KR102213427B1 - Graft copolymer having a multi-layer structure and method for preparing the same - Google Patents

Abstract

In one embodiment of the present invention, (a) reacting 5 to 15 parts by weight of an aromatic vinyl monomer, 0.2 to 1.0 parts by weight of a polymerization initiator, and 1.0 to 3.0 parts by weight of an emulsifier; (b) reacting 30 to 50 parts by weight of a conjugated diene-based monomer with the product of step (a) in the presence of 0.1 to 0.5 parts by weight of a molecular weight control agent and 0.5 to 2.0 parts by weight of an electrolyte; (c) reacting 35 to 65 parts by weight of an acrylic monomer with the product of step (b) in the presence of 0.01 to 0.1 parts by weight of a polymerization initiator, 0.2 to 1.0 parts by weight of an emulsifier, and 0.1 to 1.0 parts by weight of a polyfunctional compound; And (d) reacting 30 to 70 parts by weight of an aromatic vinyl monomer and unsaturated nitrile monomer mixture with 30 to 70 parts by weight of the product of step (c) under conditions of an acidity of 10.0 to 12.0; containing, a graft copolymer and The manufacturing method is provided.

Description

Graft copolymer having a multilayer structure and its manufacturing method {GRAFT COPOLYMER HAVING A MULTI-LAYER STRUCTURE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a graft copolymer having a multilayer structure and a method for producing the same, and more particularly, to a graft copolymer in which a rubber polymer having a multilayer structure is dispersed in a matrix.

ABS (Acrylonitrile-Butadiene-Styrene) resin is a resin that is widely used in housings, toys, office equipment, automobiles, etc. of various electronic products including home appliances such as refrigerators and washing machines because of its excellent appearance characteristics in addition to mechanical properties and processability.

Conjugated diene-based rubbery polymer latex is widely used to improve the impact strength of ABS resins because it has excellent rubber properties due to its low glass transition temperature (T _g ). In particular, the fracture behavior may vary depending on the particle size and dispersibility of the rubbery polymer latex contained in the ABS resin, and the rubbery polymer latex is usually prepared according to an emulsion polymerization method in which particle size control is advantageous.

However, such a conjugated diene-based rubbery polymer contains chemically unstable double bonds and is easily decomposed and aged by ultraviolet rays, and as a result, the weather resistance of the ABS resin including the same is deteriorated, which is unsuitable for outdoor materials.

On the other hand, a method of using a chemically stable acrylic rubber instead of a butadiene rubber, a method of using a rubber polymer obtained by polymerizing butadiene and an acrylic polymerizable monomer has been used.

In particular, the ASA (Acrylate-Styrene-Acrylonitrile) graft copolymer resin obtained by graft copolymerization of styrene and acrylonitrile monomers on an acrylic rubber polymer is used for interior and exterior parts such as automotive exterior materials, building materials, agricultural equipment, antennas, etc. It is widely used in electrical and electronic products that require special weather resistance.

ASA resin does not have a chemically unstable double bond, so it can obtain a special effect on weather resistance, but has a problem with low impact resistance and colorability compared to ABS resin.

On the other hand, a method of preparing a graft polymer by mixing an acrylic rubber and a conjugated diene-based rubber has been proposed, but this has a problem in that the conjugated diene-based rubber is exposed to ultraviolet rays even though the colorability and impact resistance are improved, thereby reducing weather resistance.

In addition, a method of mixing with a separate resin having excellent colorability was proposed, but this was poor in economical efficiency because expensive PMMA resin was used.

As a method of modifying the rubber contained in the ASA resin itself, a method of preparing a multilayered core by introducing an aromatic vinyl compound having excellent colorability into the rubber was also proposed, but there was a problem in that the impact strength was lowered due to the hard aromatic vinyl compound. .

Therefore, there is a need for technology development for an ASA-based graft copolymer having excellent mechanical properties as well as appearance quality.

The present invention is to solve the problems of the prior art described above, and an object of the present invention is to provide a graft copolymer having excellent impact resistance, coloring property, and weather resistance harmoniously, and a method for producing the same.

