KR20220052562A - Acrylic graft copolymer and method for preparing the same - Google Patents

Abstract

Disclosed are an acrylic graft copolymer which comprises: a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å; a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å; and a third polymer comprising an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit and grafted onto the first and second alkyl acrylate polymers, and a preparation method thereof.

Description

Acrylic graft copolymer and its manufacturing method

It relates to an acrylic graft copolymer and a method for manufacturing the same.

Acrylonitrile-Butadiene-Styrene (ABS) is an acrylate-styrene-acrylonitrile (ASA) resin obtained by graft copolymerization of styrene and acrylonitrile monomers to an acrylic rubber polymer. As a resin with improved weather resistance, which is a disadvantage of resin, it is widely used in automobile exterior materials, construction materials, agricultural tools, outdoor antennas, etc.

Although ASA resin has excellent weather resistance, its appearance and impact strength are inferior to ABS. Although a method for producing an ASA polymer having improved weather resistance and aging resistance by using a large-diameter rubber polymer as a core has been proposed, the graft copolymer including the large-diameter rubber polymer is a graft copolymer prepared using a small-diameter rubber polymer. Although the impact resistance was improved compared to , there was a problem in that it was difficult to color and the bronze phenomenon occurred, in which the surface color shows a characteristic metallic luster such as copper depending on the type or angle of light.

An object of the present invention is to provide a method for preparing an acrylic graft copolymer that prevents the occurrence of bronze and has excellent weather resistance, mechanical strength, gloss and coloring properties.

According to one aspect, the first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å; a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å; and an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit, and comprising a third polymer grafted to the first and second alkyl acrylate polymers, an acrylic graft copolymer is provided.

In one embodiment, the first alkyl acrylate polymer may include a structure derived from a monomer having two or less double bonds.

In one embodiment, the second alkyl acrylate polymer may include a structure derived from a monomer having three or more double bonds.

In one embodiment, the graft rate may be 40-60%.

In one embodiment, the content of the third polymer may be 35 to 55 parts by weight based on 100 parts by weight of the acrylic graft copolymer.

According to another aspect, in the presence of a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å and a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å, reacting an aromatic vinyl monomer and an unsaturated nitrile monomer mixture A method for producing an acrylic graft copolymer is provided, comprising the steps.

In one embodiment, the first alkyl acrylate polymer, 0.5 to 5 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having two or less double bonds, and 0.0005 to 0.01 parts by weight of a polymerization initiator to react the average preparing a first alkyl acrylate precursor having a particle diameter of 2,000 to 3,000 Å; and the first alkyl acrylate precursor, 25-50 parts by weight of an alkyl acrylate monomer, 0.05-1.0 parts by weight of a monomer having two or less double bonds, 0.01-0.2 parts by weight of a polymerization initiator, and 0.2-1.0 parts by weight of an emulsifier. to prepare a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å.

In one embodiment, the second alkyl acrylate polymer comprises 10 to 15 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having three or more double bonds, 0.001 to 0.05 parts by weight of a polymerization initiator, and 0.1 to 0.1 parts by weight of an emulsifier. It may be prepared by a method comprising the step of preparing a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å by reacting 2.0 parts by weight.

In one embodiment, in the presence of 45 to 65 parts by weight of the first and second alkyl acrylate polymers, 35 to 55 parts by weight of the monomer mixture, 0.1 to 0.5 parts by weight of the polymerization initiator, and 0.5 to 2.0 parts by weight of the emulsifier can be reacted. there is.

In an embodiment, the preparation of the first and second alkyl acrylate polymers and the reaction of the monomer mixture may be continuously performed in a single reactor.

According to one aspect, it is possible to prepare an acrylic graft copolymer that prevents the occurrence of a bronze phenomenon and has excellent weather resistance, mechanical strength, gloss and coloring properties.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a comparison of Examples and Comparative Example specimens prepared according to the specification to confirm whether or not the bronze phenomenon occurs.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is "connected" with another part, this includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

When a range of numerical values is recited herein, the values have the precision of the significant figures provided in accordance with the standard rules in chemistry for significant figures, unless the specific range is otherwise stated. For example, 10 includes the range of 5.0 to 14.9 and the number 10.0 includes the range of 9.50 to 10.49.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Acrylic graft copolymer

The acrylic graft copolymer according to one aspect includes: a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å; a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å; and an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit, and may include a third polymer grafted to the first and second alkyl acrylate polymers.

