KR20200076248A - Method for preparing graft copolymer - Google Patents

Abstract

The present invention relates to a method for manufacturing a graft copolymer which comprises a copolymer of a monomer mixture comprising: a first hypertrophy step of manufacturing a hypertrophied diene-based rubbery polymer by adding a coagulant to a diene-based rubbery polymer; a first copolymerization step of manufacturing the first copolymer by adding and copolymerizing the hypertrophied diene-based rubbery polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; a second hypertrophy step of manufacturing a hypertrophied second copolymer by adding a coagulant to the first copolymer; and a second copolymerization step of copolymerizing the second copolymer, wherein the coagulant contains a copolymer of the monomer mixture containing a (meth)acrylate-based monomer and a carboxylic acid-based monomer. The present invention can manufacture the graft copolymer having excellent impact resistance.

Description

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

The present invention relates to a method for producing a graft copolymer, and more particularly, to a method for producing a graft copolymer having excellent impact resistance.

Acrylonitrile-butadiene-styrene copolymer (ABS copolymer) is a thermoplastic copolymer, and is prepared by graft copolymerizing styrene and acrylonitrile with a butadiene rubbery polymer.

ABS copolymer has excellent impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity, processability, and other properties, compared to the existing high-strength polystyrene (HIPS: High-Impact polystyrene). Do. Due to these characteristics, the ABS copolymer can be used in parts and toys, such as interior and exterior materials for automobiles, office equipment, and various electric and electronic products.

On the other hand, in order to prepare an ABS copolymer having excellent impact resistance, it is necessary to appropriately adjust the particle diameter of the diene-based rubbery polymer, and in general, when the average particle diameter is 0.25 to 0.5 μm, the surface gloss characteristics are not deteriorated and excellent impact resistance is obtained. Can be implemented. However, when the diene-based rubbery polymer having the above-described average particle diameter is produced by emulsion polymerization, the polymerization time is too long, resulting in poor productivity. Accordingly, a method of preparing a diene-based rubbery polymer having an average particle diameter of about 0.1 µm or less and then enlarging the diene-based rubbery polymer using a coagulant has been proposed. However, when acetic acid was used as a coagulant during hypertrophy, excessive clots were generated, and in order to reduce the generation of clots, lowering the concentration of diene-based rubbery polymer latex resulted in a problem of lowering productivity. In order to solve this problem, a method of using a copolymer containing an acid group and having a core-shell structure as a coagulant has been proposed, but in this case, the polymerization of the diene-based rubbery polymer continues during polymerization of the ABS copolymer, resulting in latex stability and product properties. There was a problem of deterioration.

KR2004-0147655A

The present invention is to solve the above problems, to provide a method for producing a graft copolymer having excellent productivity and excellent latex stability while realizing excellent impact resistance.

In order to solve the above-described problems, the present invention is a primary non-sintering step of preparing a diene-based rubbery polymer that is increased by adding a coagulant to the diene-based rubbery polymer; A primary copolymerization step of introducing and copolymerizing the non-enlarged diene-based rubbery polymer, aromatic vinyl monomer and vinyl cyan monomer, to prepare a first copolymer; A second non-consolidation step of preparing a non-consolidated second copolymer by adding a flocculant to the first copolymer; And a second copolymerization step of copolymerizing the second copolymer, wherein the flocculant comprises a copolymer of a monomer mixture comprising a (meth)acrylate-based monomer and a carboxylic acid-based monomer. to provide.

According to the production method of the graft copolymer of the present invention, not only is the stability of the diene-based rubbery polymer latex and the graft copolymer latex excellent, but also a graft copolymer excellent in impact resistance can be produced.

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 copolymer contained in the diene-based rubbery polymer, graft copolymer, and flocculant can be measured using a dynamic light scattering method, and specifically, Nicomp 380 equipment (product name, manufacturer: Nicomp ).

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.

In the present invention, the weight average molecular weight may be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent.

In the present invention, the polymerization conversion rate refers to the polymerization rate of the monomers input in the method for preparing the graft copolymer, that is, the degree in which the monomers are polymerized to form a copolymer, that is, a shell, and can be calculated by the following equation.

Polymerization conversion rate (%) = {((total weight of rubbery polymers and monomers added in the manufacture of the graft copolymer))-(total weight of unreacted monomers)}/(total of the rubbery polymer and monomers added in the production of the graft copolymer) Weight)×100

In the present invention, the aromatic vinyl monomer may be one or more selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, of which styrene is preferred. In the present invention, the aromatic vinyl-based unit may mean a unit derived from an aromatic vinyl-based monomer.

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 vinyl cyan-based unit may mean a unit derived from a vinyl cyan-based monomer.

