KR20200078065A - Method for preparing graft copolymer powder - Google Patents

Abstract

The present invention relates to a method for preparing a graft copolymer powder, which comprises the steps of: preparing a first graft copolymer latex by inputting and copolymerizing a diene-based rubbery polymer; a monomer mixture including at least two selected from the group consisting of alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer and vinylcyan-based monomer; and a compound represented by formula 1; preparing a second graft copolymer latex by adding and reacting a compound represented by formula 2 to the first graft copolymer latex; and preparing an aggregate by inputting the second graft copolymer latex to silica. According to the preparation method of the present invention, mechanical properties may be improved.

Description

Manufacturing method of graft copolymer powder{METHOD FOR PREPARING GRAFT COPOLYMER POWDER}

The present invention relates to a method for producing a graft copolymer powder, and more particularly, to a method for producing a graft copolymer powder having excellent mechanical properties.

The thermoplastic resin composition comprises a graft copolymer obtained by copolymerizing a diene-based rubbery polymer with a monomer mixture comprising an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer, and an aromatic vinyl monomer and a vinyl cyan monomer. And aromatic vinyl-based copolymers. In general, when the graft copolymer is prepared by emulsion polymerization, since the manufacturing cost is high, rather than using the graft copolymer alone, a thermoplastic resin composition mixed with an aromatic vinyl-based copolymer prepared by bulk polymerization or suspension polymerization is used. do.

On the other hand, in order to improve the functionality of the graft copolymer, the impact modifier, modified silica, is introduced during the production of the shell of the graft copolymer, thereby improving the dispersibility of the diene-based rubbery polymer, and ultimately maintaining high transparency while impact strength. , A method of greatly improving mechanical properties such as tensile strength has been proposed, but in the process of pulverizing the graft copolymer, there is a problem in that modified silica not fixed to the shell of the graft copolymer is removed. In addition, in order to improve the impact strength, a method of injecting poly(dimethylsiloxane) into the graft copolymer latex has been proposed, but similarly, a problem in that poly(dimethylsiloxane) is removed during the powdering process of the graft copolymer latex occurs. Did.

KR2017-0071845A

The present invention is to solve the above problems, to provide a method for producing a graft copolymer powder having excellent mechanical properties. When the graft copolymer powder is a transparent graft copolymer powder, it is to provide a method for producing a graft copolymer powder capable of improving mechanical properties without affecting transmittance and transparency.

In order to solve the above problems, the present invention is a diene-based rubbery polymer; A monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers; And preparing a first graft copolymer latex by adding and copolymerizing a compound represented by the following Chemical Formula 1; Preparing a second graft copolymer latex by adding and reacting a compound represented by the following Chemical Formula 2 in the first graft copolymer latex; And it provides a method for producing a graft copolymer powder comprising the step of adding the second graft copolymer latex to silica and preparing an aggregate:

<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,

R ₁ is a C ₂ to C ₁₀ alkenyl group,

R ₂ to R ₈ are each independently the same as or different from each other, and are hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group.

According to the method for producing the graft copolymer powder of the present invention, the mechanical properties of the graft copolymer powder can be excellent. In addition, when the graft copolymer powder is a transparent graft copolymer powder, mechanical properties can be improved without affecting transmittance and transparency.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the present specification and claims should not be interpreted as being limited to ordinary or dictionary meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle that it should be interpreted as a meaning and a concept consistent with the technical idea of the present invention.

The terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present invention, the average particle diameter of the diene-based rubber polymer and graft copolymer can be measured using a dynamic light scattering method, and specifically, measured using Nicomp 380 equipment (product name, manufacturer: Nicomp). Can.

In the present specification, the average particle diameter may mean an arithmetic average particle size in the particle size distribution measured by the dynamic light scattering method, that is, the average particle size of the scattering intensity.

Here, the diene-based rubbery polymer and the graft copolymer may be in the form of latex or powder.

In the present invention, the average particle diameter of silica is dispersed in methanol so that the silica has a concentration of 0.1% by weight, and after sonication with a sonicator (trade name: Malik Scientific Glass Works) for 1 hour, NICOMP 370 HPL (product name) , Manufacturer: Nicomp).

In the present invention, the alkyl (meth)acrylate-based monomer may be a C ₁ to C ₁₀ alkyl (meth)acrylate-based monomer. The C ₁ to C ₁₀ alkyl (meth)acrylate-based monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, and decyl ( It may be one or more selected from the group consisting of meth)acrylates, of which methyl methacrylate is preferred.

In the present invention, the aromatic vinyl monomer is composed of styrene, α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, p-bromo styrene, o-bromo styrene, and p-chloro styrene. It may be one or more selected from the group, of which styrene is preferred.

Vinyl cyan-based monomer in the present invention may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile This is preferred.

In the present invention, the C ₁ to C ₁₀ alkyl group may be a C ₁ to C ₁₀ linear or branched alkyl group. Specific examples of the alkyl group of C ₁ to C ₁₀ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, sec-butyl group, 1-methyl-butyl group , 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4 -Methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, t -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited to these.