One aspect of the present invention, (a) reacting 5 to 15 parts by weight of an aromatic vinyl monomer, 0.2 to 1.0 parts by weight of a polymerization initiator, and 1.0 to 3.0 parts by weight of an emulsifier; (b) reacting 30 to 50 parts by weight of a conjugated diene-based monomer with the product of step (a) in the presence of 0.1 to 0.5 parts by weight of a molecular weight control agent and 0.5 to 2.0 parts by weight of an electrolyte; (c) reacting 35 to 65 parts by weight of an acrylic monomer with the product of step (b) in the presence of 0.01 to 0.1 parts by weight of a polymerization initiator, 0.2 to 1.0 parts by weight of an emulsifier, and 0.1 to 1.0 parts by weight of a polyfunctional compound; And (d) reacting 30 to 70 parts by weight of an aromatic vinyl monomer and unsaturated nitrile monomer mixture with 30 to 70 parts by weight of the product of step (c) under the condition of an acidity of 10.0 to 12.0; containing, of a graft copolymer Provides a manufacturing method.

In one embodiment, the reaction of step (a) may be carried out under the conditions of 40 ~ 70 ℃.

In one embodiment, the product of step (a) may have an average particle diameter of 500 to 1,500 Å.

In one embodiment, the reaction of step (b) may be carried out at 60 ~ 80 ℃.

In one embodiment, the product of step (b) may have an average particle diameter of 2,700 to 3,300 Å.

In one embodiment, the product of step (b) may have a gel content of 75 to 90%.

In one embodiment, the reaction of step (c) may be carried out at 45 ~ 60 ℃.

In one embodiment, the product of step (c) may have an average particle diameter of 3,200 to 4,000 Å.

In one embodiment, the product of step (d) may have a graft rate of 30 to 70%.

In one embodiment, the reactants in steps (a) to (d) may be administered in batches or continuously to perform polymerization reaction.

Another aspect of the present invention is a seed composed of an aromatic vinyl monomer; A first rubber layer composed of a conjugated diene-based monomer and surrounding at least a portion of the seed surface; A second rubber layer composed of a polyfunctional compound and an acrylic monomer and covering the entire surface of the first rubber layer; And an aromatic vinyl monomer and an unsaturated nitrile monomer, and a matrix grafted with the second rubber layer; containing, a graft copolymer.

In one embodiment, the average particle diameter of the seed may be 500 ~ 1500 Å.

In one embodiment, the content of the monomer constituting the seed may be 5 to 15 parts by weight based on 100 parts by weight of the monomer constituting the seed, the first rubber layer, and the second rubber layer.

In one embodiment, the average particle diameter of the first rubber layer may be 2,700 ~ 3,300 Å.

In one embodiment, the content of the monomer constituting the first rubber layer may be 30 to 50 parts by weight based on 100 parts by weight of the monomer constituting the seed, the first rubber layer, and the second rubber layer.

In one embodiment, the average particle diameter of the second rubber layer may be 3,200 to 4,000 Å.

In an embodiment, the content of the monomer constituting the second rubber layer may be 35 to 65 parts by weight based on 100 parts by weight of the monomer constituting the seed, the first rubber layer, and the second rubber layer.

In one embodiment, the grafting rate of the matrix may be 30 to 70%.

In one embodiment, the content of the monomer constituting the matrix may be 30 to 70 parts by weight based on 100 parts by weight of the monomer constituting the graft copolymer.

Another aspect of the present invention, the above-described graft copolymer; And a copolymer prepared by bulk or solution polymerization and composed of an aromatic vinyl monomer and an unsaturated nitrile monomer.

According to an aspect of the present invention, it is possible to provide a graft copolymer having excellent impact resistance, colorability, and weather resistance compared to the prior art, and a method of manufacturing the same.

