KR100708988B1 - Method for preparing graft copolymer - Google Patents

Abstract

The present invention relates to a method for producing a graft copolymer, in particular a monomer mixture of rubber latex having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95% by weight, optionally an aromatic vinyl compound and a vinyl cyan compound. , Initiating the reaction by administering a peroxycarbonate-based redox initiator, an activator, an emulsifier, a molecular weight regulator, and deionized water at the same time, concurrently with or after the initiation of the reaction, the aromatic vinyl compound and vinyl cyan Continuously reacting a monomer mixture comprising a compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water, and simultaneously administering a peroxycarbonate-based redox initiator and an activator to the reactants Method for producing a graft copolymer characterized in that it comprises the step of further reacting and prepared by the method A thermoplastic resin composition comprising a graft copolymer.

According to the present invention, the graft ratio of the graft copolymer may be improved, and the glossiness and thermal stability may be significantly improved while maintaining mechanical and appearance properties.

Graft copolymer, thermoplastic resin, peroxycarbonate-based redox initiator, activator, graft rate

Description

Production Method of Graft Copolymer {METHOD FOR PREPARING GRAFT COPOLYMER}

The present invention relates to a method for producing a graft copolymer, and more particularly, it is possible to improve the graft ratio of the graft copolymer and to significantly improve gloss and thermal stability while maintaining mechanical and appearance properties. It relates to a thermoplastic resin composition comprising a method for producing a graft copolymer and a graft copolymer prepared by the above method.

Acrylonitrile-butadiene-styrene (ABS) resins have excellent mechanical properties, colorability, and moldability, so that they can be used for various kinds of housings and toys for home appliances such as refrigerators and washing machines. Widely used in offices, office equipment, automobiles, etc.

In order to disperse the rubber component in the acrylonitrile-styrene resin, such an ABS resin may be dissolved in a monomer acrylonitrile, styrene and a solvent and polymerized in a solution to the rubber latex prepared by emulsion polymerization. A graft copolymer is prepared by grafting acrylonitrile and styrene, and there is a method of mixing and processing a styrene-acrylonitrile resin prepared by separate solution polymerization.

In the case of the ABS resin manufactured by the solution polymerization method, although the mass production and relatively low manufacturing cost and excellent color, it is difficult to produce a variety of quality products and there is a problem that can not achieve a specialized high value-added. In addition, the physical properties such as surface gloss, impact strength, thermal stability, etc. are reduced, the use thereof is limited, and it is mainly used in combination with ABS resin produced by emulsion polymerization method.

Typically, the ABS resin is prepared by combining a rubber latex prepared by emulsion polymerization with a graft copolymer obtained by copolymerizing one or more monomers and a styrene copolymer prepared by bulk polymerization or solution polymerization. ABS resin produced by emulsion polymerization method is made of ABS resin as a final product by mixing with styrene copolymer prepared by solution polymerization method despite high manufacturing cost. It has monomer composition and molecular weight which has excellent surface gloss and impact strength. It is manufactured from a variety of different types of products.

In order to improve the functionalization and diversification of the ABS resin, the high value of the ABS resin is required through the emulsion polymerization as described above. The key technology is to secure the desired physical properties of the final ABS resin while reducing and increasing the input of solution-polymerized SAN resin, which has a relatively low manufacturing cost.

To this end, it is possible to reduce the ABS resin content through the emulsion polymerization to the final ABS resin by increasing the rubber content during ABS emulsion polymerization. However, this method reduces the amount of acrylonitrile-based and styrene-based monomers grafted as the rubber content increases, which may destabilize the form of the rubber, thereby lowering mechanical properties as well as gloss and thermal stability. . Therefore, there is a technical problem very difficult to raise the rubber content more than a certain amount.

In order to manufacture such a high value ABS resin, it is important to control the morphology and gel content of the rubber, the molecular weight, the graft ratio, and the monomer composition ratio of the copolymer grafted to the rubber latex. In particular, effective rubber grafting of the monomers is important for producing a high rubber content resin.