In the present invention, C ₂ to C ₁₀ alkenyl groups may be C ₁ to C ₁₀ linear or branched alkenyl groups. Specific examples of the C ₂ to C ₁₀ alkenyl group include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1- Diary, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, and the like, but are not limited to these.

In the present invention, the input amount of the diene-based rubbery polymer may be based on solids.

One. Graft Method for preparing copolymer powder

Method for producing a graft copolymer powder according to an embodiment of the present invention is 1) diene-based rubbery polymer; A monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers; And preparing a first graft copolymer latex by adding and copolymerizing a compound represented by the following Chemical Formula 1; 2) preparing a second graft copolymer latex by adding and reacting a compound represented by the following Chemical Formula 2 into the first graft copolymer latex; And 3) adding the second graft copolymer latex to silica and preparing an aggregate:

<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,

R ₁ is a C ₂ to C ₁₀ alkenyl group,

R ₂ to R ₈ are each independently the same as or different from each other, and are hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group.

Hereinafter, each step of the method for producing a graft copolymer according to an embodiment of the present invention will be described in detail.

1) First Graft Preparation of copolymer latex

First, the diene-based rubbery polymer, the monomer mixture, and the compound represented by Chemical Formula 1 are added and copolymerized to prepare a first graft copolymer latex.

The diene-based rubbery polymer is prepared by emulsion polymerization of a conjugated diene-based monomer, specifically crosslinking reaction, and may be in the form of latex. The conjugated diene-based monomer may be at least one member selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene is preferred.

The diene-based rubbery polymer may have an average particle diameter of 50 to 500 nm or 80 to 400 nm, of which 80 to 400 nm is preferred. If the above-mentioned range is satisfied, both the impact strength and the surface gloss of the graft copolymer can be excellent.

The monomer mixture may include two or more selected from the group consisting of alkyl (meth)acrylate-based monomers, aromatic vinyl-based monomers, and vinyl cyan-based monomers, and the monomer mixture is used to prepare a transparent graft copolymer. An alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer may be included as essential components, and a vinyl cyan-based monomer may be further included as an optional component. In addition, in order to prepare a general graft copolymer in which transparency is not important, the monomer mixture may include an aromatic vinyl monomer and a vinyl cyan monomer as essential components.

The diene-based rubbery polymer and the monomer mixture may be added in a weight ratio of 40:60 to 60:40 or 45:55 to 55:45, of which it is preferably added in a weight ratio of 45:55 to 55:45. . If the above-described range is satisfied, the impact strength and surface gloss characteristics of the graft copolymer can be improved.

The compound represented by Chemical Formula 1 may serve to improve the mechanical properties of the graft copolymer powder. Since the compound represented by Formula 1 includes a double bond, it can participate in copolymerization. Accordingly, when copolymerized, the compound represented by Chemical Formula 1 may be chemically bonded to one or more selected from the group consisting of the components of the diene-based rubbery polymer and the monomer mixture to be fixed to the graft copolymer. Accordingly, the loss of the derivative of the compound represented by Chemical Formula 1 may be minimized in the powdering process of the graft copolymer latex, and thus the mechanical properties of the graft copolymer powder may be improved.

In Chemical Formula 1, R ₁ is preferably a C ₂ to C ₄ alkenyl group. Further, R ₂ to R ₄ are each independently the same as or different from each other, and may be a C ₁ to C ₁₀ alkyl group, and preferably a C ₁ to C ₄ alkyl group.

The compound represented by Chemical Formula 1 may be at least one selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane, and vinyl triisohydroxysilane, of which vinyl triethoxysilane is preferred.

The compound represented by Chemical Formula 1 may be added in an amount of 0.01 to 0.5 parts by weight or 0.05 to 0.3 parts by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture, and 0.05 to 0.3 parts by weight is preferable. If the above-described range is satisfied, mechanical properties, that is, tensile strength and impact strength can be improved without affecting the basic properties of the graft copolymer. In addition, when the graft copolymer is a transparent graft copolymer, mechanical properties can be improved without affecting transparency.

The copolymerization may be performed by adding one or more selected from the group consisting of an initiator, an emulsifier, an activator, a molecular weight modifier, and water.

The initiator is sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-mentanhydro peroxide, di-t-butyl peroxide, t-butylcumyl per Oxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyronitrile, azo Bis-2,4-dimethyl valeronitrile, azobiscyclohexane carbonitrile, and azobis isonoxy acid (butyl acid) methyl may be one or more selected from the group consisting of cumene hydroperoxide. The initiator may be added in an amount of 0.001 to 0.5 parts by weight or 0.01 to 0.1 parts by weight based on 100 parts by weight of the diene-based rubbery polymer and monomer mixture, and preferably 0.01 to 0.1 parts by weight. If the above-mentioned range is satisfied, a graft copolymer latex having an appropriate molecular weight and a graft rate can be obtained, and reaction time and reaction heat management can be facilitated.