In the present invention, the (meth)acrylate-based monomer may be a C ₁ to C ₄ alkyl (meth)acrylate-based monomer. The alkyl (meth)acrylate monomers of C ₁ to C ₄ are selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate and n-butyl (meth)acrylate. It may be one or more, of which one or more selected from the group consisting of ethyl (meth)acrylate and n-butyl (meth)acrylate is preferred. In the present invention, the (meth)acrylate-based unit may mean a unit derived from a (meth)acrylate-based monomer.

In the present invention, the carboxylic acid-based monomer may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, of which methacrylic acid is preferred. In the present invention, the carboxylic acid-based unit may be a unit derived from a carboxylic acid-based monomer.

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

One. Graft Method for preparing copolymer

A method of manufacturing a graft copolymer according to an embodiment of the present invention includes: 1) a first non-sintering step of preparing a diene-based rubbery polymer by adding a coagulant to the diene-based rubbery polymer; 2) a primary copolymerization step of preparing a first copolymer by incorporating and copolymerizing the non-enlarged diene-based rubbery polymer, aromatic vinyl monomer, and vinyl cyan monomer; 3) a second non-consolidation step of preparing a non-consolidated second copolymer by adding a flocculant to the first copolymer; And 4) a second copolymerization step of copolymerizing the second copolymer, and the flocculant comprises a copolymer of a monomer mixture comprising a (meth)acrylate-based monomer and a carboxylic acid-based monomer.

The copolymer of the monomer mixture may be a linear or branched copolymer, preferably a linear or branched copolymer comprising (meth)acrylate units and carboxylic acid units. The copolymer of the monomer mixture may have a glass transition temperature, unlike a copolymer of a core-shell structure in which a (meth)acrylate-based monomer and a carboxylic acid-based monomer are polymerized on a (meth)acrylate-based polymer.

The copolymer of the monomer mixture may have an average particle diameter of 50 to 150 nm, 80 to 120 nm or 90 to 110 nm, and preferably 90 to 110 nm. If the above-mentioned range is satisfied, a diene-based rubbery polymer having a suitable average particle diameter and excellent latex stability can be produced while the diene-based rubbery polymer can be easily enlarged.

The copolymer of the monomer mixture may be at least one selected from the group consisting of ethyl acrylate/methacrylic acid copolymer and n-butyl acrylate/methacrylic acid copolymer, and the ethyl acrylate/methacrylic acid copolymer Is preferred.

The copolymer of the monomer mixture is preferably in the form of a latex in order to more easily perform mixing and aggregation with a diene-based rubbery polymer in the form of a latex. The latex copolymer may be prepared by emulsion polymerization.

Meanwhile, the copolymer of the monomer mixture may be prepared by emulsion polymerization of the monomer mixture in a reactor.

The monomer mixture may include a (meth)acrylate-based monomer and a carboxylic acid-based monomer in a weight ratio of 97:3 to 80:20 or a weight ratio of 94:6 to 82:18, of which 94:6 to 82:18 It is preferred to include in a weight ratio of. If the above-mentioned range is satisfied, the carboxylic acid unit in the copolymer of the monomer mixture can sufficiently enlarge the diene-based rubbery polymer, and generation of clumps during production of the copolymer of the monomer mixture can be suppressed.

The emulsion polymerization may be performed by adding one or more selected from the group consisting of an initiator, an emulsifier, a molecular weight modifier, and water together with the monomer mixture.

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-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isonoxy acid (butyl acid) methyl, and may be one or more selected from the group consisting of potassium persulfate.

The initiator may be added in an amount of 0.02 to 2 parts by weight or 0.07 to 0.8 parts by weight based on 100 parts by weight of the monomer mixture, preferably 0.07 to 0.8 parts by weight. If the above-mentioned range is satisfied, the copolymer of the monomer mixture has an appropriate molecular weight, so that the diene-based rubbery polymer can be easily enlarged.

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 salt, sodium dodecyl sulfate, potassium octadecyl sulfate, potassium rosinate and sodium rosinate It may be the above, among which sodium dodecyl benzene sulfonate is preferred.

The emulsifier may be added in 0.1 to 2 parts by weight or 0.3 to 0.7 parts by weight based on 100 parts by weight of the monomer mixture, and preferably 0.3 to 0.7 parts by weight. If the above-mentioned range is satisfied, the average particle diameter of the copolymer of the monomer mixture is appropriate, so that the diene-based rubbery polymer can be easily enlarged while minimizing generation of clots when enlarged.

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

On the other hand, the emulsion polymerization may be carried out at 50 to 90 ℃ or 60 to 80 ℃, it is preferably carried out at 60 to 80 ℃.

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) 1st stage of hypertrophy

A diene-based rubbery polymer is prepared by adding a coagulant to the diene-based rubbery polymer.

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

The diene-based rubbery polymer may have an average particle diameter of 50 to 150 nm, or 80 to 120 nm, and preferably 80 to 120 nm. If the above-mentioned range is satisfied, non-large diene-based rubbery polymers having an appropriate average particle diameter and excellent latex stability can be produced because it is easy to enlarge.

