier.
• the method for preparing a core-shell copolymer according to the present invention comprises the steps of: preparing a core by polymerizing a core-forming mixture comprising a conjugated diene-based monomer and a phosphate-based crosslinking agent represented by Formula 1; And a repeating unit derived from a first alkyl (meth) acrylate monomer, a repeating unit derived from a second alkyl (meth) acrylate monomer, and a sulfonate-based ionic monomer represented by Formula 2 in the presence of the core prepared in the above step.
• a core-shell copolymer wherein the core is 68 parts by weight to 92 parts by weight, based on 100 parts by weight of the core-shell copolymer.
• the shell is 8 parts by weight to 32 parts by weight, the swell index of the core is 2.7 to 10.9, and the shell contains 1 to 16% by weight of repeat units derived from sulfonate-based ionic monomers,
• the shell may have a weight average molecular weight of 105,000 g / mol to 645,000 g / mol.
• the core-shell copolymer manufacturing method may include a step of manufacturing the core and the shell, and then polymerizing the core and the shell, respectively, by producing the core and preparing the core-shell copolymer, respectively. It may be to polymerize the core of the core-shell copolymer through the step of manufacturing, and then to polymerize the shell on the core through the step of preparing the core-shell copolymer.
• the step of preparing the core may be a step of preparing a core of a core-shell copolymer, and the type and content of each monomer in the core forming mixture input in the step of preparing the core are included in the core described above It may be the same as the type and content of each monomer for forming a repeat unit derived from the monomer.
• the step of preparing the core-shell copolymer may be a step for preparing a shell of the core-shell copolymer, and each of the monomers in the shell-forming mixture introduced in the step of preparing the core-shell copolymer may be The type and content may be the same as the type and content of each monomer for forming a repeating unit derived from each monomer included in the shell described above.
• the polymerization of the step of preparing the core and the step of preparing the core-shell copolymer may be polymerized using methods such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, and the like, initiator, emulsifier, molecular weight modifier, and activation It can be polymerized by further using additives such as a redox catalyst and ion-exchanged water.
• the initiator examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl Organic peroxides such as peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutylate; Nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis isobutyrate (butyl acid) methyl, and the like, but are not limited to these initiators.
• the emulsifier may be one or more selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, for example, sulfonate-based, carboxylate-based, succinate-based, sulfosuccinate and metal salts thereof, For example, alkylbenzenesulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkylsulfonate, sodium polyoxyethylene nonylphenyl ether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium la
• Anionic emulsifiers generally used in emulsion polymerization, such as uryl sulfate, sodium dodecyl sulfosuccinate, potassium oleate and abietic acid salts;
• One or more types can be selected from the group consisting of non-ionic emulsifiers such as polyvinyl alcohol and polyoxyethylene nonylphenyl, and is not limited to these emulsifiers.
• the emulsifier may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the core-shell copolymer.
• the molecular weight modifier examples include mercaptans such as a-methylstyrene dimer, t-dodecylmercaptan, n-dodecylmercaptan, and octylmercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; Sulfur-containing compounds such as tetraethyl diuram disulfide, dipentamethylene diuram disulfide, and diisopropylkisanthogen disulfide, and the like, but are not limited to these molecular weight modifiers.
• the molecular weight modifier may be used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the core-shell copolymer.
• the activator may, for example, select one or more selected from sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium ethyl diamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium linolenic acid, and sodium sulfate. It is not limited to these activators.
• the activator may be used in an amount of 0.01 to 0.15 parts by weight based on 100 parts by weight of the core-shell copolymer.
• the redox catalyst may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediamine tetraacetate, cupric sulfate, and the like, but is not limited to these redox catalysts.
• the redox catalyst may be used in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the core-shell copolymer.
• the core and core-shell copolymers prepared in the step of manufacturing the core and the core-shell copolymer are core latex and core-shell copolymers in which the core and core-shell copolymer are dispersed in a solvent, respectively. It can be obtained in the form of a coalescence latex, and in order to obtain a core-shell copolymer in the form of a powder from the core-shell copolymer, processes such as agglomeration, aging, dehydration and drying may be carried out.
• thermoplastic resin composition according to the present invention may include the core-shell copolymer as an impact modifier, and a chlorinated vinyl chloride resin. That is, the thermoplastic resin composition may be a chlorinated vinyl chloride resin composition.