Korean Patent Laid-Open Publication No. 10-2002-7010992 has a rubber latex having an average particle diameter of 0.15 to 0.22 μm and a gel content of 50 to 85 wt%, and a rubber latex having an average particle diameter of 0.26 to 0.34 μm and a gel content of 45 to 70 wt%. A method for grafting monomers in which acrylonitrile and styrene have a weight ratio of 27:73 is disclosed. The patent discloses a rubber having a relatively small rubber particle size to compensate for disadvantages in manufacturing a high rubber content, but there is a problem in that mechanical and appearance properties may be reduced.

In addition, Korean Patent Publication No. 10-2001-0073352 has an effective physical property using a rubber latex having a high rubber content through thermal decomposition of a water-soluble initiator in a rubber latex having an average particle diameter of 0.28 to 0.33 μm and a gel content of 75 to 85 wt%. However, since the thermal decomposition of the water-soluble initiator is effectively decomposed at about 65 ℃ or more, it is not easy to control the reaction heat during the emulsion polymerization, and the reaction for a long time, there was a problem that requires a high polymerization operation cost.

In order to solve the problems of the prior art as described above, the present invention can improve the graft ratio of the graft copolymer, while maintaining the mechanical properties and appearance properties, while the graft copolymer can significantly improve the gloss and thermal stability It is an object of the present invention to provide a thermoplastic resin composition comprising a method for producing the graft copolymer prepared by the method, and the graft copolymer prepared by the method.

In order to achieve the above object, the present invention provides a method for producing a graft copolymer,

a) a monomer mixture of rubber latex having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95 wt%, an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an activator, an emulsifier, Initiating the reaction by batch administration of a molecular weight modifier and deionized water;

b) simultaneously or after the start of the reaction of step a), the reaction mixture is continuously administered with a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water. Reacting; And

c) further reacting the reaction product of step b) with a peroxycarbonate-based redox initiator and an activator

It provides a method for producing a graft copolymer comprising a.

In addition, the present invention is a method for producing a graft copolymer,

a) After a batch administration of rubber latex, emulsifier, molecular weight regulator, and deionized water having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95 wt%, a peroxycarbonate-based redox initiator and an activator are Administering to initiate the reaction;

b) simultaneously or after the start of the reaction of step a), the reaction mixture is continuously administered with a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water. Reacting; And

c) further reacting the reaction product of step b) with a peroxycarbonate-based redox initiator and an activator

It provides a method for producing a graft copolymer comprising a.

In addition, the present invention is a thermoplastic resin composition,

a) graft copolymer prepared by the above method; And

b) styrenic copolymer

It provides a thermoplastic resin composition comprising a.

Hereinafter, the present invention will be described in detail.

The graft copolymer of the present invention is a monomer mixture of rubber latex, aromatic vinyl compound and vinyl cyan compound having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95% by weight, and a peroxycarbonate-based redox initiator. Activating, emulsifying, molecular weight adjusting, and deionized water in a batch to initiate a reaction; At the same time as or after the start of the reaction of the above step, the reaction mixture is continuously reacted with a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water; And reacting the reaction product of the step with a batch of peroxycarbonate-based redox initiator and activator to further react, wherein the batch-containing monomer mixture is subjected to continuous administration as necessary. Full doses may be administered.

The preparation method of the graft copolymer of the present invention will be described in detail as follows.

a) reaction initiation step

This step comprises the steps of: i) a rubber latex having an average particle diameter of 0.26 to 0.34 μm and a gel content of 65 to 95% by weight, a monomer mixture consisting of ii) a) an aromatic vinyl compound and b) a vinyl cyan compound, iii) peroxycarbo It is the step of starting the reaction by batch administration of the nate-based redox initiator, (i) activator, (iii) emulsifier, (iii) molecular weight regulator, and (iii) deionized water.