The flocculant may be added in an amount of 0.3 to 2 parts by weight or 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the diene-based rubbery polymer, and preferably 0.5 to 1.5 parts by weight. If the above-described range is satisfied, it is possible to easily enlarge the diene-based rubbery polymer and minimize generation of clots.

The non-large diene-based rubbery polymer may have an average particle diameter of 200 to 500 nm, or 250 to 350 nm, and preferably 250 to 350 nm. If the above-mentioned range is satisfied, not only can the graft copolymer be implemented with excellent impact resistance, but also excellent surface gloss can be realized.

2) 1st copolymerization step

Subsequently, the above-mentioned enlarged diene rubber polymer, aromatic vinyl monomer and vinyl cyan monomer are added and copolymerized to prepare a first copolymer.

The copolymerization may be emulsion polymerization.

The non-enlarged diene-based rubbery polymer may be added in an amount of 50 to 70 parts by weight or 55 to 65 parts by weight based on 100 parts by weight of the non-enlarged diene-based rubbery polymer, aromatic vinyl monomer, and vinyl cyan monomer. It is preferably added in 55 to 65 parts by weight. If the above-described range is satisfied, a graft copolymer having excellent impact resistance and surface gloss characteristics can be produced.

The aromatic vinyl-based monomer may be added in an amount of 20 to 40 parts by weight or 25 to 35 parts by weight based on 100 parts by weight of the combined diene-based rubbery polymer, aromatic vinyl-based monomer, and vinyl cyan-based monomer, 25 of which It is preferred to add from 35 parts by weight. When the above-described range is satisfied, processability becomes excellent, and compatibility with a copolymer containing an aromatic vinyl-based unit and a vinyl cyan-based unit mixed together during production of a thermoplastic resin composition may be remarkably improved.

The vinyl cyan-based monomer may be added in an amount of 1 to 35 parts by weight or 5 to 15 parts by weight based on 100 parts by weight of the combined diene rubber-based polymer, aromatic vinyl monomer, and vinyl cyan monomer. It is preferable to add it to 15 parts by weight. When the above-described range is satisfied, compatibility with an aromatic vinyl-based unit and a copolymer containing a vinyl cyan-based unit may be remarkably improved while chemical resistance is excellent.

The copolymerization may be performed by adding one or more selected from the group consisting of an initiator, an activator, a molecular weight modifier, and water together with the non-sized diene rubber polymer, aromatic vinyl monomer, and vinyl cyan monomer.

The type of the initiator is as described above, of which cumene hydroperoxide is preferred. The initiator may be added in 0.001 to 0.5 parts by weight or 0.005 to 0.1 parts by weight, and 0.005 to 0.1 parts by weight based on 100 parts by weight of the combined diene rubber polymer, aromatic vinyl monomer, and vinyl cyan monomer. It is preferred to be poured in parts. If the above-described range is satisfied, a graft copolymer having excellent impact resistance and fluidity can be produced.

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 0.01 to 0.5 parts by weight or 0.05 to 0.2 parts by weight, based on 100 parts by weight of the sum of the non-enlarged diene rubber polymer, aromatic vinyl monomer, and vinyl cyan monomer, and 0.05 to 0.2 It is preferably added in parts by weight. If the above-described range is satisfied, a graft copolymer having excellent impact resistance and fluidity can be produced.

The kind of the molecular weight modifier is as described above, of which t-dodecyl mercaptan is preferred. The molecular weight modifier may be added in an amount of 0.1 to 0.6 parts by weight or 0.25 to 0.4 parts by weight, based on 100 parts by weight of the combined diene rubbery polymer, aromatic vinyl monomer, and vinyl cyan monomer, of which 0.25 to 0.4 It is preferably added in parts by weight. If the above-described range is satisfied, a graft copolymer having improved impact resistance can be produced.

On the other hand, when the diene-based rubbery polymer and flocculant are added in the form of latex, the emulsifier may not be separately added in the first copolymerization step due to the emulsifier contained in these latexes.

The primary copolymerization may be performed for 10 to 50% of the time or 15 to 50% for the total polymerization time, and is preferably performed for 15 to 50% of the time. When the primary copolymerization is performed too shortly, during the secondary copolymerization to be described later, there are too many of the non-sized diene-based rubbery polymers, so that the non-sized diene-based rubbery polymers aggregate a lot and help improve impact resistance. The aggregation of the non-enlarged diene-based rubbery polymer and the grafting copolymer occurs less. Accordingly, the impact resistance of the final product, the graft copolymer, may not be improved. When the primary copolymerization is performed for too long, the secondary copolymerized to be described later, the non-large diene-based rubbery polymer is present in too little compared to the grafting copolymer, resulting in agglomeration between the grafting copolymers, resulting in excessive coagulation. Therefore, the polymerization stability may be significantly lowered.

