Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0049959 dated April 29, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
technical field
[4]
The present invention relates to a polymer coagulant that can be used for preparing a graft copolymer having excellent impact resistance and fluidity, and a graft copolymer including the same.
background
[5]
The acrylonitrile-butadiene-styrene copolymer (ABS copolymer) is a thermoplastic copolymer, prepared by graft copolymerization of styrene and acrylonitrile to butadiene rubbery polymer.
[6]
ABS copolymer has excellent physical properties such as high impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity, and workability compared to conventional high-impact polystyrene (HIPS), and of these, processability is particularly excellent. do. Due to these characteristics, the ABS copolymer can be used in interior and exterior materials for automobiles, office equipment, parts of various electric and electronic products, or toys.
[7]
On the other hand, in order to prepare an ABS copolymer having excellent impact resistance, the particle size of the diene-based rubber polymer must be appropriately adjusted. In general, when the average particle diameter is 0.25 to 0.5 μm, the surface gloss property is 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 prepared by emulsion polymerization, the polymerization time is too long, resulting in poor productivity. Accordingly, after preparing a diene-based rubbery polymer having an average particle diameter of about 0.1 μm, a method of enlarging the diene-based rubbery polymer using a coagulant has been proposed. However, when acetic acid is used as a coagulant during hypertrophy, excess agglomerates are generated, and in order to reduce the occurrence of agglomerates, lowering the concentration of diene-based rubbery polymer latex causes a problem in that productivity is lowered. In addition, when an acrylate-based polymer is used as the coagulant, a significant amount of the polymer coagulant remains in the finally prepared ABS copolymer, thereby limiting improvement in processability.
[8]
Therefore, there is a need to develop a polymer coagulant capable of improving processability while suppressing the generation of agglomerates, and also improving physical properties including impact resistance.
[9]
[10]
Prior art literature
[11]
(Patent Document 1) KR 10-1432633
[12]
(Patent Document 2) KR 2004-0147655A
[13]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
An object of the present invention is to provide a polymer coagulant capable of suppressing the occurrence of agglomerates during hypertrophy and improving the impact resistance and fluidity of the final graft copolymer prepared after hypertrophy.
means of solving the problem
[15]
In order to solve the above problems, the present invention includes a conjugated diene-based polymer core and a shell including an ethyl acrylate-derived unit and a methacrylamide-derived unit, wherein the shell includes an ethyl acrylate-derived unit and a methacrylamide-derived unit. It provides a polymer coagulant comprising a weight ratio of 92:8 to 83:17.
[16]
In addition, the present invention is a step of enlarging the polymer coagulant by adding the polymer coagulant to the conjugated diene-based polymer (S1), and graft polymerization of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer to the enlarged conjugated diene-based polymer (S2) It provides a method for producing an enlarged graft copolymer comprising a.
Effects of the Invention
[17]
The polymer coagulant of the present invention can enlarge the conjugated diene-based polymer to an appropriate particle size range, and can improve the impact resistance and fluidity of the graft copolymer prepared from the enlarged conjugated diene-based polymer.
Best mode for carrying out the invention
[18]
Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.
[19]
[20]
Preparation Example 1
[21]
76.4 parts by weight of ion-exchanged water and 75 parts by weight of polybutadiene having a particle size of 1000 Å were added to the nitrogen-substituted polymerization reactor, and then the temperature was raised to 80° C. while stirring for 30 minutes, after which 21.2 parts by weight of ethyl acrylate monomer and methacrylamide monomer Graft polymerization was carried out while continuously adding 3.8 parts by weight of the mixture, 0.15 parts by weight of sodium dodecylbenzenesulfonate (SDBS), and 0.2 parts by weight of potassium persulfate (KPS) at 80° C. over 1 hour, and polymerization was performed when the polymerization conversion rate was 98%. to prepare a polymer coagulant A.