The acrylic graft copolymer may prevent the surface bronze phenomenon because the average particle diameter of the alkyl acrylate polymer does not overlap the range of 1,900 to 3,900 Å, which is a half-wavelength region of visible light.

The first alkyl acrylate polymer is a large-diameter rubber component, and if the average particle diameter is less than 4,000 Å, a bronze phenomenon may occur due to light interference or the impact strength may decrease, and if it exceeds 6,000 Å, the gloss property may be reduced. . The content of the first alkyl acrylate polymer may be 30 to 55 parts by weight, but is not limited thereto. If the content is out of the above range, impact strength may be lowered or colorability may be insufficient.

The first alkyl acrylate polymer may comprise a structure derived from a monomer having up to two double bonds. When the first alkyl acrylate polymer having a large diameter includes a structure derived from a monomer having two or less double bonds, it may be advantageous in terms of impact strength compared to a structure derived from a monomer having three or more double bonds.

The second alkyl acrylate polymer is a small-diameter rubber component. If the average particle diameter is less than 500 Å, the mechanical properties of the final product may be reduced, and if it exceeds 1,800 Å, the gloss and coloring properties are reduced, and the Bronze may occur.

The second alkyl acrylate polymer may include a structure derived from a monomer having three or more double bonds. When the small-diameter second alkyl acrylate polymer includes a structure derived from a monomer having three or more double bonds, the graft rate is increased compared to a structure derived from a monomer having two or less double bonds, which will be advantageous in terms of appearance characteristics. can

The acrylic graft copolymer may have a graft rate of 40 to 60%. When the graft rate is out of the above range, the distribution of rubber particles may become non-uniform during the manufacture of a product using the acrylic graft copolymer, thereby deteriorating gloss characteristics and coloring characteristics.

The content of the second alkyl acrylate polymer may be 10 to 15 parts by weight based on 100 parts by weight of the acrylic graft copolymer. If the content is less than 10 parts by weight, the colorability may be reduced, and if it exceeds 15 parts by weight, the impact strength may be reduced.

Based on 100 parts by weight of the acrylic graft copolymer, the content of the third polymer may be 35 to 55 parts by weight. If the content of the third polymer is less than 35 parts by weight, the graft rate may be lowered, and if it exceeds 55 parts by weight, productivity may be lowered and the cost may be unnecessarily increased.

By using the acrylic graft copolymer, a thermoplastic resin having excellent weather resistance, mechanical properties, gloss properties and colorability can be prepared.

Method for producing acrylic graft copolymer

In the method for preparing an acrylic graft copolymer according to another aspect, in the presence of a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å and a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å, aromatic vinyl It may include reacting the monomer and the unsaturated nitrile monomer mixture.

The first alkyl acrylate polymer is prepared by reacting 0.5 to 5 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having two or less double bonds, and 0.0005 to 0.01 parts by weight of a polymerization initiator to have an average particle size of 2,000 to 3,000 Å preparing a first alkyl acrylate precursor which is phosphorus; and the first alkyl acrylate precursor, 25-50 parts by weight of an alkyl acrylate monomer, 0.05-1.0 parts by weight of a monomer having two or less double bonds, 0.01-0.2 parts by weight of a polymerization initiator, and 0.2-1.0 parts by weight of an emulsifier. to prepare a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å.

1) Preparation of alkyl acrylate precursors

The alkyl acrylate monomer may have an alkyl group having 1 to 8 carbon atoms among acrylic monomers, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, t-butyl acrylate, n -Butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, and may be at least one selected from the group consisting of 2-ethylhexyl acrylate, but is not limited thereto.

The first alkyl acrylate precursor may be prepared by reacting an allyl acrylate monomer with a monomer having two or less double bonds without an emulsifier.

The monomer having two or less double bonds is, for example, divinylbenzene, allyl methacrylate, dihydrodicyclopentadienyl acrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene Glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol diacrylate rate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, aryl acrylate, aryl methacrylate 1,6-hexanediol dimethacrylate, It may be at least one selected from the group consisting of neopentyl glycol dimethacrylate and diallylamine, but is not limited thereto.