Here, the grafting polymer may mean an intermediate in which the graft polymerization of the aromatic vinyl-based monomer and the vinyl cyan-based monomer is not sufficiently performed on the diene-based rubbery polymer.

When the total polymerization time of the graft copolymer is 180 minutes, the primary copolymerization may be performed for 18 minutes to 90 minutes or 27 to 90 minutes, and it is preferably performed for 27 to 90 minutes. When the primary copolymerization is performed too shortly, during the secondary copolymerization to be described later, there are too many of the non-sized diene-based rubbery polymers, so that the non-sized diene-based rubbery polymers aggregate a lot and help improve impact resistance. The aggregation of the non-enlarged diene-based rubbery polymer and the grafting copolymer occurs less. Accordingly, the impact resistance of the final product, the graft copolymer, may not be improved. When the primary copolymerization is performed for too long, the secondary copolymerized to be described later, the non-large diene-based rubbery polymer is present in too little compared to the grafting copolymer, resulting in agglomeration between the grafting copolymers, resulting in excessive coagulation. Therefore, the polymerization stability may be significantly lowered.

3) 2nd stage of hypertrophy

The coagulant is introduced into the first copolymer and then enlarged to prepare a second copolymer.

When the polymerization conversion rate is 55 to 80% or when the polymerization conversion rate is 60 to 75%, the coagulant may be added to the first copolymer, and when the polymerization conversion rate is 60 to 75%, to the first copolymer It is preferred to add the coagulant. When the flocculant is added too quickly, the second copolymerization to be described later has too much of the non-enlarged diene-based rubbery polymers, so that the non-enlarged diene-based rubbery polymers aggregate a lot and help improve the impact resistance. The agglomeration of the non-large diene-based rubbery polymer and the grafting copolymer occurs less. Accordingly, the impact resistance of the final product, the graft copolymer, may not be improved. When the coagulant is added too late, during the second copolymerization, which will be described later, the non-large diene-based rubbery polymer is present in too little compared to the grafting copolymer, resulting in agglomeration between the grafting copolymers, resulting in excessive coagulation and polymerization. Stability can be significantly reduced.

The coagulant is preferably continuously added in order to minimize a decrease in polymerization stability.

The flocculant may be added in an amount of 0.3 to 2 parts by weight or 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the diene-based rubbery polymer, and preferably 0.5 to 1.5 parts by weight. If the above-described range is satisfied, it is possible to easily enlarge the diene-based rubbery polymer and minimize generation of clots.

4) Secondary copolymerization stage

The second copolymer is copolymerized.

The secondary copolymerization may be performed for 50 to 90% of the time or 50 to 85% for the total polymerization time, and is preferably performed for 50 to 85% of the time. When the secondary copolymerization is carried out too long, the secondary copolymerization causes too many of the non-sized diene-based rubbery polymers to cohesively occur between the non-sized diene-based rubbery polymers, and helps to improve impact resistance. The agglomeration of the non-large diene-based rubbery polymer and the grafting copolymer occurs less. Accordingly, the impact resistance of the final product, the graft copolymer, may not be improved. If the secondary copolymerization is performed too short, the secondary copolymerized diene-based rubbery polymer is present in too little compared to the grafting copolymer, resulting in a lot of aggregation between the grafting copolymers, resulting in excessive coagulation and polymerization Stability can be significantly reduced.

The secondary copolymerization may be performed for 90 minutes to 162 minutes or 90 to 153 minutes when the total polymerization time of the graft copolymer is 180 minutes, and is preferably performed for 90 to 153 minutes. When the secondary copolymerization is carried out too long, the secondary copolymerization causes too many of the non-sized diene-based rubbery polymers to cohesively occur between the non-sized diene-based rubbery polymers, and helps to improve impact resistance. The agglomeration of the non-large diene-based rubbery polymer and the grafting copolymer occurs less. Accordingly, the impact resistance of the final product, the graft copolymer, may not be improved. If the secondary copolymerization is performed too short, the secondary copolymerized diene-based rubbery polymer is present in too little compared to the grafting copolymer, resulting in a lot of aggregation between the grafting copolymers, resulting in excessive coagulation and polymerization Stability can be significantly reduced.

When the second copolymerization step is completed, a graft copolymer latex may be prepared.

Meanwhile, in the method of preparing a graft copolymer according to an embodiment of the present invention, when the secondary copolymerization step is completed, a step of preparing a graft copolymer powder may be further performed.

In detail, one or more selected from the group consisting of sulfuric acid, calcium chloride and magnesium sulfate as a coagulant is added to the graft copolymer latex obtained in the secondary copolymerization step to aggregate, mature, dehydrate, wash, and dry. After the graft copolymer powder can be prepared.