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

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

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

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

Method for producing a graft copolymer

A method of preparing a graft copolymer according to an aspect of the present invention includes: (a) reacting 5 to 15 parts by weight of an aromatic vinyl monomer, 0.2 to 1.0 parts by weight of a polymerization initiator, and 1.0 to 3.0 parts by weight of an emulsifier; (b) reacting 30 to 50 parts by weight of a conjugated diene-based monomer with the product of step (a) in the presence of 0.1 to 0.5 parts by weight of a molecular weight control agent and 0.5 to 2.0 parts by weight of an electrolyte; (c) reacting 35 to 65 parts by weight of an acrylic monomer with the product of step (b) in the presence of 0.01 to 0.1 parts by weight of a polymerization initiator, 0.2 to 1.0 parts by weight of an emulsifier, and 0.1 to 1.0 parts by weight of a polyfunctional compound; And (d) reacting 30 to 70 parts by weight of an aromatic vinyl monomer and unsaturated nitrile monomer mixture with 30 to 70 parts by weight of the product of step (c) under conditions of an acidity of 10.0 to 12.0.

The step (a) is a step of preparing a polymer seed to shorten the reaction time when preparing the rubber component included in the graft copolymer, and the presence of the polymer seed increases the polymerization reaction rate in the subsequent step. In this way, the overall reaction time can be shortened and productivity can be improved. In addition, it is possible to control the particle size distribution of the graft copolymer, thereby improving the impact resistance of the final product.

The aromatic vinyl monomers are styrene, α-methylstyrene, α-ethylstyrene, paramethylstyrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, 2,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, and Among these, it may be one selected from the group consisting of a mixture of two or more, and preferably, styrene, but is not limited thereto.

The aromatic vinyl monomer may have a high refractive index compared to the conjugated diene-based monomer. The refractive index of the aromatic vinyl monomer is 1.5 or more, and the refractive index of the conjugated diene-based monomer is 1.4 or more. If a seed composed of an aromatic vinyl monomer having a high refractive index is used, the coloring property of the graft copolymer can be improved.

In the step (a), 5 to 15 parts by weight of the aromatic vinyl monomer may be used. If the amount of the aromatic vinyl monomer is less than 5 parts by weight, the average particle diameter of the rubber component of the graft copolymer decreases, so that the impact resistance of the final product may be reduced or the refractive index may not be sufficiently improved, so that the effect of improving colorability may be insignificant. When the amount of the aromatic Vinly monomer exceeds 15 parts by weight, the thickness of the first rubber layer or the second rubber layer becomes thin, so that impact resistance may decrease.

The polymerization initiator may be persulfate-based, peroxycarbonate-based, peroxide-based, or a mixture thereof. The persulfate-based initiator may be one selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, and a mixture of two or more of them, but is not limited thereto. The peroxycarbonate-based or peroxide-based initiator is 2,5-dimethyl-2,5-di-(2-ethylhexanonylperoxy)hexane, t-amylperoxy-2-ethylhexanoate, t-butyl Peroxy-2-ethylhexanoate, t-amyl (2-ethylhexyl) monoperoxy carbonate, t-butylisopropyl monoperoxy carbonate, 2,5-dimethyl-2,5-di (benzoyl peroxy) Hexane, t-butyl-(2-ethylhexyl) monoperoxycarbonate, t-amylperoxybenzoate, tertiary butylperoxyacetate, t-butylperoxy-3,5,5-trimethylhexanoate, t -Butylperoxybenzoate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, butyl hydroperoxide, tertiary butyl hydroperoxide, benzoyl peroxide, and may be one selected from the group consisting of a mixture of two or more thereof, and , Preferably, cumene hydroperoxide, t-butyl isopropyl monoperoxy carbonate may be, but is not limited thereto.

In the step (a), 0.2 to 1.0 parts by weight of a persulfate-based initiator, which is a hydrophilic initiator, may be used as the polymerization initiator. If the content of the polymerization initiator is less than 0.2 parts by weight, the polymerization rate may be lowered, and if it exceeds 1.0 part by weight, the seed particle diameter may be significantly reduced.