The polymerization initiator may be a hydroperoxide-based initiator, for example, tert-butyl hydroperoxide, cumene hydroperoxide, isopropylbenzene hydroperoxide, potassium persulfate salt, sodium persulfate salt and ammonium persulfate salt It may be at least one selected from the group consisting of, but is not limited thereto.

When the content of the polymerization initiator is out of the above-described range in the preparation of the first alkyl acrylate precursor, the reaction rate may be reduced or the average particle diameter of the precursor may be excessively reduced, thereby reducing mechanical properties of the thermoplastic resin. In addition, if the average particle diameter of the first alkyl acrylate precursor is out of the above range, it may be difficult for the average particle diameter to satisfy the above-described range when the first alkyl acrylate polymer, which is a large-diameter rubber component, is prepared.

In the step of preparing the first alkyl acrylate precursor, each monomer and polymerization initiator is used for 10 to 60 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, or two of them. It may be administered continuously for a time in a range between values. If the continuous administration time is excessively long, polymerization stability may be lowered, and coagulation may occur. If the continuous administration time is excessively short, the reproducibility of the average particle size may decrease.

Preparation of the first alkyl acrylate precursor may be performed in the presence of ion-exchanged water and an activator. 0.1 to 0.5 parts by weight of the activator may be added based on 100 parts by weight of the ion-exchanged water, and if it is out of the above range, mechanical properties of the final product may become unbalanced.

2) Preparation of first alkyl acrylate polymer

The first alkyl acrylate polymer may use the same or different monomers and polymerization initiators as those used in the preparation of the above-described precursor, respectively, and the dosage and administration time may be adjusted the same or differently to control the average particle size. .

The reaction may be performed by administering 0.2 to 1.0 parts by weight of an emulsifier when preparing the first alkyl acrylate polymer. If the dosage of the emulsifier is less than 0.2 parts by weight, the stability of the latex may be lowered and coagulation may be excessively generated.

The emulsifier may be, for example, at least one selected from the group consisting of fatty acid soaps, alkali salts of rosin acid, alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, and alkali alkyl sulfosuccinates. , but is not limited thereto.

In the preparation of the first alkyl acrylate polymer, the average particle diameter can be easily controlled by continuously administering reactants such as a monomer, a polymerization initiator, and an emulsifier for 3 to 5 hours, but is not limited thereto.

Preparation of the first alkyl acrylate polymer may be carried out in the presence of ion-exchanged water and an activator, and may be carried out in the same reactor as the preparation of the precursor.

3) Preparation of the second alkyl acrylate polymer

The second alkyl acrylate polymer is prepared by reacting 10 to 15 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having three or more double bonds, 0.001 to 0.05 parts by weight of a polymerization initiator, and 0.1 to 2.0 parts by weight of an emulsifier. It may be prepared by a method comprising the step of preparing a second alkyl acrylate polymer having a particle diameter of 500 to 1,800 Å.

The second alkyl acrylate polymer may be prepared by reacting an allyl acrylate monomer with a monomer having three or more double bonds in the presence of an emulsifier.

The monomer having three or more double bonds is, for example, at least selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, triallyl trimetate, trimethylolpropane triacrylate and triallylamine It may be one, but is not limited thereto.

In the preparation of the second alkyl acrylate polymer, the same or different monomers, polymerization initiators and emulsifiers may be used, respectively, and the dosage and administration time may be adjusted the same or differently to control the average particle size.

If the content of the alkyl acrylate monomer is less than 10 parts by weight, the colorability may be reduced, and if it exceeds 15 parts by weight, the impact strength may be reduced.

If the content of the emulsifier is less than 0.1 parts by weight, the average particle diameter of the second alkyl acrylate polymer may deviate from the above range, and if it exceeds 2.0 parts by weight, an excessively large amount of coagulant may be required to obtain the acrylic graft copolymer.

When preparing the second alkyl acrylate polymer, each reactant is 30 to 120 minutes, for example, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, The administration may be continuous for 120 minutes or a period of time ranging between the two of these values.

The preparation of the second alkyl acrylate polymer may be carried out in the presence of ion-exchanged water and an activator, and may be carried out in the same reactor as the preparation of the precursor or the first alkyl acrylate polymer.