Specifically, this step is an average particle diameter of 0.26 ~ 0.34 ㎛, 60 to 70 parts by weight of rubber latex having a gel content of 65 to 95% by weight, 70 to 75% by weight aromatic vinyl compound and 25 to 30% by weight vinyl cyan compound 5 to 30% by weight (1.5 to 12 parts by weight), 0.1 to 0.5 parts by weight of emulsifier, 0.1 to 1.0 parts by weight of molecular weight modifier, and 100 to 150 parts by weight of deionized water in a total of 30 to 40 parts by weight of the monomer mixture, After heating up to a temperature of ˜50 ° C., it is contained in 30 to 40% by weight (0.015 to 0.2 parts by weight) and iii) 0.061 to 0.61 parts by weight of 0.05 to 0.5 parts by weight of the peroxycarbonate-based redox initiator. After the polymerization reaction is initiated by administering 60 to 80% by weight (0.0366 to 0.488 parts by weight), the temperature is gradually raised to 60 to 70 ° C.

The rubber latex of vi) preferably has an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95% by weight. If the average particle diameter is less than 0.26 ㎛, there is a problem that the impact strength is lowered according to the small rubber particle size, if it exceeds 0.34 ㎛ there is a problem that the surface gloss is lowered, if the gel content is less than 65% by weight the surface There is a problem that the overall mechanical properties are lowered according to the graft lowering, and when it exceeds 95% by weight, the impact strength is lowered as the glass transition temperature of the rubber increases.

The rubber latex is preferably contained in 60 to 70 parts by weight based on 100 parts by weight of the total monomers used in the graft copolymer production, when the content is less than 60 parts by weight, the efficiency of the thermoplastic resin is low, the production cost is high There is a problem, when the amount exceeds 70 parts by weight, there is a problem that the graft ratio is lowered because the amount of the monomer that can be grafted is insufficient.

As the aromatic vinyl compound of ii) a), styrene, alphamethylstyrene, alphaethylstyrene, or paramethylstyrene may be used, and styrene is particularly preferable.

Preferably, the aromatic vinyl compound is included in the monomer mixture in an amount of 70 to 75% by weight, and if the content is less than 70% or more than 75% by weight, a problem in mixing with the SAN resin produced in solution polymerization, namely There is a problem that the ratio used is changed according to the type of SAN resin produced.

As the vinyl cyan compound of ii) b), acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, and acrylonitrile is particularly preferable.

The vinyl cyan compound is preferably included in the monomer mixture in an amount of 25 to 30% by weight, and when the content is less than 25% or more than 30% by weight, a problem in mixing with the SAN resin produced in solution polymerization, namely There is a problem that the ratio used is changed according to the type of SAN resin produced.

As described above, the monomer mixture composed of the aromatic vinyl compound and the vinyl cyan compound may be, in addition to the above components, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methyl methacrylate, Vinyl monomers such as methyl acrylate, butyl acrylate, acrylic acid, maleic anhydride, or mixtures thereof can be further used. In this case, the vinyl monomer may be used in a small amount in the monomer mixture.

The monomer mixture including the above components may be administered in a batch in this step (reaction initiation step), and step b) may be continuously performed simultaneously if necessary.

The monomer mixture of ii) as described above is preferably included in an amount of 5 to 30% by weight (1.5 to 12 parts by weight) out of a total of 30 to 40 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer. If the content is less than 5% by weight (1.5 parts by weight) there is a problem that the mechanical properties are lowered, when the content exceeds 30% by weight (12 parts by weight) there is a problem that the control of the reaction heat is difficult.

The peroxycarbonate-based redox initiator of iii) serves to improve the graft rate and to improve mechanical properties, glossiness, and thermal stability when preparing the graft copolymer.

The peroxycarbonate-based redox initiator may be butyl peroxy isopropyl carbonate, butyl peroxy acetate, butyl peroxy laurate, or butyl peroxy ethylhexyl carbonate.