[22]
[23]
Preparation 2
[24]
A polymer coagulant B was prepared in the same manner as in Preparation Example 1, except that 21.9 parts by weight of ethyl acrylate and 3.1 parts by weight of methacrylamide were used as monomers.
[25]
[26]
Preparation 3
[27]
A polymer coagulant C was prepared in the same manner as in Preparation Example 1, except that 22.5 parts by weight of ethyl acrylate and 2.5 parts by weight of methacrylamide were used as monomers.
[28]
[29]
Comparative Preparation Example 1
[30]
A polymer coagulant D was prepared in the same manner as in Preparation Example 1, except that 23.1 parts by weight of ethyl acrylate and 1.9 parts by weight of methacrylamide were used as monomers.
[31]
[32]
Comparative Preparation Example 2
[33]
A polymer coagulant E was prepared in the same manner as in Preparation Example 1, except that 20.6 parts by weight of ethyl acrylate and 4.4 parts by weight of methacrylamide were used as monomers.
[34]
[35]
Comparative Preparation Example 3
[36]
Polymer flocculant F was prepared in the same manner as in Preparation Example 1, except that 80 parts by weight of polybutadiene was used, and 18 parts by weight of ethyl acrylate and 2 parts by weight of methacrylic acid were used as monomers.
[37]
[38]
Comparative Preparation Example 4
[39]
In Preparation Example 1, 50 parts by weight of ethyl acrylate polymer was used instead of polybutadiene as the core, and 41 parts by weight of ethyl acrylate and 9 parts by weight of methacrylic acid were used as monomers. Flocculant G was prepared.
[40]
[41]
The components of the polymer coagulant prepared in Preparation Examples and Comparative Preparation Examples are summarized and shown in Table 1 below.
[42]
[Table 1]
classification Polymer Flocculant Components
Core/Shell Weight Ratio Core component (parts by weight) Shell component (parts by weight)
PBL EA EA MAM MAA
Preparation Example 1 A 75/25 75 - 21.2 3.8 -
Preparation 2 B 75/25 75 - 21.9 3.1 -
Preparation 3 C 75/25 75 - 22.5 2.5 -
Comparative Preparation Example 1 D 75/25 75 - 23.1 1.9 -
Comparative Preparation Example 2 E 75/25 75 - 20.6 4.4 -
Comparative Preparation Example 3 F 80/20 80 - 18 - 2
Comparative Preparation Example 4 G 50/50 - 50 41 - 9
[43]
(PBL: polybutadiene, EA: ethyl acrylate, MAM: methacrylamide, MAA: methacrylic acid)
[44]
[45]
Example 1
[46]
After raising the temperature to 50° C. while stirring 60 parts by weight of a butadiene rubber polymer having a particle size of 1000 Å, 1.32 parts by weight of the polymer coagulant A prepared in Preparation Example 1 was added and stirred for 15 minutes to enlarge the butadiene polymer to a particle size of 3000 Å. As a result of measuring the particle size of the enlarged butadiene polymer, it was 2780 Å. Then, 30 parts by weight of a styrene monomer, 10 parts by weight of an acrylonitrile monomer, 0.12 parts by weight of cumene hydroperoxide (CHP), and 0.34 parts by weight of tertiary dodecyl mercaptan (TDM) were continuously added for 3 hours to graft polymerization the monomers. to prepare an enlarged graft copolymer. The prepared graft copolymer latex was aggregated with MgSO 4 , washed to obtain a powder, and the powder and the SAN copolymer were mixed and extruded into a mixer to obtain pellets.
[47]
[48]
Example 2
[49]
In Example 1, powder and pellets were obtained in the same manner except that B was used as the polymer coagulant. As a result of measuring the particle size of the enlarged butadiene polymer, it was 2690 Å.
[50]
[51]
Example 3
[52]
In Example 1, powder and pellets were obtained in the same manner except that C was used as the polymer coagulant. As a result of measuring the particle size of the enlarged butadiene polymer, it was 2620 Å.