4) Preparation of acrylic graft polymer

In the presence of 45 to 65 parts by weight of the first and second alkyl acrylate polymers, 35 to 55 parts by weight of a mixture of the aromatic vinyl monomer and unsaturated nitrile monomer, 0.1 to 0.5 parts by weight of a polymerization initiator, and 0.5 to 2.0 parts by weight of an emulsifier to react can If the content of the first and second alkyl acrylate polymers is excessively small, a large amount of the monomer mixture cannot be added through continuous polymerization, and thus the manufacturing cost may be excessively increased. The mechanical properties of the product may be deteriorated.

The preparation of the first alkyl acrylate precursor, the second alkyl acrylate polymer, and the second alkyl acrylate polymer and the reaction of these with the monomer mixture may be continuously performed in a single reactor.

In the preparation of the acrylic graft copolymer, the same or different polymerization initiators and emulsifiers may be used, respectively, and the dosage and administration time may be adjusted the same or differently to control the graft rate.

If the dosage of the polymerization initiator is less than 0.1 parts by weight, the graft rate may be lowered, and if it exceeds 0.5 parts by weight, the molecular weight is reduced and the mechanical properties of the final product are reduced, and the gloss properties may be deteriorated due to discoloration to yellow during high temperature molding. .

If the dosage of the monomer mixture is less than 35 parts by weight, the graft rate may be insufficient, and if it exceeds 55 parts by weight, productivity may decrease.

The aromatic vinyl monomer may be at least one of styrene, alphamethylstyrene, alphaethylstyrene, paramethylstyrene, and vinyltoluene, but is not limited thereto.

The unsaturated nitrile monomer may be at least one of acrylonitrile, methacrylonitrile, and ethacrylonitrile, but is not limited thereto.

The aromatic vinyl monomer and the unsaturated nitrile monomer may be mixed in a weight ratio of 65 to 80: 20 to 35, respectively. If the weight ratio of the unsaturated nitrile monomer is less than 20, the kneading property may be poor or the impact strength may be reduced when mixed with the styrene-acrylonitrile resin prepared by bulk or solution polymerization method, and if it exceeds 35, the kneading property may be poor or high temperature During molding, it may be discolored to yellow and the gloss properties may be deteriorated.

In the preparation of the acrylic graft copolymer, reaction materials such as a monomer mixture, a polymerization initiator, and an emulsifier may be administered in a batch to a reactor, or may be continuously administered for a predetermined time. In case of continuous administration, it may be administered for 3 to 5 hours in consideration of the graft rate of the acrylic graft copolymer, but is not limited thereto.

In addition, 0.1 to 0.5 parts by weight of the activator may be collectively administered to the reactor prior to administration of the reactant. If the dose of the activator is out of the above range, the mechanical properties of the final product may be unbalanced.

After the reaction, the acrylic graft copolymer may be mixed with an antioxidant, aggregated with a coagulant, washed, dehydrated and dried to obtain a powder state.

As the coagulant, conventional coagulants such as sulfuric acid, magnesium sulfate, calcium chloride and aluminum sulfate may be used.

In addition, the characteristics of the first and second alkyl acrylate polymers and acrylic graft copolymers are as described above.

Hereinafter, an embodiment of the present invention will be described in more detail. However, the following experimental results describe only representative experimental results among the above examples, and the scope and contents of the present invention may not be construed as being reduced or limited by the examples. Each effect of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

The average particle diameter and graft rate of each component were measured and calculated by the following instruments and test methods.

-Average particle diameter (Å): It was measured using a Nanorac 150 by a dynamic laser light scattering method.

- Graft rate (%): Graft rate is determined by adding 2 g of powdery graft copolymer resin to 100 mL of acetone and stirring for 24 hours to dissolve the ungrafted styrenic copolymer in the rubber component, followed by ultracentrifugation. The gel and the sol were separated, and the graft rate was calculated according to Equation 1 below.

[Equation 1]

Graft rate (%) = [((gel weight)-(rubber weight)/(rubber weight)]×100

Example 1

1) First Alkyl Acrylate Polymer Precursor Preparation Step

100 parts by weight of ion-exchanged water, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, and 0.25 parts by weight of an activator composed of ferrous sulfate were administered to a reactor substituted with nitrogen, and the mixture was maintained at 55° C. for 10 minutes, followed by butyl A first alkyl acrylate polymer precursor was prepared by continuously administering 2.5 parts by weight of an acrylate monomer, 0.05 parts by weight of dihydrodicyclopentadienyl acrylate, and 0.001 parts by weight of cumene hydroperoxide for 30 minutes. The average particle diameter of the precursor was 2,500 Å.