The peroxycarbonate-based redox initiator is preferably included in 30 to 40% by weight (0.015 to 0.2 parts by weight) out of a total of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer production. Do. If the content is less than 30% by weight (0.015 parts by weight) there is a problem that the graft is lowered, when the content exceeds 40% by weight (0.2 parts by weight) there is a problem that a low molecular weight graft copolymer is prepared.

The activator of iii) is used together with the peroxycarbonate-based redox initiator to function to improve the graft rate in the manufacture of the graft copolymer.

The activator may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrroline, or sodium sulfate, preferably dextrose, sodium pyrrolate, and Ferrous sulfate is used.

The activator is preferably included in 60 to 80% by weight (0.0366 to 0.488 parts by weight) of 0.061 to 0.61 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer, more preferably Dex 0.03 to 0.3 parts by weight of trorose, 0.03 to 0.3 parts by weight of sodium pyrolate, and 0.001 to 0.01 parts by weight of ferrous sulfate. If the content is less than 60% by weight (0.0366 parts by weight) or more than 80% by weight (0.488 parts by weight), there is a problem that it is difficult to balance mechanical properties.

The emulsifier of i) may be used alone or in combination of two or more of alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, or alkali salt of rosin acid.

The emulsifier is preferably included in 0.1 to 0.5 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer.

It is preferable to use mercaptans, and it is preferable to use a tertiary dodecyl mercaptan especially as said molecular weight modifier of (i).

The molecular weight modifier is preferably included in 0.1 to 1.0 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer production.

b) reaction step

This step is carried out simultaneously with or after the start of the reaction of step a), and a monomer mixture consisting of iii) a) an aromatic vinyl compound and b) a vinylcyan compound in the reactant of step a), ii) peroxycarb The carbonate-based redox initiator, iii) emulsifier, and iii) ion-exchanged water are continuously reacted.

Specifically, this step is 70 to 95% by weight (21 to 38 parts by weight) of the total monomer mixture of 30 to 40 parts by weight of the monomer mixture consisting of 70 to 75% by weight of the aromatic vinyl compound and 25 to 30% by weight of the vinyl cyan compound. Polymerization while continuously administering 30 to 50% by weight (0.015 to 0.25 parts by weight) of 1.5 parts by weight, 10 to 30 parts by weight of deionized water, and 0.05 to 0.5 parts by weight of peroxycarbonate-based redox initiator The reaction is carried out while maintaining the temperature at 70 to 80 ° C.

In this case, the monomer mixture may be administered in the form of a monomer mixture in which an aromatic vinyl compound and a vinyl cyan compound are mixed, and may be administered in the form of a monomer emulsion in which a monomer mixture, an emulsifier, and deionized water are mixed as necessary.

Of course, each component used in this step may use the same components as described in step a) above.

c) further reaction steps

This step is a step of further reacting the batch of peroxycarbonate-based redox initiator and activator to the reactant of step b). Specifically, this step is 10 to 30% by weight (0.005 to 0.15 parts by weight) of 0.05 to 0.5 parts by weight of the peroxycarbonate-based redox initiator and iii) 20 to 40% by weight (0.0244 to 0.61) of activator 0.061 to 0.61. 0.122 parts by weight) is administered in a batch and further polymerized for 1 to 2 hours at a reaction temperature of 70 to 80 ℃. At this time, the polymerization is terminated when the conversion of the monomer is 99% or more.

The graft copolymer of the present invention is then aggregated with sulfuric acid, MgSO ₄ , CaCl ₂ , or Al ₂ (SO ₄ ) ₃ , which is a common flocculant, and then washed, dehydrated, and dried to obtain a graft copolymer in powder form. Can be obtained.

The graft copolymer of the present invention prepared by the above method is preferably a final graft rate of at least 25%, more preferably 25 to 50%.

In another aspect, the present invention provides a thermoplastic resin composition comprising a graft copolymer and a styrene copolymer prepared as described above.

The graft copolymer is preferably included in 20 to 80 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition, when the content is less than 20 parts by weight there is a problem that the impact strength is lowered, if it exceeds 80 parts by weight There is a problem in that fluidity and gloss decrease.