The emulsifier is sodium dicyclohexyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate Nate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, sodium dodecyl sulfate, potassium octadecyl sulfate, potassium rosinate and sodium rosinate. And sodium dodecyl benzene sulfonate is preferred. The emulsifier may be added in an amount of 0.01 to 5 parts by weight or 0.1 to 3 parts by weight, and preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture. If the above-mentioned range is satisfied, a graft copolymer latex having an appropriate molecular weight, graft ratio, thermal stability and color can be obtained, and production of micelles can be facilitated.

The activator may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate unhydirose and sodium sulfate, Of these, at least one member selected from the group consisting of sodium ethylenediamine tetraacetate, ferrous sulfate and sodium aldehyde sulfoxylate is preferred. The activator may be added in an amount of 0.001 to 1 part by weight or 0.01 to 0.1 part by weight, preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture. If the above-mentioned ranges are satisfied, a graft copolymer latex having an appropriate molecular weight and graft ratio can be obtained.

The molecular weight modifier is α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram It may be at least one selected from the group consisting of di sulfide and diisopropylkisanthogen di sulfide, of which t-dodecyl mercaptan is preferred. The molecular weight modifier may be added in an amount of 0.01 to 3 parts by weight or 0.1 to 1 part by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture. If the above-mentioned range is satisfied, a graft copolymer latex having an appropriate molecular weight, PDI and graft ratio, and excellent odor characteristics can be obtained.

The water may be ion-exchanged water or distilled water.

On the other hand, in the step of preparing the first graft copolymer latex, the copolymerization may be terminated at a time when the polymerization conversion rate is 90% or more, preferably at 95% or more.

2) Second Graft Preparation of copolymer latex

Subsequently, a compound represented by Chemical Formula 2 is introduced into the first graft copolymer latex and reacted to prepare a second graft copolymer latex.

The step of preparing the second graft copolymer latex may be a step of reacting a derivative of the compound represented by Formula 1 contained in the first graft copolymer latex with a compound represented by Formula 2 below. And, the reaction may be a condensation reaction.

The compound represented by Chemical Formula 2 is a derivative of the compound represented by Chemical Formula 1 included in the first graft copolymer latex, specifically, the compound represented by Chemical Formula 1 fixed to the first graft copolymer latex The second graft copolymer latex may be prepared by modifying the first graft copolymer latex by reacting with a derivative of. And, the residue of the compound represented by Chemical Formula 1 and the reactant of the compound represented by Chemical Formula 2 bound to the second graft copolymer latex can physically fix the silica to be described later, so that silica is The loss of the graft copolymer latex in the powdering process can be minimized. If the compound represented by the formula (2) is not added, the derivative of the compound represented by the formula (1) and silica cannot be physically fixed, so that the silica is lost during the powdering process of the graft copolymer latex. , The effect of improving mechanical properties due to silica cannot be realized at all.

In Formula 2, R ₅ to R ₈ are each independently the same as or different from each other, and may be a C ₁ to C ₁₀ alkyl group, and preferably a C ₁ to C ₄ alkyl group.

The compound represented by Formula 2 is preferably one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and tetraethoxysilane is preferred.

Meanwhile, the following Reaction Formula 1 shows a reaction formula when the compound represented by Chemical Formula 1 is vinyltriethoxysilane (VTES) and the compound represented by Chemical Formula 2 is tetraethoxysilane (TEOS). The following scheme 1 is only for helping understanding of the present invention, but is not limited thereto.

<Scheme 1>

Referring to Reaction Scheme 1, it can be confirmed that the vinyl triethoxysilane is chemically bonded to the unit derived from the butadiene rubbery polymer, and the vinyltriethoxysilane derivative and the tetraethoxysilane are condensed. Here, the structural units x and y are units derived from a butadiene rubbery polymer, and the structural unit z may be a unit derived from styrene.

Meanwhile, the compound represented by Chemical Formula 2 may be added in an amount of 0.01 to 1 part by weight, 0.05 to 0.5 part by weight, or 0.05 to 0.3 part by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture, of which Preference is given to 0.05 to 0.3 parts by weight. If the above-mentioned range is satisfied, the process of pulverizing the graft copolymer latex by modifying the derivative of the compound represented by Formula 1 fixed to the shell of the graft copolymer without affecting the basic properties of the graft copolymer It can minimize the loss of the derivative of the compound represented by the formula (1).

3) Aggregates Manufacturing steps

Subsequently, the second graft copolymer latex is added to silica to prepare an aggregate.

Here, after adding the second graft copolymer latex to the silica, the step of aging may be further included.

The silica is physically firmly fixed to the residue of the compound represented by Formula 1 and the reactant of the compound represented by Formula 2 contained in the second graft copolymer latex, during the powdering process, that is, Agglomeration can be minimized during washing, dehydration and drying.