The emulsifier may be one selected from the group consisting of fatty acid soap, alkali salt of rosin acid, alkylaryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, alkali alkyl sulfosuccinate, and mixtures of two or more thereof. , But is not limited thereto.

In the step (a), the emulsifier may be used in an amount of 1.0 to 3.0 parts by weight. If the content of the emulsifier is less than 1.0 part by weight, the seed particle size may be excessively large, and if it is more than 3.0 parts by weight, the average seed particle diameter may be less than 300 Å.

The reaction of step (a) may be carried out under conditions of 40 to 70°C. If the temperature of the reaction is out of the above range, polymerization stability may be lowered, polymerization rate may be significantly decreased, resulting in poor productivity, or it may be difficult to manufacture a product having a desired physical property.

The product of step (a) may have an average particle diameter of 500 to 1,500 Å. If the average particle diameter of the product is less than 500 Å, the particle diameter of the rubber component of the graft copolymer may decrease, and if it exceeds 1,500 Å, the thickness of the first rubber layer or the second rubber layer becomes thin, so that impact resistance may decrease.

The step (b) is a step of forming a first rubber layer on at least a part of the seed surface, and the impact resistance of the graft copolymer may be improved compared to a conventional ASA resin due to the presence of the first rubber layer.

The conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and Among these, it may be one selected from the group consisting of a mixture of two or more, preferably 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, but is not limited thereto.

In the step (b), 30 to 50 parts by weight of the conjugated diene-based monomer may be used. If the conjugated diene-based monomer is less than 30 parts by weight, impact resistance may not be improved compared to the conventional ASA resin, and if it exceeds 50 parts by weight, weather resistance may decrease.

The molecular weight modifier may be one selected from the group consisting of tert-butyl mercaptan, tert-dodecyl mercaptan, methyl mercaptan, and a mixture of two or more thereof, and preferably tert-dodecyl mercaptan, but this It is not limited.

In step (b), the molecular weight control agent may be used in an amount of 0.1 to 0.5 parts by weight. If the molecular weight control agent is less than 0.1 parts by weight, the rubber component gel may be excessively formed, and if the molecular weight control agent is more than 0.5 parts by weight, the gel content may be insufficient and the mechanical properties of the final product may be deteriorated.

The electrolyte is Na ₂ SO ₄ , K ₂ SO ₄ , KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , Na ₂ HPO ₄ and may be one selected from the group consisting of a mixture of two or more of them, preferably Na ₂ SO ₄ , K ₂ SO ₄ , KCl, NaCl, and a mixture of two or more thereof It may be one selected from the group, but is not limited thereto.

In the step (b), 0.5 to 2.0 parts by weight of the electrolyte may be used. If the electrolyte is less than 0.5 parts by weight, the viscosity increases and the particle diameter decreases, making it difficult to implement the desired physical properties, and if it exceeds 2.0 parts by weight, polymerization stability may be inferior.

The reaction of step (b) may be performed at 60 to 80°C. When the temperature of the reaction is out of the above range, the polymerization rate is significantly reduced, resulting in a decrease in productivity, polymerization stability, or it may be difficult to manufacture a product having a desired physical property.

The product of step (b) may have an average particle diameter of 2,700 to 3,300 Å. If the average particle diameter of the product is less than 2,700 Å, the impact resistance of the final product may be lowered, and if it exceeds 3,300 Å, the appearance quality may be poor.

The product of step (b) may have a gel content of 75 to 90%. When the gel content of the product is out of the above range, mechanical properties may be deteriorated.

The step (c) is a step of forming a second rubber layer on the entire surface of the first rubber layer, and the weather resistance of the graft copolymer may be improved compared to a conventional ABS resin due to the presence of the second rubber layer.

The acrylic monomer may be one selected from the group consisting of (meth)acrylic acid, an alkyl (meth)acrylate having an alkyl group having 1 to 16 carbon atoms, and a mixture of two or more of them, and preferably, may be a butyl acrylate, It is not limited thereto.