The styrene copolymer may be prepared by bulk polymerization or solution polymerization, and the vinyl cyan compound is included in the monomer composition in an amount of 20 to 35 parts by weight, and the weight average molecular weight is 80,000 to 200,000.

Specifically, the styrene copolymer is acrylonitrile-styrene copolymer having an acrylonitrile content of 20 to 35% by weight; Terpolymers of acrylonitrile-styrene-alphamethylstyrene having an acrylonitrile content of 25 to 35% by weight, an alphamethylstyrene content of 60 to 70% by weight, and a styrene content of 1 to 10% by weight; Or mixtures thereof.

The styrene copolymer is preferably included in 20 to 80 parts by weight of the graft copolymer with respect to 100 parts by weight of the thermoplastic resin composition, when the content is less than 20 parts by weight there is a problem that the fluidity and gloss decrease occurs, 80 weight If the amount is exceeded, the impact strength is lowered.

In addition, the thermoplastic resin composition of the present invention composed of the above components, if necessary, light stabilizers, lubricants, ultraviolet absorbers, plasticizers, colorants, flame retardants, enhancers, compatibilizers, foaming agents, wood powder, fillers, Of course, metal powder, antimicrobial agent, antifungal agent, silicone oil, or peeling agent can be further used.

According to the production method of the present invention as described above can improve the graft ratio of the graft copolymer, while maintaining the mechanical and appearance properties can be significantly improved gloss and thermal stability.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

In the polymerization reactor equipped with a heating device, 65 parts by weight of rubber latex having an average particle diameter of 0.31 μm and a gel content of 75%, 90 parts by weight of deionized water, and 0.4 parts by weight of potassium rosinate emulsifier were maintained at 50 ° C. Next, 5.4 parts by weight of styrene, 2.1 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.087 parts by weight of sodium pyrolate, 0.11 parts by weight of dextrose, 0.002 parts by weight of ferrous sulfide, and butyl peroxy 0.1 parts by weight of isopropyl carbonate was administered in a batch.

At the same time, 10 parts by weight of ion-exchanged water, 19.8 parts by weight of styrene, 7.7 parts by weight of acrylonitrile, 0.8 parts by weight of potassium rosinate, 0.019 parts by weight of sodium pyrolate, 0.025 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, And butyl peroxy isopropylcarbonate 0.1 part by weight of the mixed emulsion solution were continuously administered for 140 minutes. At this time, the reaction temperature was raised to 70 ℃ for 50 minutes and maintained at this temperature for 90 minutes.

After the continuous administration, 0.019 parts by weight of sodium pyrolate, 0.025 parts by weight of dextrose, 0.001 part by weight of ferrous sulfide, and 0.05 parts by weight of butyl peroxy isopropylcarbonate were collectively administered, and the temperature was raised to 80 ° C. After aging for 1 hour to terminate the reaction to prepare a polymer latex. At this time, the polymerization conversion rate was 98.9%, the total solid content was 46.2%, solid coagulation was 0.02%.

Then, 0.7 parts by weight of antioxidant emulsion IR-1076 (hindered phenol-based antioxidant, Ciba) was added to the polymerization latex, solidified with 2 parts by weight of aqueous sulfuric acid solution, washed and dried to obtain a powdery graft copolymer resin. Obtained. At this time, the graft ratio of the graft copolymer resin was 40%.

The graft rate is 2 g of a powdered rubber-reinforced thermoplastic resin with 100 mL of acetone for 24 hours to dissolve the grafted styrene copolymer in the rubber component, and then separated into a gel and a sol by ultracentrifugal formula 1 Calculated according to.

[Equation 1]

Graft Rate = [(Gel Weight-Rubber Weight) / Rubber Weight] × 100

Example 2

Except for using butyl peroxy laurate as the peroxycarbonate-based redox initiator in Example 1 was carried out in the same manner as in Example 1. At this time, the graft ratio of the obtained graft copolymer resin was 37%.