[53]
[54]
Comparative Example 1
[55]
In Example 1, powder and pellets were obtained in the same manner except that D was used as the polymer coagulant. As a result of measuring the particle size of the enlarged butadiene polymer, it was 1980Å.
[56]
[57]
Comparative Example 2
[58]
In Example 1, the same procedure was performed except that E was used as the polymer coagulant, and when E was used as the polymer coagulant, agglomeration occurred during hypertrophy, and a graft copolymer was not obtained thereafter.
[59]
[60]
Comparative Example 3
[61]
Powder and pellets were obtained in the same manner as in Example 1, except that 58 parts by weight of butadiene rubbery polymer was used and 2 parts by weight of F was used as a polymer flocculant. As a result of measuring the particle size of the enlarged butadiene polymer, it was 2830 Å.
[62]
[63]
Comparative Example 4
[64]
Powder and pellets were obtained in the same manner as in Example 1, except that 58 parts by weight of the butadiene rubbery polymer was used and 2 parts by weight of G was used as the polymer flocculant. As a result of measuring the particle size of the enlarged butadiene polymer, it was 2930 Å.
[65]
[66]
The graft copolymers prepared in Examples and Comparative Examples are summarized in Table 2 below.
[67]
[Table 2]
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
polymer flocculant A B C D E F G
Butadiene rubbery latex content 60 60 60 60 60 58 58
Polymer Flocculant Content 1.32 1.32 1.32 1.32 1.32 2 2
Hypertrophic rubber particle size (Å) 2780 2690 2620 1980 clot during hyperconversation 2830 2930
[68]
[69]
From Table 2, it was confirmed that the polymer flocculant containing methacrylamide of the present invention can enlarge the butadiene rubber polymer to a particle size within an appropriate range, like the conventional polymer flocculant containing methacrylic acid. In addition, when the content of methacrylamide in the polymer coagulant containing methacrylamide is out of the scope of the present invention, it was confirmed that the butadiene rubbery polymer could not be enlarged, or the effect was not sufficient even if it was enlarged.
[70]
[71]
Experimental Example - Confirmation of physical properties of powders and pellets
[72]
[73]
For the powders and pellets prepared in Examples and Comparative Examples, physical properties were measured using the following method.
[74]
[75]
* Flow index (MI, g/10 min): measured under the conditions of 220 °C and 10 kg in accordance with ASTM D1238.
[76]
* Izod impact strength (IMP, kgfcm/cm): In accordance with ASTM D256, it was measured by making a notch in a pellet specimen having a thickness of 1/4 inch.
[77]
[78]
The physical property values ​​measured by the above method are summarized in Table 3 below.
[79]
[Table 3]
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
MI 21.0 19.9 21.4 16.5 clotting during hypertrophy 19.8 17.1
IMP(1/4'') 27.1 27.5 27.0 10.9 25.0 25.3
[80]
[81]
From Table 3 above, the graft copolymer enlarged through the polymer coagulant of the present invention exhibits superior flow index and impact strength compared to the graft copolymers enlarged through the polymer coagulant containing methacrylic acid (Comparative Examples 3 and 4). was confirmed. In addition, even in the polymer coagulant including methacrylamide, if the content of methacrylamide is outside the scope of the present invention, enlargement itself is impossible, or the effect of enlargement is insignificant, so that the physical properties of the graft copolymer prepared therefrom are also poor. could confirm that
Modes for carrying out the invention
[82]
Hereinafter, the present invention will be described in more detail.
[83]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[84]
[85]
In the present invention, the particle size of the conjugated diene-based polymer and the enlarged graft copolymer can be measured using a dynamic light scattering method, and in detail, it can be measured using Nicomp 380 equipment (product name, manufacturer: Nicomp). can
[86]
In the present specification, "particle diameter" may mean an arithmetic mean particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of scattering intensity.