• the chlorinated vinyl chloride resin may mean that the vinyl chloride resin is chlorinated, and for example, the chlorine content in the vinyl chloride resin is higher than the chlorine content contained in the unchlorinated vinyl chloride resin. It may mean a high vinyl chloride resin of about 10% by weight or more. As a specific example, the chlorinated vinyl chloride resin contains about 66% to 69% by weight of chlorine in the vinyl chloride resin, and thus has a high tensile strength and heat deformation temperature because the chlorine content in the resin is high.
• the thermoplastic resin composition may contain 5 parts by weight to 10 parts by weight, 5 parts by weight to 9 parts by weight, or 6 parts by weight to 8 parts by weight based on 100 parts by weight of the chlorinated vinyl chloride resin. , Within this range, there is an excellent effect of thermal stability, impact strength and tensile strength of a molded article molded using a thermoplastic resin composition comprising the core-shell copolymer according to the present invention as an impact modifier.
• thermoplastic resin composition in addition to the core-shell copolymer and chlorinated vinyl chloride resin, flame retardants, lubricants, antioxidants, light stabilizers, reaction catalysts, mold release agents, within a range that does not lower the properties as necessary Additives such as pigments, antistatic agents, conductivity imparting agents, EMI shielding agents, magnetic imparting agents, crosslinking agents, antibacterial agents, processing aids, metal inactivating agents, smoke retardants, fluorine-based anti-dropping agents, inorganic fillers, glass fibers, anti-friction wear-resistant agents, coupling agents, etc. It may further include.
• the method for melt-kneading and processing the thermoplastic resin composition is not particularly limited, but for example, after primary mixing in a supermixer, one of the conventional compounding processing machines such as a twin-screw extruder, single-screw extruder, roll mill, kneader or a barbary mixer, etc. It can be melt-kneaded using a pelletizer to obtain pellets, and then dried sufficiently with a dehumidifying dryer or a hot air dryer, followed by injection processing to obtain a final molded product.
• chlorinated vinyl chloride resin 100 parts by weight of chlorinated vinyl chloride resin (HA series, Sekisui), 3.0 parts by weight of tin as a heat stabilizer, 0.3 parts by weight of antioxidant (IR1010), 1.5 parts by weight of processing aid (PA912), 5 parts by weight of filler (CaCO 3 ), After mixing 2 parts by weight of titanium dioxide and 0.2 parts by weight of wax-type lubricant (AC316A) with 7 parts by weight of the core-shell copolymer powder, the mixture was heated and heated to 110 ° C using a Henschel blender to mix it to obtain a chlorinated vinyl chloride resin composition. It was prepared.
• Example 3 in the preparation of the core, 1,3-butadiene was added at 78.0 parts by weight instead of 79.2 parts by weight, and 2 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) Except that it was carried out in the same manner as in Example 1.
• Example 1 when preparing the core, 0.8 weight parts of bis [2- (acryloxy) ethyl] phosphate (Formula 4) instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) 0.8 weight It was carried out in the same manner as in Example 1, except that it was added as a part.
• Example 1 the preparation of the core-shell copolymer, except that 0.6 parts by weight of vinyl sulfonate sodium salt (Formula 7) instead of 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5) is It was carried out in the same manner as in Example 1.
• Example 1 in the preparation of the core-shell copolymer, the polymerization temperature was 50 ° C instead of 60 ° C, 0.01 part by weight instead of 0.05 part by weight of the polymerization initiator t-butyl hydroperoxide, and 0.01% by weight instead of 0.05 part by weight of the redox activator It was carried out in the same manner as in Example 1, except that it was added as a part.
• Example 1 in the preparation of the core-shell copolymer, instead of 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5), 0.6 parts by weight of 3-sulfopropyl acrylate potassium salt (Formula 6) was added. It was carried out in the same manner as in Example 1 except for.
• Example 1 when preparing the core-shell copolymer, 3-methyl sulfopropyl methacrylate potassium salt (Formula 5) instead of 0.6 parts by weight of 2-methyl-2-propene-1-sulfonic acid sodium salt (Formula 8) It was carried out in the same manner as in Example 1, except that 0.6 parts by weight.