(b) preparing a first alkyl acrylate polymer

37.5 parts by weight of butyl acrylate, 0.7 parts by weight of dihydrodicyclopentadienyl acrylate, 0.4 parts by weight of sodium dodecylbenzenesulfonate, and 0.05 parts by weight of cumene hydroperoxide were continuously administered to the precursor for 4 hours, and the average particle diameter A first alkyl acrylate polymer of 5,000 A was prepared.

3) Second Alkyl Acrylate Polymer Preparation Step

15 parts by weight of butyl acrylate, 1.0 parts by weight of triallyl cyanurate, 0.2 parts by weight of sodium dodecylbenzenesulfonate and 0.01 parts by weight of cumene hydroperoxide were continuously administered to the reactor for 1 hour, and the average particle diameter was 1,200 Å. Alkyl acrylate polymers were prepared.

(d) acrylic graft copolymer preparation step

0.25 parts by weight of an activator composed of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate was administered to the first and second alkyl acrylate polymers in a batch, and the temperature was raised to 70° C. and maintained for 30 minutes, After reacting by continuously administering 31.5 parts by weight of styrene and 13.5 parts by weight of acrylonitrile, 0.25 parts by weight of cumene hydroperoxide, and 1.7 parts by weight of fatty acid soap to a monomer mixture for 4 hours, 60 minutes to achieve a final monomer conversion of 99% or more It was aged for a while to prepare a graft copolymer latex.

Then, the latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery acrylic graft copolymer resin. The graft ratio of the obtained acrylic graft copolymer was 50%.

Example 2

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor having an average particle diameter of 2,000 Å was prepared in the same manner as in Example 1, except that 0.5 parts by weight of the butyl acrylate monomer was used.

(b) preparing a first alkyl acrylate polymer

A first alkyl having an average particle diameter of 6,000 Å in the same manner as in Example 1 except that 50 parts by weight of butyl acrylate, 1.0 parts by weight of dihydrodicyclopentadienyl acrylate, and 1.0 parts by weight of sodium dodecylbenzenesulfonate were used. An acrylate polymer was prepared.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer having an average particle diameter of 1,600 Å was prepared in the same manner as in Example 1, except that 10 parts by weight of butyl acrylate and 0.5 parts by weight of sodium dodecylbenzenesulfonate were used.

(d) acrylic graft copolymer preparation step

An acrylic graft copolymer resin having a graft rate of 43% was obtained in the same manner as in Example 1, except that a monomer mixture consisting of 27.65 parts by weight of styrene and 11.85 parts by weight of acrylonitrile was added.

Example 3

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor having an average particle diameter of 3,000 Å was prepared in the same manner as in Example 1, except that 5 parts by weight of the butyl acrylate monomer was used.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl having an average particle diameter of 4,000 Å in the same manner as in Example 1, except that 25 parts by weight of butyl acrylate, 0.1 parts by weight of dihydrodicyclopentadienyl acrylate, and 0.2 parts by weight of sodium dodecylbenzenesulfonate were used. An acrylate polymer was prepared.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer having an average particle diameter of 600 Å was prepared in the same manner as in Example 1, except that 2.0 parts by weight of sodium dodecylbenzenesulfonate was used.

4) Preparation of acrylic graft copolymer

An acrylic graft copolymer resin having a graft rate of 58% was obtained in the same manner as in Example 1, except that a monomer mixture consisting of 38.5 parts by weight of styrene and 16.5 parts by weight of acrylonitrile was added.

Comparative Example 1

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor was prepared in the same manner as in Example 1.

(b) preparing a first alkyl acrylate polymer

A first alkyl acrylate polymer having an average particle diameter of 3,000 Å was prepared in the same manner as in Example 1, except that 1.5 parts by weight of sodium dodecylbenzenesulfonate was used.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1.

4) Preparation of acrylic graft copolymer

In the same manner as in Example 1, an acrylic graft copolymer resin having a graft rate of 53% was obtained.

Comparative Example 2

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor having an average particle diameter of 1,500 Å was prepared in the same manner as in Example 1, except that butyl acrylate monomer, dihydrodicyclopentadienyl acrylate, and cumene hydroperoxide were administered in batches. prepared.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer having an average particle diameter of 3,500 Å was prepared in the same manner as in Example 1.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1.