2. Thermoplastic resin composition

The thermoplastic resin composition according to another embodiment of the present invention includes a graft copolymer powder prepared according to an embodiment of the present invention and a matrix copolymer comprising an aromatic vinyl-based unit and a vinyl cyan-based unit.

The matrix copolymer may be a copolymer of a second monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer.

The matrix copolymer may be at least one selected from the group consisting of styrene/acrylonitrile copolymer and α-methyl 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

Prepared a polymerization solution of 82 parts by weight of butyl acrylate, 18 parts by weight of methacrylic acid, 0.15 parts by weight of potassium persulfate as an initiator, 0.4 parts by weight of sodium dodecyl benzene sulfonate as an emulsifier, and 38 parts by weight of ion-exchanged water Did.

After adding 170 parts by weight of ion-exchanged water to the nitrogen-substituted polymerization reactor, 0.05 parts by weight of potassium persulfate as an initiator, and 0.1 parts by weight of sodium dodecyl benzene sulfonate as an emulsifier, after raising the internal temperature of the polymerization reactor to 80° C., the Polymerization was performed while continuously injecting the polymerization solution at a constant rate for 4 hours to obtain a copolymer latex (weight average molecular weight: 250,000 g/mol, average particle diameter: 110 nm).

Manufacturing example 2

A polymerization solution was prepared by uniformly mixing 94 parts by weight of ethyl acrylate, 6 parts by weight of methacrylic acid, 0.15 parts by weight of potassium persulfate as an initiator, 0.5 parts by weight of sodium dodecyl benzene sulfonate as an emulsifier, and 38 parts by weight of ion-exchanged water. .

After adding 170 parts by weight of ion-exchanged water to the nitrogen-substituted polymerization reactor, 0.05 parts by weight of potassium persulfate as an initiator, and 0.1 parts by weight of sodium dodecyl benzene sulfonate as an emulsifier, after raising the internal temperature of the polymerization reactor to 80°C, the Polymerization was performed while continuously injecting the polymerization solution at a constant rate for 4 hours to obtain a copolymer latex (weight average molecular weight: 30,0000 g/mol, average particle diameter: 105 nm).

Manufacturing example 3

208 parts by weight of ion-exchanged water and 0.75 parts by weight of dioctyl sulfosuccinate sodium salt as an emulsifier were added to the nitrogen-substituted polymerization reactor, the internal temperature of the polymerization reactor was raised to 80° C. and stirred, and potassium persulfate as an initiator. Cores were prepared by adding 0.034 parts by weight and 50 parts by weight of butyl acrylate and polymerizing for 90 minutes.

In the presence of the core, 41 parts by weight of butyl acrylate, 9 parts by weight of methacrylic acid, and 0.099 parts by weight of an aqueous potassium persulfate solution (concentration: 3% by weight) as an initiator were polymerized while continuously being charged at a constant rate for 90 minutes, and the polymerization conversion rate was At 98%, polymerization was terminated to prepare a core-shell copolymer latex (average particle size: 110 nm).

Manufacturing example 4

208 parts by weight of ion-exchanged water and 0.75 parts by weight of dioctyl sulfosuccinate sodium salt as an emulsifier were added to the nitrogen-substituted polymerization reactor, the internal temperature of the polymerization reactor was raised to 80° C. and stirred, and potassium persulfate as an initiator. Cores were prepared by adding 0.034 parts by weight and 50 parts by weight of ethyl acrylate and polymerizing for 90 minutes.

In the presence of the core, 47 parts by weight of ethyl acrylate, 3 parts by weight of methacrylic acid, and 0.099 parts by weight of potassium persulfate aqueous solution (concentration: 3% by weight) as an initiator were continuously graft polymerized for 90 minutes at a constant rate, followed by polymerization. When the conversion was 98%, polymerization was terminated to prepare a core-shell copolymer latex (average particle size: 105 nm).

Example One

<1st stage of dialogue>

Butadiene rubbery polymer latex (average particle size: 100 nm) was added to 0.45 parts by weight (based on solids) of copolymer latex of Preparation Example 1 to 60 parts by weight (based on solids), and stirred for 30 minutes to increase the size of butadiene rubbery polymer A (average) Particle size: 200 nm) was prepared.

<1st polymerization step>

In the polymerization reactor having a nitrogen substitution and an internal temperature of 60° C., 60 parts by weight of the non-spherical butadiene rubbery polymer A, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.35 parts by weight of t-dodecyl mercaptan as an initiator, and an initiator Cumene hydroperoxide 0.02 parts by weight, 0.06 parts by weight of dextrose as an activator, 0.04 parts by weight of sodium pyrophosphate, 0.001 part by weight of ferrous sulfate, and 2.1 parts by weight of ion-exchanged water are added in batch, and the polymerization rate of primary polymerization is 55 %. At this time, the primary polymerization time was 30 minutes.