• Example 1 when preparing the core, 1,3-butadiene was added to 69.3 parts by weight instead of 79.2 parts by weight, and 0.7 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) was added.
• Formula 3 bis [2- (methacryloxy) ethyl] phosphate
• 27 parts by weight instead of 18 parts by weight of methyl methacrylate 27 parts by weight instead of 18 parts by weight of methyl methacrylate, 2.1 parts by weight instead of 1.4 parts by weight of butyl acrylate, 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5) It was carried out in the same manner as in Example 1, except that 0.9 parts by weight.
• Example 1 in the preparation of the core, 1,3-butadiene was added to 89.1 parts by weight instead of 79.2 parts by weight, and 0.9 parts by weight instead of 0.8 parts by weight of bis [2- (methacrylooxy) ethyl] phosphate (Formula 3) was added.
• Form 3 bis [2- (methacrylooxy) ethyl] phosphate
• 8.0 parts by weight instead of 18 parts by weight of methyl methacrylate 0.7 parts by weight instead of 1.4 parts by weight of butyl acrylate, and 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5) It was carried out in the same manner as in Example 1, except that 0.3 parts by weight.
• Example 3 when preparing the core, 1,3-butadiene was added to 73.6 parts by weight instead of 79.2 parts by weight, and 6.4 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) Except that it was carried out in the same manner as in Example 1.
• Example 3 in the preparation of the core, 1,3-butadiene was added to 79.99 parts by weight instead of 79.2 parts by weight, and 0.01 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) Except that it was carried out in the same manner as in Example 1.
• Example 1 when the core-shell copolymer was prepared, the polymerization temperature was 45 ° C instead of 60 ° C, 0.005 parts by weight instead of 0.05 parts by weight of the polymerization initiator t-butyl hydroperoxide, and 0.005% by weight instead of 0.05 parts by weight of the redox activator. It was carried out in the same manner as in Example 1, except that it was added as a part.
• Example 1 in the preparation of the core-shell copolymer, the polymerization temperature is 40 ° C instead of 60 ° C, 0.0005 parts by weight instead of 0.05 parts by weight of the polymerization initiator t-butyl hydroperoxide, and 0.001% by weight instead of 0.05 parts by weight of the redox activator It was carried out in the same manner as in Example 1, except that it was added as a part.
• Example 1 1,3-butadiene was added to 80.0 parts by weight instead of 79.2 parts by weight, and Example 1 except that bis [2- (methacryloxy) ethyl] phosphate (Formula 3) was not added. It was carried out in the same manner as.
• Example 1 in the preparation of the core-shell copolymer, butyl acrylate was added in an amount of 2.0 parts by weight instead of 1.4 parts by weight, except that the 3-sulfo propyl methacrylate potassium salt (Formula 5) was not added. It was carried out in the same manner as in Example 1.
• Example 1 when the core-shell copolymer was prepared, the polymerization temperature was 80 ° C instead of 60 ° C, 0.15 parts by weight instead of 0.05 parts by weight of the polymerization initiator t-butyl hydroperoxide, and 0.15% by weight instead of 0.05 parts by weight of the redox activator It was added in parts, and was carried out in the same manner as in Example 1 except that 0.01 t-dodecyl mercaptan, which is a molecular weight modifier, was further added.
• Example 1 in the preparation of the core, instead of 79.2 parts by weight of 1,3-butadiene, 59.4 parts by weight, and 0.6 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) instead of 0.8 parts by weight were added.
• Formula 3 bis [2- (methacryloxy) ethyl] phosphate
• 0.8 parts by weight were added.
• Example 1 in the preparation of the core-shell copolymer, 13.5 parts by weight instead of 18 parts by weight of methyl methacrylate, 0.5 parts by weight instead of butylacrylate 1.4, and potassium 3-sulfo propyl methacrylate (Formula 5) 0.6 It was carried out in the same manner as in Example 1, except that 6.0 parts by weight instead of parts by weight.
• Example 1 when the core-shell copolymer was prepared, the polymerization temperature was 40 ° C instead of 60 ° C, 0.05 part by weight of the polymerization initiator t-butyl hydroperoxide, 0.001 part by weight of dash, and 0.002 part by weight of 0.05 parts by weight of the redox activator It was carried out in the same manner as in Example 1, except that the input.