In the step (c), the acrylic monomer may be used in an amount of 35 to 65 parts by weight. When the amount of the acrylic monomer is less than 35 parts by weight, the surface of the first rubber layer may be exposed to reduce weather resistance, and when the amount is more than 65 parts by weight, it may be difficult to improve impact resistance and colorability compared to a conventional ASA resin.

In the step (c), the polymerization initiator may be selected from the above types, and preferably, a persulfate initiator may be selected, and 0.01 to 0.1 parts by weight may be used. If the polymerization initiator is less than 0.01 part by weight, the polymerization rate may be lowered and productivity may be reduced, and if it exceeds 0.1 part by weight, it may be difficult to improve weather resistance compared to the conventional ABS resin by forming a separate acrylic rubber polymer.

In the step (c), the emulsifier may be selected from the above types, and preferably, an alkali alkyl sulfosuccinate may be selected to control the particle size, and 0.2 to 1.0 parts by weight may be used. If the emulsifier is less than 0.2 parts by weight, the stability of the latex may decrease during polymerization, and if it exceeds 1.0 part by weight, separate acrylic particles may be formed and a multilayer core-shell structure may not be formed.

The polyfunctional compound may be triallyl isocyanurate, triallyl cyanurate, triallyl trimetate, etc., and preferably, triallyl isocyanurate or cyanuric acid having a triazine ring. Triallyl acid may be used, and more preferably, triallyl cyanurate may be used in consideration of polymerization stability, but is not limited thereto.

The polyfunctional compound may connect the radical generated in the product of step (b) and the acrylic monomer by a polymerization initiator, or may connect the acrylic rubber generated by interpolymerizing the acrylic monomer and the radical.

In step (c), 0.1 to 1.0 parts by weight of the polyfunctional compound may be used. When the content of the polyfunctional compound is out of the above range, mechanical properties of the final product may be deteriorated.

The reaction of step (c) may be carried out at 45 ~ 60 ℃. If the temperature of the reaction is less than 45° C., the polymerization rate significantly decreases and productivity may decrease. If the reaction temperature exceeds 60° C., the crosslinking density of the first rubber layer may increase excessively and the impact resistance of the final product may decrease.

The product of step (c) may have an average particle diameter of 3,200 to 4,000 Å. When the average particle diameter of the product satisfies the above range, the impact resistance, appearance characteristics, and weather resistance of the final product can be harmoniously improved.

The step (d) is a step of graft-reacting a surface of a rubbery polymer, which is a rubber component having a multilayer core-shell structure prepared in steps (a) to (c), and a matrix including an aromatic vinyl monomer and an unsaturated nitrile monomer, The multilayered rubbery polymer dispersed in the matrix can improve the mechanical properties and appearance quality of the final product.

The acrylic monomer introduced in step (c) may have an acidity (pH) of less than 7.0, and the unreacted polymerization initiator may reduce the acidity of the reactant to less than 10.0. In the step (d), 0.5 to 1.0 parts by weight of the base may be added to maintain an acidity of 10.0 to 12.0. If the acidity is out of the above range in step (d), the stability of the reactant is significantly lowered, and the amount of waste generated may increase rapidly.

The aromatic vinyl monomer may be selected from the above types.

The unsaturated nitrile monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, and mixtures of two or more thereof, preferably acrylonitrile. However, it is not limited thereto.

In step (d), 30 to 70 parts by weight of a mixture of the aromatic vinyl monomer and the unsaturated nitrile monomer may be reacted with 30 to 70 parts by weight of the product of step (c). If the multilayered rubbery polymer, which is the product of step (c), is less than 30 parts by weight, the input amount of the graft copolymer may be excessively increased during the manufacture of the final product, resulting in an increase in cost, and if it exceeds 70 parts by weight, the graft rate is lowered. The dispersibility of the multilayered rubbery polymer may be reduced, and as a result, the mechanical properties of the final product may be poor.

In step (d), the weight ratio of the aromatic vinyl monomer and the unsaturated nitrile monomer may be 1 to 5: 1 or 2 to 4: 1, respectively, but is not limited thereto.