[87]
[88]
polymer flocculant
[89]
The present invention includes a conjugated diene-based polymer core and a shell including ethyl acrylate-derived units and methacrylamide-derived units, wherein the shell comprises ethyl acrylate-derived units and methacrylamide-derived units from 92:8 to 83:17 It provides a polymer flocculant that is included in a weight ratio of.
[90]
[91]
The polymer flocculant of the present invention may have a core-shell form of a shell including a conjugated diene-based polymer core, ethyl acrylate-derived units, and methacrylamide-derived units. When the polymer flocculant has such a core-shell form, it may have an advantage in that it has excellent thickening efficiency compared to a polymer flocculant that is not a core-shell form having the same monomer content.
[92]
[93]
In the polymer coagulant of the present invention, the shell may be formed by graft polymerization of ethyl acrylate and methacrylamide on a conjugated diene-based polymer core. In the case of the prior art, a graft copolymer obtained by graft polymerization of ethyl acrylate and methacrylic acid to a conjugated diene-based polymer was used as a polymer coagulant, but the inventor of the present invention used methacrylamide containing amide instead of methacrylic acid. The present invention was completed by discovering that when included in the shell of the polymer coagulant, the physical properties, in particular, fluidity and impact resistance, of the finally prepared enlarged graft copolymer can be further improved.
[94]
[95]
In the polymer flocculant of the present invention, the conjugated diene-based polymer contained in the core may be in the form of a latex prepared by emulsion polymerization, specifically, crosslinking reaction of a diene-based monomer, and the diene-based monomer is 1,3-butadiene, It may be at least one selected from the group consisting of isoprene, chloroprene and piperylene, of which 1,3-butadiene may be preferable.
[96]
The conjugated diene-based polymer may have a particle diameter of 500 to 1500 Å, preferably 800 to 1200 Å. If it satisfies the above-mentioned range, it has an appropriate particle size when enlarged, and latex stability may also be excellent.
[97]
[98]
In the polymer flocculant of the present invention, when graft polymerization of ethyl acrylate and methacrylamide to the conjugated diene-based polymer is performed, the ethyl acrylate monomer and the methacrylamide monomer may be continuously or dividedly added. When the monomers are continuously or dividedly added, a uniform graft polymerization result can be obtained compared to the case of batch input.
[99]
[100]
In the polymer coagulant of the present invention, the input temperature of the monomers may be 60 to 100 ℃, preferably 70 to 90 ℃. When the graft polymerization is carried out by input in the above temperature range, uniform graft polymerization can be achieved because the two monomers can be uniformly mixed.
[101]
[102]
In the polymer coagulant of the present invention, the weight ratio of the core to the shell may be 70:30 to 80:20, preferably 73:27 to 77:23. If the core contains less than this, latex may coagulate during hypertrophy, and if it contains more than this, hypertrophy may not occur sufficiently.
[103]
In the polymer flocculant of the present invention, the weight ratio of the ethyl acrylate-derived unit and the methacrylamide-derived unit included in the shell may be 92:8 to 83:17, preferably 90:10 to 85:15. have. When the ethyl acrylate-derived unit and the methacrylamide-derived unit are included in the above weight ratio, the impact resistance and fluidity of the enlarged graft copolymer to be prepared can be further improved.
[104]
[105]
Hypertrophic graft copolymer
[106]
The present invention provides an enlarged graft copolymer comprising the aforementioned polymer flocculant, a conjugated diene-based polymer, a unit derived from a vinyl cyanide-based monomer, and a unit derived from an aromatic vinyl-based monomer.
[107]
[108]
In the hypertrophic graft copolymer of the present invention, the above-described polymer flocculant serves to agglomerate and enlarge the conjugated diene-based polymer. By graft polymerization of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer to a conjugated diene-based polymer enlarged through a polymer flocculant, an enlarged graft copolymer to be provided by the present invention can be prepared.