<2nd stage of hypertrophy>

Subsequently, 0.45 parts by weight of the copolymer latex of Preparation Example 1 (based on solid content) was added to the polymerization reactor at a constant rate for 5 minutes, and then enlarged.

<Secondary polymerization step>

Subsequently, after the secondary polymerization while raising the internal temperature of the polymerization reactor to a constant temperature over 70 minutes to 70° C., polymerization was terminated to prepare a graft copolymer latex A (average particle diameter: 310 nm).

<Preparation of graft copolymer powder>

2 parts by weight of MgSO ₄ was added to the entire amount of the graft copolymer latex A to aggregate, aged, dehydrated, washed, and dried to obtain graft copolymer powder A.

<Production of thermoplastic resin composition>

The thermoplastic resin composition A was prepared by mixing 23 parts by weight of the graft copolymer powder A and 77 parts by weight of 92HR of LG Chem.

Example 2

After performing the first polymerization until the polymerization conversion rate was 70% (the first polymerization time: 60 minutes), the copolymer latex of Preparation Example 1 was added, and the second polymerization was performed except that the polymerization was performed for 120 minutes. In the same manner as in Example 1, a graft copolymer latex B (average particle diameter: 310 nm) was prepared.

In addition, a graft copolymer powder B was prepared in the same manner as in Example 1, except that the graft copolymer latex B was used instead of the graft copolymer latex 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

After performing the first polymerization until the polymerization conversion rate was 80% (the first polymerization time: 90 minutes), the copolymer latex of Preparation Example 1 was added, and the second polymerization was performed except that the polymerization was performed for 90 minutes. In the same manner as in Example 1, a graft copolymer latex C (average particle diameter: 320 nm) was prepared.

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

Example 4

<1st stage of dialogue>

Butadiene rubbery polymer latex (average particle size: 100 nm) was added to 60 parts by weight (based on solids) of 0.45 parts by weight of copolymer latex of Preparation Example 2, and stirred for 30 minutes to increase the size of butadiene rubbery polymer D (average particle size: 230 nm) Was prepared.

<1st polymerization step>

In the polymerization reactor having a nitrogen substitution and an internal temperature of 60° C., 60 parts by weight of the above-mentioned butadiene rubbery polymer D, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.35 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, as an initiator Cumene hydroperoxide 0.02 parts by weight, 0.06 parts by weight of dextrose as an activator, 0.04 parts by weight of sodium pyrophosphate, 0.001 part by weight of ferrous sulfate, and 2.1 parts by weight of ion-exchanged water are added in batch, and the polymerization rate of primary polymerization is 55 %. At this time, the primary polymerization time was 30 minutes.

<2nd stage of hypertrophy>

Subsequently, 0.45 parts by weight of the copolymer latex of Preparation Example 1 (based on solid content) was added to the polymerization reactor at a constant rate for 5 minutes, and then enlarged.

<Secondary polymerization step>

Subsequently, after the secondary polymerization while raising the internal temperature of the polymerization reactor at a constant rate over 150 minutes to 70° C., polymerization was terminated to prepare a graft copolymer latex D (average particle diameter: 330 nm).

<Preparation of graft copolymer powder>

2 parts by weight of MgSO ₄ was added to the entire amount of the graft copolymer latex D to aggregate, aged, dehydrated, washed and dried to obtain graft copolymer powder A.

<Production of thermoplastic resin composition>

The thermoplastic resin composition D was prepared by mixing 23 parts by weight of the graft copolymer powder D and 77 parts by weight of 92HR of LG Chem.

Example 5

After the primary polymerization was performed until the polymerization conversion rate was 70% (primary polymerization time: 60 minutes), the copolymer latex of Preparation Example 2 was added, and the secondary polymerization was carried out for 120 minutes In the same manner as in Example 4, a graft copolymer latex E (average particle diameter: 340 nm) was prepared.

In addition, a graft copolymer powder E was prepared in the same manner as in Example 1, except that the graft copolymer latex E was used instead of the graft copolymer latex D.

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

Comparative example One

<De-conversation stage>

Butadiene rubbery polymer latex (average particle size: 0.1 μm) 0.9 parts by weight of copolymer latex of Preparation Example 1 (based on solid content) was added to 60 parts by weight, and stirred for 30 minutes to increase the size of butadiene rubbery polymer F (average particle size: 310 nm) ) Was prepared.

<Preparation of graft copolymer latex>

In a polymerization reactor having a nitrogen substitution and an internal temperature of 60° C., 60 parts by weight of the above-mentioned hyperbolic butadiene rubber polymer F, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.35 parts by weight of t-dodecyl mercaptan as a molecular weight modifier, and an initiator Cumene hydroperoxide 0.02 parts by weight, 0.06 parts by weight of dextrose as an activator, 0.04 parts by weight of sodium pyrophosphate and 0.001 parts by weight of ferrous sulfate, 180 parts by weight of ion-exchanged water, and polymerization for 180 minutes , Polymerization was terminated to prepare a graft copolymer latex F (average particle diameter: 320 nm).