In addition, the silica may further improve the mechanical properties of the graft copolymer powder through synergistic action with the compound represented by Chemical Formula 1. In addition, if only one of the compounds represented by Chemical Formulas 1 and 2 is added, silica cannot be physically fixed to the graft copolymer latex, and thus may be lost during the powdering process.

The silica is preferably mixed with water in order to be easily mixed with the copolymer.

The silica may be hydrophilic fumed silica in which a hydroxy group is present on the surface.

The silica may have an average particle diameter of 50 to 150 nm or 70 to 130 nm, of which 70 to 130 nm is preferred. If the above-mentioned range is satisfied, it can be uniformly dispersed in the second graft copolymer latex, and the mechanical properties of the graft copolymer powder can be further improved.

The silica may be added in an amount of 0.1 to 5 parts by weight or 0.5 to 3 parts by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture, and preferably 0.5 to 3 parts by weight. If the above-described range is satisfied, the mechanical properties of the graft copolymer powder can be improved without excessive loss of silica in the powdering process of the aggregate.

A coagulant may be used in the step of preparing the agglomerate. The coagulant may be at least one selected from the group consisting of magnesium sulfate, aluminum sulfate, calcium chloride, tartaric acid and citric acid, of which calcium chloride is preferred.

On the other hand, the method of manufacturing a graft copolymer according to an embodiment of the present invention can dehydrate, wash, and dry the aggregate to produce a graft copolymer powder.

2. Graft Copolymer powder

Graft copolymer powder according to another embodiment of the present invention is a diene-based rubbery polymer; A monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers; And a graft copolymer formed by emulsion polymerization of the compound represented by Formula 1; A derivative of a compound represented by Formula 2 below; And silica:

<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,

R ₁ is a C ₂ to C ₁₀ alkenyl group,

R ₂ to R ₈ are each independently the same as or different from each other, and are hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group.

The graft copolymer powder may have a residual Si content of 0.05% by weight or more through EDS (Energy Dispersive Spectrometry) analysis using INCA Penta FETx3 of OXFORD.

The graft copolymer powder according to another embodiment of the present invention may be prepared by a method for preparing a graft copolymer powder according to an embodiment of the present invention.

3. Thermoplastic resin composition

The thermoplastic resin composition according to another embodiment of the present invention is a group consisting of a graft copolymer powder and an alkyl (meth)acrylate-based unit, an aromatic vinyl-based unit, and a vinyl cyan-based unit prepared according to an embodiment of the present invention It includes a matrix copolymer comprising two or more selected from.

The matrix copolymer may be a copolymer of a monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers.

The matrix copolymer may be at least one selected from the group consisting of methyl methacrylate/styrene copolymer, methyl methacrylate/styrene/acrylonitrile copolymer, and styrene/acrylonitrile copolymer.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

Manufacturing example One

Silica dispersion was prepared by dispersing 1 part by weight of AERODISP's W7512S (silica, average particle size: 100 nm) in 50 parts by weight of ion-exchanged water.

Example One

<Preparation of first graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, vinyl triethoxysilane 0.1 Parts by weight, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 parts by weight of cumene hydroperoxide as an initiator, sodium form as an activator The aldehyde sulfoxylate 0.048 parts by weight, disodium ethylenediaminetetraacetate 0.012 parts by weight, and ferrous sulfate 0.001 parts by weight were copolymerized while continuously being charged at 75°C for 6 hours at a constant rate. Thereafter, the copolymerization was terminated, and a first graft copolymer latex A was prepared.

<Preparation of second graft copolymer latex>

Subsequently, after heating the reactor containing the first graft copolymer latex A to 80° C., 0.05 parts by weight of tetraethoxysilane was added and reacted for 5 hours. After that, the reaction was terminated, and a second graft copolymer latex A was prepared.

<Production of aggregates>

Subsequently, the second graft copolymer latex A was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) and 51 parts by weight of the silica dispersion of Preparation Example 1 for 20 minutes, and aged for 40 minutes. Aggregate A was prepared.

<Preparation of graft copolymer powder>

Subsequently, the aggregate A was washed and dried to prepare graft copolymer powder A.

<Production of thermoplastic resin composition>

The thermoplastic resin composition A was prepared by mixing 40 parts by weight of the graft copolymer powder A and 60 parts by weight of XT500 (methyl methacrylate/styrene/acrylonitrile copolymer) manufactured by LG Chem.

Example 2

A second graft copolymer latex B was prepared in the same manner as in Example 1, except that 0.2 parts by weight of tetraethoxysilane was added instead of 0.05 parts by weight of tetraethoxysilane.

In addition, aggregate B was prepared in the same manner as in Example 1, except that the second graft copolymer latex B was used instead of the second graft copolymer latex A.

A graft copolymer powder B was prepared in the same manner as in Example 1, except that the aggregate B was used instead of the aggregate A.

In addition, a thermoplastic resin composition B was prepared in the same manner as in Example 1, except that the graft copolymer powder B was used instead of the graft copolymer powder A.