• Example 3 when preparing the core, 1,3-butadiene was added to 70.4 parts by weight instead of 79.2 parts by weight, and 9.6 parts by weight instead of 0.8 parts by weight of bis [2-methacryloxy] ethyl] phosphate (Formula 3) It was carried out in the same manner as in Example 1 except for.
• Example 1 in the preparation of the core, 0.95 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) was added at 94.05 parts by weight instead of 79.2 parts by weight of 1,3-butadiene
• 4.5 parts by weight instead of 18 parts by weight of methyl methacrylate 0.35 parts by weight instead of 1.4 parts by weight of butyl acrylate, and 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5) It was carried out in the same manner as in Example 1, except that 0.15 parts by weight.
• Example 1 when preparing the core, 0.65 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) was added at 64.35 parts by weight instead of 79.2 parts by weight of 1,3-butadiene.
• Formula 3 bis [2- (methacryloxy) ethyl] phosphate
• 31.5 parts by weight instead of 18 parts by weight of methyl methacrylate
• 2.45 parts by weight instead of 1.4 parts by weight of butyl acrylate
• 0.6 parts by weight of 3-sulfo propyl methacrylate potassium salt (Formula 5) It was carried out in the same manner as in Example 1 except for the addition of 1.05 parts by weight.
• Example 3 when the core was prepared, 1,3-butadiene was added at 79.996 parts by weight instead of 79.2 parts by weight, and 0.004 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) Except that it was carried out in the same manner as in Example 1.
• Example 3 when preparing the core, 1,3-butadiene was added to 68.0 parts by weight instead of 79.2 parts by weight, and 12.0 parts by weight instead of 0.8 parts by weight of bis [2- (methacryloxy) ethyl] phosphate (Formula 3) Except that it was carried out in the same manner as in Example 1.
• Example 1 in the preparation of the core-shell copolymer, the polymerization temperature is 70 ° C instead of 60 ° C, 0.10 part by weight instead of 0.05 part by weight of the polymerization initiator t-butyl hydroperoxide, and 0.10% by weight instead of 0.05 part by weight of the redox activator It was carried out in the same manner as in Example 1, except that it was added as a part.
• the swelling index of the cores prepared in Examples 1 to 13 and Comparative Examples 1 to 12 were measured by the following methods, and the composition of the core-shell copolymer composition was obtained with the results. It is described in Tables 1 and 2 below.
• Swelling index weight of core swollen in toluene / weight of core dry toluene
• Weight average molecular weight (Mw, g / mol) The sample in powder form was dissolved in a tetrahydrofuran (THF) solvent at a concentration of 0.25% by weight, and measured using gel permeation chromatography (Gel Permeation Chromatography).
• THF tetrahydrofuran
• the chlorinated vinyl chloride resin composition prepared in Examples and Comparative Examples was prepared in pellet form using a single extrusion kneader at 200 ° C and 30 rpm, and then injected into the pellets to prepare a physical property specimen to measure the following physical properties. It is shown in Tables 3 and 4.
• the chlorinated vinyl chloride resin composition prepared in Examples and Comparative Examples was prepared in pellet form using a single extrusion kneader at 200 ° C and 30 rpm, and the pellet was 200 ° C using a Toyoseiki Melt Index (F-B01) machine. The weight from the cylinder was measured for 10 minutes with a 10 kg load. At this time, if it is 1 g / 10min to 5 g / 10min, it means excellent.
• Heat Deflection Temperature In order to confirm thermal stability, a heat deflection temperature was measured under a load of 18.6 kg using a specimen having a thickness of 1/4 by the ASTM D648 test method. At this time, if it is 100 °C to 120 °C means excellent.
• the core-shell copolymer according to the present invention includes a crosslinking portion derived from a phosphate-based crosslinking agent in the core, and has excellent impact strength and thermal stability by controlling the crosslinking degree of the core, and sulfonate in the shell. It was confirmed that the thermal stability and processability were excellent by controlling the glass transition temperature and the weight average molecular weight of the shell including the system ionic monomer.
• Comparative Example 1 in which the core did not include a crosslinked portion derived from a phosphate-based crosslinking agent, it was confirmed that various physical properties such as impact strength, tensile strength, and thermal stability, excluding workability, were deteriorated.

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