<Preparation of graft copolymer powder>

2 parts by weight of MgSO ₄ was added to the entire amount of the graft copolymer latex F to agglomerate, mature, dehydrate, wash and dry to obtain a graft copolymer powder F.

<Production of thermoplastic resin composition>

The thermoplastic resin composition F was prepared by mixing 23 parts by weight of the graft copolymer powder F and 77 parts by weight of 92HR of LG Chem.

Comparative example 2

Butadiene rubbery polymer G (average particle diameter) in the same manner as in Comparative Example 1, except that 0.9 parts by weight of copolymer latex of Preparation Example 2 (based on solid content) was substituted for 0.9 parts by weight of copolymer latex of Preparation Example 1 (based on solid content) : 320 nm).

In addition, a graft copolymer latex G (average particle diameter: 330 nm) was prepared in the same manner as in Comparative Example 1, except that butadiene rubbery polymer G was used instead of butadiene rubbery polymer F.

A graft copolymer powder G was prepared in the same manner as in Comparative Example 1, except that the graft copolymer latex G was used instead of the graft copolymer latex F.

A thermoplastic resin composition G was prepared in the same manner as in Comparative Example 1, except that the graft copolymer powder G was used instead of the graft copolymer powder F.

Comparative example 3

The butadiene rubbery polymer H (larged in the same manner as in Example 1) except that 0.45 parts by weight of the copolymer latex of Preparation Example 3 was added instead of 0.45 parts by weight (based on solid content) of the copolymer latex of Preparation Example 1 Average particle diameter: 200 nm) was prepared.

In addition, butadiene rubbery polymer A was substituted with butadiene rubbery polymer H instead of 0.45 parts by weight of copolymer latex of Preparation Example 1 (based on solid content), and 0.45 parts by weight of copolymer latex of Preparation Example 3 (based on solid content) was excluded. In the same manner as in Example 1, a graft copolymer latex H (average particle diameter: 300 nm) was prepared.

In addition, a graft copolymer powder H was prepared in the same manner as in Example 1, except that the graft copolymer latex H was used instead of the graft copolymer latex A.

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

Comparative example 4

The butadiene rubbery polymer I (large-sized in the same manner as in Example 1) except that 0.45 parts by weight of the copolymer latex of Preparation Example 4 was added instead of 0.45 parts by weight of the copolymer latex of Preparation Example 1 (based on solid content) Average particle diameter: 220 nm) was prepared.

In addition, butadiene rubbery polymer A instead of A butadiene rubbery polymer I was added, and 0.45 parts by weight of the copolymer latex of Preparation Example 4 instead of 0.45 parts by weight of the copolymer latex of Production Example 1 (based on solid content), Example 1 Graft copolymer latex I (average particle diameter: 320 nm) was prepared in the same manner as.

In addition, a graft copolymer powder I was prepared in the same manner as in Example 1, except that the graft copolymer latex I was used instead of the graft copolymer latex A.

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

Experimental Example One

The physical properties of the graft copolymer latex of Examples and Comparative Examples were measured as follows, and the results are shown in [Table 1] and [Table 2].

① Average particle diameter (nm): After leaving the graft copolymer latex at room temperature for 30 minutes, 1 day, 2 days, 3 days, 4 days and 5 days, the average particle size is used by Nicomp 380 HPL equipment of Nicomp. It was measured by dynamic light scattering.

② Coagulation amount of graft copolymer latex (ppm): After graft copolymer latex was filtered using a 100 mesh mesh, it was put into a convection oven, and then left at 80°C for 720 minutes. Thereafter, the weight of the clot caught in the 100 mesh net was measured and the clot amount of the graft copolymer latex was calculated according to the following formula.

The amount of coagulation of graft copolymer latex (ppm) = {(the weight of coagulation over a 100 mesh network)/(theoretical total weight of butadiene rubbery polymer, styrene, acrylonitrile and additives added during the manufacture of the graft copolymer)} × 1,000,000

Experimental Example 2

The thermoplastic resin compositions of Examples and Comparative Examples were extruded to prepare pellets. The properties of the pellets were measured as follows, and the results are shown in [Table 1] and [Table 2] below.

① Flow index (g/10 min): Measured under the conditions of 220 ℃ and 10 kg according to ASTM D1238.

Experimental Example 3

The thermoplastic resin compositions of Examples and Comparative Examples were extruded and injected to prepare specimens. The properties of the specimens were measured as follows, and the results are shown in [Table 1] and [Table 2] below.

① Impact strength (㎏·m/m, 1/4 In): Measured according to ASTM D256.