Example 3

A second graft copolymer latex C was prepared in the same manner as in Example 1, except that 0.4 parts by weight of tetraethoxysilane was added instead of 0.05 parts by weight of tetraethoxysilane.

In addition, an aggregate C was prepared in the same manner as in Example 1, except that the second graft copolymer latex C was used instead of the second graft copolymer latex A.

A graft copolymer powder C was prepared in the same manner as in Example 1, except that the aggregate C was used instead of the aggregate A.

In addition, a thermoplastic resin composition C was prepared in the same manner as in Example 1, except that the graft copolymer powder C was used instead of the graft copolymer powder A.

Example 4

A first graft copolymer latex D was prepared in the same manner as in Example 1, except that 0.5 part by weight of vinyl triethoxysilane was added instead of 0.1 part by weight of vinyl triethoxysilane.

A second graft copolymer latex D was prepared in the same manner as in Example 1, except that the first graft copolymer latex D was used instead of the first graft copolymer latex A.

In addition, an aggregate D was prepared in the same manner as in Example 1, except that the second graft copolymer latex D was used instead of the second graft copolymer latex A.

A graft copolymer powder D was prepared in the same manner as in Example 1, except that the aggregate D was used instead of the aggregate A.

In addition, a thermoplastic resin composition D was prepared in the same manner as in Example 1, except that the graft copolymer powder D was used instead of the graft copolymer powder A.

Example 5

<Preparation of first graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 100 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, vinyl triethoxysilane 0.1 Parts by weight, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight modifier, 0.04 parts by weight of cumene hydroperoxide as an initiator, sodium formaldehyde as an activator 0.048 parts by weight of sulfoxylate, 0.012 parts by weight of disodium ethylenediaminetetraacetate, and 0.001 parts by weight of ferrous sulfate were copolymerized at 75°C for 6 hours at a constant rate. After completion of the copolymerization, a first graft copolymer latex E was prepared.

<Preparation of second graft copolymer latex>

Subsequently, after heating the reactor containing the first graft copolymer latex E to 80°C, 0.2 parts by weight of tetraethoxysilane was added and reacted for 5 hours. After that, the reaction was terminated, and a second graft copolymer latex E was prepared.

<Production of aggregates>

The second graft copolymer latex E was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) and 51 parts by weight of the silica dispersion of Preparation Example 1 for 20 minutes, and aged for 40 minutes to aggregate E Was prepared.

<Preparation of graft copolymer powder>

Subsequently, the aggregate E was washed and dried to prepare graft copolymer powder E.

<Production of thermoplastic resin composition>

The thermoplastic resin composition E was prepared by mixing 60 parts by weight of the graft copolymer powder E and 40 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Comparative example One

<Preparation of graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, ion-exchanged water 100 parts by weight , 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, disodium The first copolymerization was carried out with 0.012 parts by weight of ethylenediaminetetraacetate and 0.001 parts by weight of ferrous sulfate continuously being fed at a constant rate for 5 hours at 75°C.

Subsequently, the reactor was heated to 80° C., followed by secondary copolymerization and aging for 1 hour. Thereafter, secondary copolymerization and aging were terminated, and a graft copolymer latex F was prepared.

<Production of aggregates>

The graft copolymer latex F was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) for 20 minutes, and aged for 40 minutes to prepare aggregate F.

<Preparation of graft copolymer powder>

Subsequently, the aggregate F was washed and dried to prepare graft copolymer powder F.

<Production of thermoplastic resin composition>

The thermoplastic resin composition E was prepared by mixing 60 parts by weight of the graft copolymer powder F and 40 parts by weight of XT500 (methyl methacrylate/styrene/acrylonitrile copolymer) of LG Chem.

Comparative example 2

<Preparation of graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, vinyl triethoxysilane 0.1 Parts by weight, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 parts by weight of cumene hydroperoxide as an initiator, sodium formaldehyde as an activator The first copolymerization was carried out while 0.048 parts by weight of sulfoxylate, 0.012 parts by weight of disodium ethylenediaminetetraacetate, and 0.001 parts by weight of ferrous sulfate were continuously added at 75°C for 5 hours at a constant rate.

Subsequently, the reactor was heated to 80° C., followed by secondary copolymerization and aging for 1 hour. Thereafter, secondary copolymerization and aging were terminated, and a graft copolymer latex G was prepared.

<Production of aggregates>

The graft copolymer latex G was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) for 20 minutes, and aged for 40 minutes to prepare aggregate G.

<Preparation of graft copolymer powder>

Subsequently, the aggregate G was washed and dried to prepare a graft copolymer powder G.

<Production of thermoplastic resin composition>

The thermoplastic resin composition G was prepared by mixing 60 parts by weight of the graft copolymer powder G and 40 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Comparative example 3

<Preparation of first graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, ion-exchanged water 100 parts by weight , 1 part by weight of sodium dodecylbenzene sulfonate as an emulsifier, 0.3 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, disodium 0.012 parts by weight of ethylenediaminetetraacetate and 0.001 parts by weight of ferrous sulfate were copolymerized at 75°C for 6 hours at a constant rate. Thereafter, the copolymerization was terminated, and a first graft copolymer H was prepared.