[109]
[110]
The particle size of the enlarged graft copolymer of the present invention may be 2500 to 3500 Å, preferably 2800 to 3200 Å. When the copolymer prepared by grafting after being enlarged has a particle size in this range, excellent impact resistance can be realized without deterioration of surface gloss properties.
[111]
[112]
In the present invention, the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile This is preferable. In the present invention, the vinyl cyan-based unit may mean a unit derived from a vinyl cyan-based monomer.
[113]
[114]
In the present invention, the aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, of which styrene is preferable. In the present invention, the aromatic vinyl-based unit may mean a unit derived from an aromatic vinyl-based monomer.
[115]
[116]
In the present invention, the polymer coagulant may be included in an amount of 1 to 4 parts by weight, preferably 2 to 3 parts by weight, based on 100 parts by weight of the conjugated diene-based polymer. When the polymer flocculant is included in more than this, it is not economical because the amount of the polymer flocculant used is large compared to the required degree of enlargement, or the enlarged graft copolymer of the desired particle size may not be manufactured because the amount of the polymer coagulant is too large compared to the required degree of enlargement. When included, the conjugated diene-based polymer may not be sufficiently enlarged.
[117]
[118]
In the present invention, based on 100 parts by weight of the conjugated diene-based polymer, the vinyl cyan-based monomer-derived unit may be included in 10 to 25 parts by weight, preferably 15 to 20 parts by weight, and the aromatic vinyl-based monomer-derived unit is 40 to 60 parts by weight. It may be included in parts by weight, preferably 45 to 55 parts by weight. When the vinyl cyan-based monomer-derived unit and the aromatic vinyl-based monomer-derived unit are included in less than this, the impact strength may be significantly reduced, and if more than this is included, the fluidity may be reduced.
[119]
[120]
Method for preparing hypertrophic graft copolymer
[121]
The present invention includes the step (S1) of adding the above-mentioned polymer flocculant to the conjugated diene-based polymer to enlarge it and the step (S2) of graft polymerization of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer to the enlarged conjugated diene-based polymer (S2) A method for preparing a hypertrophic graft copolymer is provided.
[122]
[123]
In the method for producing an enlarged graft copolymer of the present invention, the step S1 is a step of agglomerating the conjugated diene-based polymer using a polymer coagulant to enlarge it. The thickening may be performed by mixing and stirring a polymer flocculant and a conjugated diene-based polymer, and may be performed at a temperature of 30 to 70°C, preferably 40 to 60°C. When hypertrophy is performed under such conditions, it is possible to achieve uniform thickening of the conjugated diene-based polymer.
[124]
The conjugated diene-based polymer enlarged in step S1 may have a particle diameter of 2500 to 3500 Å, preferably 2800 to 3200 Å. When the enlarged conjugated diene-based polymer has such a particle size, the finally prepared enlarged graft copolymer may also have a particle size within the above-mentioned range.
[125]
[126]
The step S2 is a step of graft polymerization by using the enlarged conjugated diene-based polymer as a core, and adding a vinyl cyan-based monomer and an aromatic vinyl-based monomer. The input of the monomers may be continuous or divided input, and in the case of continuous or divided input, uniform graft polymerization may be achieved compared to the case of batch input. In addition, in step S2, additives such as an emulsifier, a polymerization initiator, a molecular weight regulator, an activator, and water may be added together with the monomer to perform polymerization.
[127]
[128]
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 or more, of which sodium dodecyl benzene sulfonate is preferable.
[129]
The emulsifier is preferably added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total of the diene-based rubbery polymer, the aromatic vinyl-based monomer and the vinyl cyan-based monomer. If the above-mentioned range is satisfied, the particle size of the prepared hypertrophic graft copolymer is appropriate to minimize the occurrence of agglomerates.