Example 3

19.8 parts by weight of the styrene and 7.7 parts by weight of the acrylonitrile monomers, which were collectively administered in Example 1, except that the total amount of the monomers (25.2 parts by weight of styrene and 9.8 parts by weight of acrylonitrile) was continuously administered. It carried out by the same method as Example 1. At this time, the graft ratio of the obtained graft copolymer resin was 44%.

Example 4

Except that in Example 1, 70 parts by weight of rubber latex having an average particle diameter of 0.31 μm and a gel content of 75% was used, except that 16.2 parts by weight of styrene and 6.3 parts by weight of acrylonitrile were used during continuous administration simultaneously with batch administration. It carried out in the same manner as in Example 1. At this time, the graft ratio of the obtained graft copolymer resin was 32%.

Comparative Example 1

Except for using hydroperoxide as an initiator in Example 1 was carried out in the same manner as in Example 1. At this time, the graft ratio of the obtained graft copolymer resin was 23%.

Comparative Example 2

Except for using cumene hydro peroxide as an initiator in Example 1 was carried out in the same manner as in Example 1. At this time, the graft ratio of the obtained graft copolymer resin was 27%.

Comparative Example 3

In case of batch administration in Example 1, the temperature in the reactor was maintained at 60 ° C., and then 0.15 parts by weight of potassium persulfate, a water-soluble pyrolysis initiator, was used instead of butyl peroxy isopropyl carbonate as an initiator. The same procedure as in Example 1 was carried out except that 0.25 parts by weight of potassium persulfate was used in place of oxy isopropyl carbonate. At this time, the graft ratio of the obtained graft copolymer resin was 25%.

Comparative Example 4

When continuously administering 19.8 parts by weight of styrene and 7.7 parts by weight of acrylonitrile, the total amount of monomers (25.2 parts by weight of styrene and 9.8 parts by weight of acrylonitrile) was continuously administered in Example 1, and butyl fur was continuously administered. The same procedure as in Example 1 was carried out except that 0.25 parts by weight of potassium persulfate was used instead of oxy isopropyl carbonate. At this time, the graft ratio of the obtained graft copolymer resin was 32%.

22.9 to 24.6 parts by weight of the graft copolymer resin prepared in Examples 1 to 4 and Comparative Examples 1 to 4, 75.6 to 77.1 parts by weight of a SAN resin having a weight average molecular weight of 100,000 and an acrylonitrile content of 28%, and a lubricant 1.5 parts by weight of the mixture was added, followed by extrusion and injection molding to prepare a specimen having a final rubber content of 16% by weight. Using the specimen, Izod impact strength, flow index, surface gloss, and thermal stability were measured by the following method, and the results are shown in Table 1 below.

A) Izod impact strength-measured according to ASTM D256 method. At this time, the thickness of the specimen was 1/4 inch.

B) Melt flow rate-It measured according to ASTM D1238 method under the conditions of 220 degreeC and 10 kg.

C) Surface gloss-measured at 45 ° according to ASTM D528 method.

D) Thermal stability-The surface gloss reduction rate when the resin was injected after the resin stayed in the injection screw set at 250 ° C. for 15 minutes was measured. At this time, the less the surface gloss reduction rate is a product excellent in thermal stability.

division Example Comparative example One 2 3 4 One 2 3 4 Rubber content m 16 wt% Properties Izod impact strength (1/4 ", ㎏cm / ㎝) 27 29 24 25 27 26 24 22 Fluidity (g / 10min 220 ℃, 10 kg) 21 20 22 20 18 18 19 20 Surface Gloss (45 °) 97 95 98 95 85 87 88 90 Thermal Stability (△ Gloss,%) 5 6 4 7 20 15 24 26

Through Table 1, the thermoplastic resin prepared by using the graft copolymers of Examples 1 to 4 prepared according to the present invention has a surface gloss and thermal stability without deterioration in fluidity and impact strength compared to Comparative Examples 1 to 4. It was confirmed that this remarkably excellent.