<Preparation of second graft copolymer latex>

Subsequently, after heating the reactor containing the first graft copolymer latex H to 80° C., 0.05 parts by weight of tetraethoxysilane was added and reacted for 5 hours. Thereafter, the reaction was terminated, and a second graft copolymer latex H was prepared.

<Production of aggregates>

The second graft copolymer latex H was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) for 20 minutes, and aged for 40 minutes to prepare aggregate H.

<Preparation of graft copolymer powder>

Subsequently, the aggregate H was washed and dried to prepare graft copolymer powder H.

<Production of thermoplastic resin composition>

The thermoplastic resin composition H was prepared by mixing 60 parts by weight of the graft copolymer powder H and 40 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Comparative example 4

<Preparation of graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, ion-exchanged water 100 parts by weight , 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, disodium The first copolymerization was carried out with 0.012 parts by weight of ethylenediaminetetraacetate and 0.001 parts by weight of ferrous sulfate continuously being fed at a constant rate for 5 hours at 75°C.

Subsequently, the reactor was heated to 80° C., followed by secondary copolymerization and aging for 1 hour. Thereafter, secondary copolymerization and aging were terminated, and a graft copolymer latex I was prepared.

<Production of aggregates>

Subsequently, the graft copolymer latex I was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) and 51 parts by weight of the silica dispersion of Preparation Example 1 for 20 minutes, and aged for 40 minutes to aggregate I Was prepared.

<Preparation of graft copolymer powder>

Subsequently, the aggregate I was washed and dried to prepare graft copolymer powder I.

<Production of thermoplastic resin composition>

The thermoplastic resin composition I was prepared by mixing 60 parts by weight of the graft copolymer powder I and 40 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Comparative example 5

<Preparation of graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle size: 100 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, ion-exchanged water 100 parts by weight , 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, disodium The first copolymerization was carried out with 0.012 parts by weight of ethylenediaminetetraacetate and 0.001 parts by weight of ferrous sulfate continuously being fed at a constant rate for 5 hours at 75°C.

Subsequently, the reactor was heated to 80° C., followed by secondary copolymerization and aging for 1 hour. Thereafter, secondary copolymerization and aging were terminated, and a graft copolymer latex J was prepared.

<Production of aggregates>

Subsequently, the graft copolymer latex J was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) for 20 minutes, and aged for 40 minutes to prepare aggregate J.

<Preparation of graft copolymer powder>

Subsequently, the aggregate J was washed and dried to prepare a graft copolymer powder J.

<Production of thermoplastic resin composition>

The thermoplastic resin composition J was prepared by mixing 60 parts by weight of the graft copolymer powder J and 40 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Comparative example 6

<Preparation of first graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, ion-exchanged water 100 parts by weight , 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, disodium 0.012 parts by weight of ethylenediaminetetraacetate and 0.001 parts by weight of ferrous sulfate were copolymerized at 75°C for 6 hours at a constant rate. After completion of the copolymerization, a first graft copolymer latex K was prepared.

<Preparation of second graft copolymer latex>

Subsequently, after heating the reactor containing the first graft copolymer latex K to 80° C., 0.05 parts by weight of tetraethoxysilane was added and reacted for 5 hours. After that, the reaction was terminated, and a second graft copolymer latex K was prepared.

<Production of aggregates>

Subsequently, the second graft copolymer latex K was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) and 51 parts by weight of the silica dispersion of Preparation Example 1 for 20 minutes, and aged for 40 minutes. Aggregate K was prepared.

<Preparation of graft copolymer powder>

Subsequently, the aggregate K was washed and dried to prepare a graft copolymer powder K.

<Production of thermoplastic resin composition>

The thermoplastic resin composition A was prepared by mixing 40 parts by weight of the graft copolymer powder K and 60 parts by weight of XT500 (methyl methacrylate/styrene/acrylonitrile copolymer) manufactured by LG Chem.

Comparative example 7

<Preparation of graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, vinyl triethoxysilane 0.1 Parts by weight, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecylbenzene sulfonate as an emulsifier, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 parts by weight of cumene hydroperoxide as an initiator, sodium formaldehyde as an activator The first copolymerization was carried out while 0.048 parts by weight of sulfoxylate, 0.012 parts by weight of disodium ethylenediaminetetraacetate, and 0.001 parts by weight of ferrous sulfate were continuously added at 75°C for 5 hours at a constant rate.

Subsequently, the reactor was heated to 80° C., followed by secondary copolymerization and aging for 1 hour. Then, secondary copolymerization and aging were terminated, and a graft copolymer latex L was prepared.