[130]
[131]
The kind of polymerization initiator is sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t- Butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyro It may be at least one selected from the group consisting of nitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) methyl. The polymerization initiator may be added in an amount of 0.01 to 1 part by weight or 0.05 to 0.5 parts by weight, of which 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, the aromatic vinyl-based monomer and the vinyl cyan-based monomer. It is preferable to input. When the above-mentioned range is satisfied, it is possible to prepare a diene-based graft copolymer having more excellent impact resistance.
[132]
[133]
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 disulfide and diisopropylxanthogen disulfide, of which t-dodecyl mercaptan is preferable. The molecular weight modifier may be added in an amount of 0.01 to 1.5 parts by weight or 0.1 to 1 parts by weight, of which 0.1 to 1 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, the aromatic vinyl-based monomer and the vinyl cyan-based monomer. It is preferable to input. When the above-described range is satisfied, a diene-based graft copolymer having an excellent balance between flow index and impact resistance can be prepared.
[134]
[135]
The activator may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, disodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate anhydiros and sodium sulfate, Among them, at least one selected from the group consisting of dextrose, ferrous sulfate and sodium pyrophosphate is preferable. The activator is preferably added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total of the diene-based rubbery polymer, the aromatic vinyl-based monomer, and the vinyl cyan-based monomer. When the above-mentioned range is satisfied, a diene-based graft copolymer having excellent flow index, impact resistance and color characteristics can be prepared.
[136]
[137]
The water may be ion-exchanged water or distilled water.
[138]
[139]
On the other hand, the graft copolymer prepared through the method for preparing the graft copolymer may be in the form of a latex. Accordingly, in the method for producing a graft copolymer according to an embodiment of the present invention, after step S2, the step of preparing the graft copolymer powder may be further performed.
[140]
In detail, at least one 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 step S2 to coagulate, and through aging, dehydration, washing and drying, the graft air Coalesced powder can be prepared.
Claims
[Claim 1]
conjugated diene-based polymer core; and a shell including ethyl acrylate-derived units and methacrylamide-derived units, wherein the shell contains ethyl acrylate-derived units and methacrylamide-derived units in a weight ratio of 92:8 to 83:17. Polymer Flocculant.
[Claim 2]
The polymer flocculant according to claim 1, wherein the weight ratio of the core and the shell is 7:3 to 8:2.
[Claim 3]
The polymer coagulant of claim 1, wherein the conjugated diene-based polymer has a particle diameter of 500 to 1500 Å.
[Claim 4]
The polymer coagulant of claim 1; conjugated diene-based polymers; a unit derived from a vinyl cyanide monomer; and a unit derived from an aromatic vinylic monomer.
[Claim 5]
The hypertrophic graft copolymer according to claim 4, having a particle diameter of 2500 to 3500 Å.
[Claim 6]
According to claim 4, wherein the polymer coagulant is an enlarged graft copolymer that is included in 1 to 4 parts by weight based on 100 parts by weight of the conjugated diene-based polymer.
[Claim 7]
The hypertrophic graft copolymer of claim 4, wherein the vinyl cyan-based monomer-derived unit is included in an amount of 10 to 25 parts by weight based on 100 parts by weight of the conjugated diene-based polymer.
[Claim 8]
The hypertrophy graft copolymer of claim 4, wherein the aromatic vinyl-based monomer-derived unit is included in an amount of 40 to 60 parts by weight based on 100 parts by weight of the conjugated diene-based polymer.
[Claim 9]
A step (S1) of adding the polymer coagulant of claim 1 to the conjugated diene-based polymer to enlarge it; And Graft polymerization of a vinyl cyan-based monomer and an aromatic vinyl-based monomer to the enlarged conjugated diene-based polymer (S2); Method for producing an enlarged graft copolymer comprising a.
[Claim 10]
The method of claim 9, wherein the particle diameter of the conjugated diene-based polymer enlarged in step S1 is 2500 to 3500 Å.
[Claim 11]
The method of claim 9, wherein the polymer coagulant is added in 1 to 4 parts by weight based on 100 parts by weight of the conjugated diene-based polymer.