The reaction of step (d) may be carried out in the presence of a polymerization initiator and an emulsifier, and the polymerization initiator and the emulsifier may be selected from the above types.

In addition, an activating agent may be included in the reaction of step (d), and the activating agent is sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, lactose, dextrose, sodium ryrolate , Sodium sulfate, and a combination of two or more of them may be one selected from the group consisting of, and preferably, a mixture of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate, but is not limited thereto.

The product of step (d) may have a grafting rate of 30 to 70%. When the graft rate of the product satisfies the above range, the dispersibility of the multi-layered rubbery polymer in the matrix is improved, so that the mechanical properties and appearance quality of the final product can be improved compared to conventional products.

In steps (a) to (d), the reactants may be administered in batches or continuously to perform polymerization reaction. By adjusting this method of administration, the structure of each step product can be controlled.

Each of the compounds may be of the same or different types for each step. As an example, the aromatic vinyl monomer of step (a) and the aromatic vinyl monomer of step (d) may use the same styrene monomer, or may use a styrene monomer and an α-methylstyrene monomer, respectively, to implement heat resistance.

As another example, the type and content of the polymerization initiator may be selected to achieve a desired effect according to each reaction step, for example, in the step (a), a part of a persulfate initiator is added, and the The remaining persulfate-based initiator is added to step (c), and a peroxycarbonate-based or peroxide-based initiator is further added to step (d) to control the reaction of each step and the structure of the graft copolymer. have.

After the step (d), a powdery graft copolymer may be obtained by agglomeration with sulfuric acid, MgSO ₄ , CaCl ₂ or Al ₂ (SO ₄ ) ₃ , which are conventional coagulants, followed by washing, dehydration and drying.

Graft copolymer

Graft copolymer according to an aspect of the present invention, a seed composed of an aromatic vinyl monomer; A first rubber layer composed of a conjugated diene-based monomer and surrounding at least a portion of the seed surface; A second rubber layer composed of a polyfunctional compound and an acrylic monomer and covering the entire surface of the first rubber layer; And an aromatic vinyl monomer and an unsaturated nitrile monomer, and a shell grafted with the second rubber layer.

The graft copolymer includes as an inner layer a first rubber layer composed of a conjugated diene-based monomer having excellent refractive index compared to a conventional rubber polymer including a seed composed of an aromatic vinyl monomer, excellent impact strength and colorability, and excellent weather resistance. A multi-layered core-shell structured rubber polymer including a second rubber layer composed of monomers as an outer layer may be dispersed in a matrix composed of the aromatic vinyl monomer and the unsaturated nitrile monomer, and the graft copolymer is the aforementioned graft It can be prepared by a method of preparing a copolymer.

The properties of the graft copolymer, types of monomers, and effects thereof may be the same as described above.

The average particle diameter of the seed may be 500 to 1,500 Å, and the content of the monomer constituting the seed may be 5 to 15 parts by weight based on 100 parts by weight of the monomer constituting the seed, the first rubber layer, and the second rubber layer. I can.

The average particle diameter of the first rubber layer may be 2,700 to 3,300 Å, and the content of the monomer constituting the first rubber layer is 30 based on 100 parts by weight of monomers constituting the seed, the first rubber layer, and the second rubber layer. It may be ~50 parts by weight.

The average particle diameter of the second rubber layer may be 3,200 to 4,000 Å, and the content of the monomer constituting the second rubber layer is 35 based on 100 parts by weight of the monomer constituting the seed, the first rubber layer, and the second rubber layer. It may be ~65 parts by weight.

The average particle diameter of the first rubber layer means the average particle diameter of the core-shell polymer composed of the seed and the first rubber layer, and the average particle diameter of the second rubber layer means the seed, the first rubber layer, and the second rubber layer. It means the average particle diameter of the polymer of the multilayer core-shell structure composed of.

The graft ratio between the matrix and the multilayer core-shell structured rubbery polymer may be 30 to 70%, and based on 100 parts by weight of the monomer constituting the graft copolymer, the content of the monomer constituting the matrix is 30 to 70 It may be parts by weight.