According to the present invention, the graft ratio of the graft copolymer can be improved, and the glossiness and thermal stability can be significantly improved while maintaining mechanical and appearance properties.

Although only described in detail above with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such variations and modifications belong to the appended claims. .

Claims (19)

In the method for producing a graft copolymer, a) After a batch administration of a monomer mixture consisting of rubber latex, an aromatic vinyl compound and a vinyl cyan compound, an emulsifier, a molecular weight modifier, and deionized water having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95% by weight, Initiating the reaction by administering an oxycarbonate-based redox initiator and an activator; b) simultaneously or after the start of the reaction of step a), the reaction mixture is continuously administered with a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water. Reacting; And c) further reacting the reaction product of step b) with a peroxycarbonate-based redox initiator and an activator Method for producing a graft copolymer, characterized in that it comprises a. The method of claim 1, a) 60 to 70 parts by weight of rubber latex having an average particle diameter of 0.26 to 0.34 μm and a gel content of 65 to 95% by weight, a monomer mixture comprising 70 to 75% by weight of an aromatic vinyl compound and 25 to 30% by weight of a vinyl cyan compound 5-30 weight% (1.5-12 weight part) of 30-40 weight part, 0.1-0.5 weight part of emulsifiers, 0.1-1.0 weight part of molecular weight modifiers, and 100-150 weight part of deionized water are collectively administered, and then put here 30 to 40% by weight (0.015 to 0.2 parts by weight) of 0.05 to 0.5 parts by weight of the oxycarbonate-based redox initiator and 60 to 80% by weight (0.0366 to 0.488 parts by weight) of 0.061 to 0.61 parts by weight of the activator Initiating a polymerization reaction; b) 70 to 95 parts by weight of the monomer mixture consisting of 70 to 75% by weight of the aromatic vinyl compound and 25 to 30% by weight of the vinyl cyan compound in the reaction product simultaneously or after the start of the reaction of step a). 30 to 50 weight percent (0.015 to 0.25 weight) in% (21 to 38 parts by weight), 0.5 to 1.5 parts by weight of emulsifier, 10 to 30 parts by weight of deionized water, and 0.05 to 0.5 parts by weight of peroxycarbonate-based redox initiator Reacting by continuously administering part); And c) 10 to 30% by weight (0.005 to 0.15 parts by weight) of 0.05 to 0.5 parts by weight of the peroxycarbonate-based redox initiator and 20 to 40% by weight of the activator 0.061 to 0.61 (0.0244) to the reaction of step b). To 0.122 parts by weight) to further batch reaction Method for producing a graft copolymer, characterized in that it comprises a. In the method for producing a graft copolymer, a) After a batch administration of rubber latex, emulsifier, molecular weight regulator, and deionized water having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95 wt%, a peroxycarbonate-based redox initiator and an activator are Administering to initiate the reaction; b) Continuously or simultaneously with the start of the reaction of step a), a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a peroxycarbonate-based redox initiator, an emulsifier, and ion-exchanged water are continuously administered to the reactant. To react; And c) further reacting the reaction product of step b) with a peroxycarbonate-based redox initiator and an activator Method for producing a graft copolymer, characterized in that it comprises a. The method of claim 3, a) 60 to 70 parts by weight of rubber latex having an average particle diameter of 0.26 to 0.34 µm and a gel content of 65 to 95% by weight, 0.1 to 0.5 parts by weight of an emulsifier, 0.1 to 1.0 parts by weight of a molecular weight regulator, and 100 to 150 parts by weight of deionized water After the batch was administered, 30 to 40% by weight (0.015 to 0.2 parts by weight) of 0.05 to 0.5 parts by weight of the peroxycarbonate-based redox initiator and 60 to 80% by weight of 0.061 to 0.61 parts of the activator were added thereto. 