4) Preparation of acrylic graft copolymer

In the same manner as in Example 1, an acrylic graft copolymer resin having a graft rate of 47% was obtained.

Comparative Example 3

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor was prepared in the same manner as in Example 1.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer was prepared in the same manner as in Example 1.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer having an average particle diameter of 2,600 Å was prepared in the same manner as in Example 1, except that 0.2 parts by weight of sodium dodecylbenzenesulfonate was used.

4) Preparation of acrylic graft copolymer

In the same manner as in Example 1, an acrylic graft copolymer resin having a graft rate of 41% was obtained.

Comparative Example 4

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor was prepared in the same manner as in Example 1.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer was prepared in the same manner as in Example 1, except that 57.5 parts by weight of the butyl acrylate monomer was used.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1.

4) Preparation of acrylic graft copolymer

An acrylic graft copolymer resin having a graft rate of 25% was obtained in the same manner as in Example 1, except that a monomer mixture consisting of 17.5 parts by weight of styrene and 7.5 parts by weight of acrylonitrile was added.

Comparative Example 5

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor having an average particle diameter of 3,000 Å was prepared in the same manner as in Example 1, except that 5 parts by weight of butyl acrylate was used.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer having an average particle diameter of 7,000 Å was prepared in the same manner as in Example 1, except that 0.1 parts by weight of sodium dodecylbenzenesulfonate was used.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1.

4) Preparation of acrylic graft copolymer

An acrylic graft copolymer resin having a graft rate of 40% was obtained in the same manner as in Example 1, except that a monomer mixture consisting of 29.75 parts by weight of styrene and 12.75 parts by weight of acrylonitrile was added.

Comparative Example 6

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor was prepared in the same manner as in Example 1, except that dihydrodicyclopentadienyl acrylate was replaced with 0.05 parts by weight of triallyl cyanurate.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer was prepared in the same manner as in Example 1, except that dihydrodicyclopentadienyl acrylate was replaced with 0.7 parts by weight of triallyl cyanurate.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1.

4) Preparation of acrylic graft copolymer

In the same manner as in Example 1, an acrylic graft copolymer resin having a graft rate of 55% was obtained.

Comparative Example 7

1) First Alkyl Acrylate Polymer Precursor Preparation Step

A first alkyl acrylate polymer precursor was prepared in the same manner as in Example 1.

2) First Alkyl Acrylate Polymer Preparation Step

A first alkyl acrylate polymer was prepared in the same manner as in Example 1.

3) Second Alkyl Acrylate Polymer Preparation Step

A second alkyl acrylate polymer was prepared in the same manner as in Example 1, except that triallyl cyanurate was replaced with 1.0 parts by weight of ethylene glycol dimethacrylate.

4) Preparation of acrylic graft copolymer

In the same manner as in Example 1, an acrylic graft copolymer resin having a graft rate of 28% was obtained.

The compositions and methods of Examples 1 to 3 and Comparative Examples 1 to 7 are summarized and shown in Table 1 below.

24 to 40 parts by weight of the graft copolymer resin prepared in Examples 1 to 3 and Comparative Examples 1 to 7, a styrene-acrylonitrile air having a weight average molecular weight of 100,000 and an acrylonitrile content of 25% 60 to 76 parts by weight of a synthetic (SAN) resin, 0.75 parts by weight of a lubricant, and 0.25 parts by weight of a heat stabilizer were added and mixed, followed by extrusion and injection molding to prepare a specimen having a final rubber content of 22% by weight. Izod impact strength, tensile strength, surface gloss, injection-flow thermal stability and colorability (L, a) were measured using the above specimen in the following manner, and the results are shown in Table 2 below.

-Izod impact strength: It was measured according to the method of ASTM D256. At this time, the thickness of the specimen was 1/8 inch.

-Tensile strength: It was measured according to the method of ASTM D638.

-Surface gloss: Measured using Micro Haze Plus at an angle of 60 degrees.

-Injection retention thermal stability: After the resin was allowed to stay inside the injection machine screw set at 240°C for 10 minutes, the change in glossiness (ΔGloss) before and after residence in the injection machine was measured for the molded specimen. indicates excellence.