② Surface gloss (%): Measured at 45° with a gloss meter according to ASTM D528. The higher the value, the better the surface gloss.

division Example 1 Example 2 Example 3 Example 4 Example 5 Coagulant type Preparation Example 1 Preparation Example 1 Preparation Example 1 Preparation Example 2 Preparation Example 2 First copolymerization time (minutes) 30 60 90 30 60 Second copolymerization time (minutes) 150 120 90 150 120 Graft copolymer latex
Average particle diameter
(Nm) 30 minutes 310 310 320 330 340 1 day 310 310 320 330 340 2 days 320 310 320 330 340 3 days 320 310 320 340 340 4 days 320 310 320 340 340 5 days 320 310 320 340 340 Graft Copolymer Latex Coagulation (ppm) <100 150 300 200 300 Flow index 19.2 19.8 17.8 19.0 19.5 Surface gloss 97.6 98.5 94.3 97.0 98.7 Impact strength 26.0 27.3 26.5 28.0 29.3

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Coagulant type Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 First copolymerization time (minutes) 180 180 30 30 Second copolymerization time (minutes) - - 150 150 Graft copolymer latex
Average particle diameter
(Nm) 30 minutes 320 330 300 320 1 day 320 330 300 320 2 days 320 330 300 320 3 days 320 330 300 330 4 days 320 330 300 330 5 days 320 330 300 330 Graft Copolymer Latex Coagulation (ppm) <100 300 <100 400 Flow index 18.9 19.0 18.8 18.9 Surface gloss 98.7 97.2 97.8 97.0 Impact strength 25.6 26.3 24.5 25.2

Referring to Table 1 and Table 2, in the case of Examples 1 to 5, it was confirmed that the impact strength is excellent compared to Comparative Examples 1 to 4. In addition, when comparing Examples 1 to 5, it was confirmed that Example 2 and Example 5 having a primary copolymerization time of 60 minutes have excellent flow index, surface gloss, and impact strength, and the copolymer of Preparation Example 2 It was confirmed that Example 5 using as a flocculant had the best flow index, surface gloss, and impact strength.

On the other hand, when comparing Examples 1 to 3 and Comparative Example 1, Example 4, and Example 5 and Comparative Example 2, respectively, Comparative Example 1 and Comparative Example 2 had excellent surface gloss, but confirmed that the impact strength was lowered. Could.

When Example 1, Example 4, Comparative Example 3 and Comparative Example 4 were compared, it was confirmed that Example 1 and Example 4 were superior to both Comparative Example 3 and Comparative Example 4 in terms of flow index, surface gloss, and impact strength. . From these results, it was confirmed that the use of a copolymer of a monomer mixture as a coagulant has a greater effect of improving physical properties than a core-shell structure copolymer as a coagulant.

Claims (10)

A first non-conversation step of preparing a diene-based rubbery polymer that is non-large by adding a coagulant to the diene-based rubbery polymer;
A primary copolymerization step of introducing and copolymerizing the non-enlarged diene-based rubbery polymer, aromatic vinyl monomer and vinyl cyan monomer, to prepare a first copolymer;
A second non-consolidation step of preparing a non-consolidated second copolymer by adding a flocculant to the first copolymer; And
And a second copolymerization step of copolymerizing the second copolymer.
The coagulant is a method for producing a graft copolymer comprising a copolymer of a monomer mixture comprising a (meth)acrylate-based monomer and a carboxylic acid-based monomer.
The method according to claim 1,
The second step of preparing the graft copolymer is a step of preparing a second copolymerized by adding the flocculant to the first copolymer at a time when the polymerization conversion rate is 55 to 80%.
The method according to claim 1,
The second hypertrophy step is a step of preparing a graft copolymer by adding the coagulant to the first copolymer at a time when the polymerization conversion rate is 60 to 75%.
The method according to claim 1,
Method for producing a graft copolymer in which the flocculant is added in an amount of 0.3 to 2 parts by weight based on 100 parts by weight of the diene-based rubbery polymer in the first hypertrophy step.
The method according to claim 1,
Method for producing a graft copolymer in which the flocculating agent is added in an amount of 0.3 to 2 parts by weight based on 100 parts by weight of the diene-based rubbery polymer in the second hypertrophy step.
The method according to claim 1,
The method of preparing a graft copolymer, wherein the copolymer of the monomer mixture has an average particle diameter of 50 to 150 nm.
The method according to claim 1,
The copolymer of the monomer mixture is a method for producing a graft copolymer that is at least one selected from the group consisting of ethyl acrylate/methacrylic acid copolymer and n-butyl acrylate/methacrylic acid copolymer.
The method according to claim 1,
The method of preparing a graft copolymer, wherein the copolymer of the monomer mixture is in the form of latex.
The method according to claim 8,
The latex type copolymer is a method for producing a graft copolymer that is prepared by emulsion polymerization.
The method according to claim 1,
The monomer mixture is a (meth) acrylate-based monomer and a carboxylic acid-based monomer comprising a 97:3 to 80:20 weight ratio of the graft copolymer production method.