0.0366 to 0.488 parts by weight) to initiate the polymerization; b) 30 to 40 parts by weight of a monomer mixture consisting of 70 to 75% by weight of an aromatic vinyl compound and 25 to 30% by weight of a vinyl cyan compound in the reaction product simultaneously with or after the start of the reaction of step a), and an emulsifier of 0.5 to 1.5. Reacting by continuously administering 30 to 50% by weight (0.015 to 0.25 parts by weight) of 0.05 parts by weight of deionized water, 10 to 30 parts by weight of deionized water, and 0.05 to 0.5 parts by weight of peroxycarbonate-based redox initiator; And c) 10 to 30% by weight (0.005 to 0.15 parts by weight) of 0.05 to 0.5 parts by weight of the peroxycarbonate-based redox initiator and 20 to 40% by weight of the activator 0.061 to 0.61 (0.0244) to the reaction of step b). To 0.122 parts by weight) to further batch reaction Method for producing a graft copolymer, characterized in that it comprises a. The method according to any one of claims 1 to 4, After the batch administration of the components in step a), the reaction temperature is raised to 40 to 50 ° C., and the temperature is raised to 60 to 70 ° C. after administration of the peroxycarbonate-based redox initiator and activator. The manufacturing method of the graft copolymer made into. The method according to any one of claims 1 to 4, Method of producing a graft copolymer, characterized in that the reaction is carried out while maintaining the polymerization temperature at 70 ~ 80 ℃ during continuous administration in step b). The method according to any one of claims 1 to 4, Method for producing a graft copolymer, characterized in that for further polymerization for 1 to 2 hours at 70 ~ 80 ℃ after batch administration in step c). The method according to any one of claims 1 to 4, The aromatic vinyl compound is at least one selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, and paramethylstyrene. The method according to any one of claims 1 to 4, The vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method according to any one of claims 1 to 4, The monomer mixture is maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methyl methacrylate, methyl acrylate, butyl acrylate, acrylic acid, and maleic anhydride. A method for producing a graft copolymer, characterized in that it further comprises a vinyl monomer selected from the group consisting of one or more. The method according to any one of claims 1 to 4, Wherein the peroxycarbonate-based redox initiator is selected from the group consisting of butyl peroxy isopropyl carbonate, butyl peroxy acetate, butyl peroxy laurate, and butyl peroxy ethylhexyl carbonate Method for producing a graft copolymer characterized in that. The method according to any one of claims 1 to 4, Preparation of graft copolymers characterized in that the activator is selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium sulfate Way. The method according to any one of claims 1 to 4, The method of producing a graft copolymer, characterized in that the emulsifier is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. The method according to any one of claims 1 to 4, Method for producing a graft copolymer, characterized in that the molecular weight regulator is mercaptans. The method according to any one of claims 1 to 4, A graft ratio of the graft copolymer is at least 25%, characterized in that the graft copolymer production method. In the thermoplastic resin composition, a) 20 to 80 parts by weight of the graft copolymer prepared by the method of any one of claims 1 to 4; And b) 20 to 80 parts by weight of styrenic copolymer Thermoplastic resin composition comprising a. The method of claim 16, The vinyl cyan compound in the monomer composition of the styrene copolymer is contained in 20 to 35 parts by weight, the thermoplastic resin composition characterized in that the weight average molecular weight is 80,000 to 200,000. The method of claim 16, Acrylonitrile-styrene copolymer wherein the styrene copolymer has an acrylonitrile content of 20 to 35% by weight; Terpolymers of acrylonitrile-styrene-alphamethylstyrene having an acrylonitrile content of 25 to 35% by weight, an alphamethylstyrene content of 60 to 70% by weight, and a styrene content of 1 to 10% by weight; Or a mixture thereof. The method of claim 16, The thermoplastic resin composition is a light stabilizer, lubricant, ultraviolet absorber, plasticizer, colorant, flame retardant, enhancer, compatibilizer, foaming agent, wood flour, filler, metal powder, antibacterial agent, antifungal, silicone oil, and a filling agent from the group consisting of The thermoplastic resin composition further comprises an additive selected from above.