-Colorability (L, a): 0.5 parts by weight of an easily identifiable black colorant was added with respect to 100 parts by weight of the resin and then injected, and each L, a value was measured using a spectrophotometer (Datacolor 650). When the L value was low, it was judged that the black coloration was good, and when the a value was high, it was confirmed that the bronze phenomenon was severe. 1 shows the surfaces of Example 1 in which the bronze phenomenon did not occur and Comparative Example 1 in which the bronze phenomenon occurred.

division Example comparative example One 2 3 One 2 3 4 5 6 7 graft copolymer
Content (parts by weight) 33 30 40 33 33 33 24 31 33 33 SAN resin content (parts by weight) 67 70 60 67 67 67 76 69 67 67 Izod impact strength (1/4”, Kg cm/cm) 18 19 17 11 13 19 18 19 10 18 Tensile strength (kg/㎠) 430 435 425 450 440 420 420 400 430 425 Surface gloss (60 degrees) 96 95 96 96 96 94 96 92 96 91 Injection retention thermal stability
(△Gloss) 4 4 4 6 6 3 20 6 3 18 Blackness (L) 27.8 27.9 27.7 27.6 27.7 27.9 27.8 28.6 27.7 28.3 bronze (a) -1.0 -1.2 -0.8 1.0 0.8 0.6 -0.9 -0.8 -1.1 -0.5

Referring to Table 2, the specimens prepared from the graft copolymers of Examples 1 to 3 have excellent impact strength compared to Comparative Examples 1, 2 and 6, and Comparative Examples 1 to 3 Unlike this, it can be confirmed that the bronze phenomenon did not develop, and compared to Comparative Examples 4 to 5 and Comparative Example 7, the appearance quality such as gloss, injection retention thermal stability, blackness, etc. was excellent while maintaining the impact strength. .

The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

Claims (10)

a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å;
a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å; and
An acrylic graft copolymer comprising an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit, and comprising a third polymer grafted to the first and second alkyl acrylate polymers. According to claim 1,
The first alkyl acrylate polymer comprises a structure derived from a monomer having two or less double bonds, an acrylic graft copolymer. According to claim 1,
The second alkyl acrylate polymer is an acrylic graft copolymer comprising a structure derived from a monomer having three or more double bonds. According to claim 1,
An acrylic graft copolymer having a graft rate of 40 to 60%. According to claim 1,
Based on 100 parts by weight of the acrylic graft copolymer, the content of the third polymer is 35 to 55 parts by weight, the acrylic graft copolymer. In the presence of a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å and a second alkyl acrylate polymer having an average particle diameter of 500 to 1,800 Å, reacting an aromatic vinyl monomer and an unsaturated nitrile monomer mixture. Acrylic-based, Method for producing a graft copolymer. 7. The method of claim 6,
The first alkyl acrylate polymer,
0.5 to 5 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having two or less double bonds, and 0.0005 to 0.01 parts by weight of a polymerization initiator to prepare a first alkyl acrylate precursor having an average particle size of 2,000 to 3,000 Å manufacturing; and
The first alkyl acrylate precursor, 25-50 parts by weight of an alkyl acrylate monomer, 0.05-1.0 parts by weight of a monomer having two or less double bonds, 0.01-0.2 parts by weight of a polymerization initiator, and 0.2-1.0 parts by weight of an emulsifier are reacted. A method for producing an acrylic graft copolymer, which is prepared by a method comprising the step of preparing a first alkyl acrylate polymer having an average particle diameter of 4,000 to 6,000 Å. 7. The method of claim 6,
The second alkyl acrylate polymer,
10 to 15 parts by weight of an alkyl acrylate monomer, 0.01 to 0.2 parts by weight of a monomer having three or more double bonds, 0.001 to 0.05 parts by weight of a polymerization initiator, and 0.1 to 2.0 parts by weight of an emulsifier to react with an average particle diameter of 500 to 1,800 Å. A method for producing an acrylic graft copolymer, which is prepared by a method comprising the step of preparing an alkyl acrylate polymer. 7. The method of claim 6,
In the presence of 45 to 65 parts by weight of the first and second alkyl acrylate polymers, 35 to 55 parts by weight of the monomer mixture, 0.1 to 0.5 parts by weight of the polymerization initiator, and 0.5 to 2.0 parts by weight of the emulsifier are reacted. manufacturing method. 7. The method of claim 6,
The preparation of the first and second alkyl acrylate polymers and the reaction of the monomer mixture are continuously performed in a single reactor, a method for producing an acrylic graft copolymer.

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