<Production of aggregates>

Subsequently, the graft copolymer latex L was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) and 51 parts by weight of the silica dispersion of Preparation Example 1 for 20 minutes, and aged for 40 minutes to aggregate L Was prepared.

<Preparation of graft copolymer powder>

Subsequently, the agglomerate L was washed and dried to prepare a graft copolymer powder L.

<Production of thermoplastic resin composition>

The thermoplastic resin composition L was prepared by mixing 40 parts by weight of the graft copolymer powder L and 60 parts by weight of XT500 (methyl methacrylate/styrene/acrylonitrile copolymer) of LG Chem.

Comparative example 8

<Preparation of first graft copolymer latex>

In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, refractive index: 1.516) 50 parts by weight, methyl methacrylate 32 parts by weight, styrene 11 parts by weight, acrylonitrile 7 parts by weight, vinyl triethoxysilane 0.1 Parts by weight, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecyl benzene sulfonate as an emulsifier, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 parts by weight of cumene hydroperoxide as an initiator, sodium form as an activator The aldehyde sulfoxylate 0.048 parts by weight, disodium ethylenediaminetetraacetate 0.012 parts by weight, and ferrous sulfate 0.001 parts by weight were copolymerized while continuously being charged at 75°C for 6 hours at a constant rate. Thereafter, the copolymerization was terminated, and a first graft copolymer latex M was prepared.

<Preparation of second graft copolymer latex>

Subsequently, after heating the reactor containing the first graft copolymer latex M to 80° C., 0.05 parts by weight of tetraethoxysilane was added and reacted for 5 hours. After that, the reaction was terminated, and a second graft copolymer latex M was prepared.

<Production of aggregates>

Subsequently, the second graft copolymer latex M was continuously added to the coagulation bath containing 1 part by weight of an aqueous calcium chloride solution (concentration: 23% by weight) for 20 minutes, and aged for 40 minutes to prepare aggregate M.

<Preparation of graft copolymer powder>

Subsequently, the aggregate M was washed and dried to prepare a graft copolymer powder M.

<Production of thermoplastic resin composition>

The thermoplastic resin composition M was prepared by mixing 40 parts by weight of the graft copolymer powder M and 60 parts by weight of LG Chem's XT500 (methyl methacrylate/styrene/acrylonitrile copolymer).

Experimental Example One

The physical properties of the graft copolymer powders of Examples and Comparative Examples were measured in the following manner, and the results are shown in [Table 1] and [Table 2].

① Si residual ratio (% by weight): Residual Si was calculated through EDS (Energy Dispersive Spectrometry) analysis using INCA Penta FETx3 from OXFORD.

Experimental Example 2

2 parts by weight of ethylene bis-acrylamide as a lubricant in the thermoplastic resin compositions of Examples and Comparative Examples and pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydro) as an antioxidant Cinematite) (Pentaerythritoltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) 0.2 parts by weight of the mixture was uniformly mixed, and then put into a twin-screw extruder set at 230°C and extruded to prepare pellets. The flow index of the pellet was measured by the following method, and the results are shown in [Table 1] and [Table 2].

② Flow index (g/10min): Measured under 220 ℃ and 10 kg according to ASTM D-1238.

Experimental Example 3

The pellets prepared in Experimental Example 2 were injected at 230° C. and aged at 25° C. and 50±5% relative humidity for 12 hours to prepare specimens. And the physical properties of the specimen were measured by the method described below, and the results are shown in [Table 1] and [Table 2].

③ Transmittance (%) and Transparency (haze, %): Permeability and transparency of 3 mm thick sheets were measured according to ASTM D-1003.

④ Notched Izod Impact Strength (㎏·㎝/㎝, 1/4 In): Measured according to ASTM D256.

⑤ Tensile strength (㎏f/㎠): Measured according to ASTM D638.

division Example One 2 3 4 5 Butadiene rubbery polymer latex (parts by weight)
(Average particle diameter: 300 nm) 50 50 50 50 - Butadiene rubbery polymer latex (parts by weight) (average particle diameter: 100 nm) - - - - 50 Methyl methacrylate
(Parts by weight) 32 32 32 32 32 Styrene (parts by weight) 11 11 11 11 11 Acrylonitrile (parts by weight) 7 7 7 7 7 Vinyl triethoxysilane
(Parts by weight) 0.1 0.1 0.1 0.5 0.1 Tetraethoxysilane
(Parts by weight) 0.05 0.2 0.4 0.05 0.2 Silica (parts by weight) One One One One One Si residual rate 0.07 0.15 0.4 0.7 0.2 Flow index 24.2 24.0 20.2 16.2 5.9 Transmittance 90.8 90.6 90.0 87.0 91.3 transparency 1.8 1.8 2.0 3.0 0.8 Impact strength 15.1 14.5 15.2 18.2 9.1 The tensile strength 590 587 585 605 380

division Comparative example One 2 3 4 5 6 7 8 Butadiene rubbery polymer latex (parts by weight)
(Average particle diameter: 300 nm) 50 50 50 50 - 50 50 50 Butadiene rubbery polymer latex (parts by weight)
(Average particle diameter: 100 nm) - - - - 50 - - - Methyl methacrylate
(Parts by weight) 32 32 32 32 32 32 32 32 Styrene (parts by weight) 11 11 11 11 11 11 11 11 Acrylonitrile (parts by weight) 7 7 7 7 7 7 7 7 Vinyl triethoxysilane
(Parts by weight) - 0.1 - - - - 0.1 0.1 Tetraethoxysilane
(Parts by weight) - - 0.05 - - 0.05 - 0.05 Silica (parts by weight) - - - One - One One - Si residual rate - 0.01 - 0.01 - 0.01 0.01 0.01 Flow index 24.4 24.1 24.0 24.1 5.6 23.9 24.3 24.0 Transmittance 90.6 90.8 90.7 90.5 91.5 90.6 90.7 90.5 transparency 1.8 1.7 1.8 1.8 0.8 1.7 1.7 1.7 Impact strength 10.4 11.4 11.1 10.9 5.7 10.6 11.0 10.8 The tensile strength 537 549 545 547 349 540 541 547

Referring to Table 1 and Table 2, it was confirmed that Examples 1 to 5 had significantly higher Si residual ratios than Comparative Examples, and excellent impact strength and tensile strength. Specifically, referring to Examples 1 to 3, it was confirmed that tetraethoxysilane, when used in an appropriate amount, does not affect permeability and transparency. Further, referring to Examples 1 and 4, when the vinyl triethoxysilane is used in excess, the impact strength and tensile strength are improved, but since the Si remains in the graft copolymer, the flow index, permeability and transparency are lowered. I could confirm that. From these results, when preparing the transparent graft copolymer powder, it was confirmed that the mechanical properties were improved without affecting the permeability and transparency only when appropriate amounts of tetraethoxysilane and vinyltriethoxysilane were used.

On the other hand, since Comparative Example 1 did not use vinyl triethoxysilane, tetraethoxysilane and silica, it was confirmed that the mechanical properties were not improved at all. In Comparative Examples 2 to 4, since only one of vinyl triethoxysilane, tetraethoxysilane, and silica was used, it was confirmed that mechanical properties were improved compared to Comparative Example 1, but significantly decreased compared to Examples. In the case of Comparative Examples 6 to 8, since two types of vinyl triethoxysilane, tetraethoxysilane, and silica were used, it was confirmed that mechanical properties were improved compared to Comparative Example 1, but significantly lower than those of Examples.

Claims (11)

Diene-based rubbery polymers; A monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers; And preparing a first graft copolymer latex by adding and copolymerizing a compound represented by the following Chemical Formula 1;
Preparing a second graft copolymer latex by adding and reacting a compound represented by the following Chemical Formula 2 in the first graft copolymer latex; And
Method of producing a graft copolymer powder comprising the step of adding the second graft copolymer latex to silica and preparing an aggregate:
<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,
R ₁ is a C ₂ to C ₁₀ alkenyl group,
R ₂ to R ₈ are each independently the same as or different from each other, and are hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group.
The method according to claim 1,
In Chemical Formula 1, R ₁ is a C ₂ to C ₄ alkenyl group, R ₂ to R ₄ are each independently the same as or different from each other, and C ₁ to C ₁₀ are alkyl groups. .
The method according to claim 1,
The compound represented by the formula (1) is a method for producing a graft copolymer powder that is at least one member selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane, and vinyl triisohydroxysilane.
The method according to claim 1,
The compound represented by Chemical Formula 1 is a method for producing a graft copolymer powder, which is added in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture.
The method according to claim 1,
In Chemical Formula 2, R ₄ to R ₈ are each independently the same as or different from each other, and C ₁ to C ₁₀ are alkyl groups.
The method according to claim 1,
The compound represented by the formula (2) is a method for producing a graft copolymer powder that is at least one member selected from the group consisting of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane.
The method according to claim 1,
The compound represented by Chemical Formula 2 is a method for producing a graft copolymer powder, which is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture.
The method according to claim 1,
The silica is a method for preparing a graft copolymer powder, which is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the mixture of the diene-based rubbery polymer and the monomer mixture.
The method according to claim 1,
The silica is a method for producing a graft copolymer powder having an average particle diameter of 50 to 150 nm.
The method according to claim 1,
The step of preparing the second graft copolymer latex is
Method of producing a graft copolymer powder that is a step of reacting the compound represented by the formula (2) with a derivative of the compound represented by the formula (1) contained in the first graft copolymer latex.
Diene-based rubbery polymers; A monomer mixture comprising two or more selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyan monomers; And a graft copolymer formed by emulsion polymerization of the compound represented by Formula 1;
A derivative of a compound represented by Formula 2 below; And
Graft copolymer powder comprising silica:
<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,
R ₁ is a C ₂ to C ₁₀ alkenyl group,
R ₂ to R ₈ are each independently the same as or different from each other, and are hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group.