Thermoplastic resin composition

Thermoplastic resin composition according to an aspect of the present invention, the above-described graft copolymer; And a copolymer prepared by bulk or solution polymerization and composed of an aromatic vinyl monomer and an unsaturated nitrile monomer.

The thermoplastic resin composition may be harmoniously excellent in colorability, impact resistance, and weather resistance compared to a composition including a conventional ABS resin or ASA resin.

Hereinafter, embodiments of the present invention will be described in more detail. However, the following experimental results are only representative of the above examples, and the scope and contents of the present invention are reduced or limited by the examples and cannot be interpreted. Effects of each of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

Example 1

(1) Preparation of polymer seed

100 parts by weight of ion-exchanged water in a reactor substituted with nitrogen, 10 parts by weight of styrene (SM) as an aromatic vinyl monomer, 0.5 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator, 2.0 parts by weight of fatty acid soap as an emulsifier Batch administration and reaction for 2 hours at 50 ℃ to prepare a polymer seed.

(2) Preparation of the first rubber layer

In the polymer seed prepared in step (1), 30 parts by weight of 1,3-butadiene (BD) as a monomer, 0.3 parts by weight of tert-dodecylmercaptan (TDDM) as a molecular weight control agent, sodium sulfate as an electrolyte (Na ₂ SO ₄ ) 1.2 parts by weight were administered in a batch and reacted at a temperature of 75°C to prepare a rubbery polymer.

(3) Preparation of the second rubber layer

In the rubber polymer prepared in step (2) above, 60 parts by weight of butyl acrylate (BA) as a monomer, 0.05 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator, 0.7 as an emulsifier alkali alkyl sulfosuccinate Parts by weight and 0.3 parts by weight of triallyl cyanurate as a polyfunctional compound were collectively administered, and reacted at a temperature of 50°C to prepare a multilayered rubbery polymer.

(4) Graft copolymer preparation

The acidity (pH) was maintained at 11.0 by administering 0.6 parts by weight of potassium chloride to 50 parts by weight of the multilayered rubbery polymer prepared in step (3) for 1 hour. 0.25 parts by weight of an activator composed of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate was administered in a batch, and the temperature was raised to 65°C and then maintained for 30 minutes. A monomer mixture consisting of 35 parts by weight of styrene (SM) and 15 parts by weight of acrylonitrile (AN), 0.2 parts by weight of cumene hydroperoxide as a polymerization initiator, and 1.5 parts by weight of fatty acid soap as an emulsifier were continuously administered for 4 hours to react, 99% In order to obtain the above monomer conversion rate, it was aged for 60 minutes to prepare a graft copolymer latex. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Example 2

(1) Preparation of polymer seed

In a reactor substituted with nitrogen, 100 parts by weight of ion-exchanged water, 15 parts by weight of styrene (SM) as an aromatic vinyl monomer, 0.2 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator, 1.0 parts by weight of fatty acid soap as an emulsifier Batch administration and reaction for 2 hours at 50 ℃ to prepare a polymer seed.

(2) Preparation of the first rubber layer

In the polymer seed prepared in step (1), 50 parts by weight of 1,3-butadiene (BD) as a monomer, 0.5 parts by weight of tert-dodecylmercaptan as a molecular weight control agent, and 2.0 parts by weight of sodium sulfate (Na ₂ SO ₄ ) as an electrolyte Batch administration and reaction at a temperature of 75 ℃ to prepare a rubbery polymer.

(3) Preparation of the second rubber layer

To the rubber polymer prepared in step (2) above, 35 parts by weight of butyl acrylate (BA) as a monomer, 0.01 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator, 0.2 as an emulsifier alkali alkyl sulfosuccinate Parts by weight and 0.1 parts by weight of triallyl cyanurate as a polyfunctional compound were collectively administered and reacted at a temperature of 50° C. to prepare a multilayered rubbery polymer.

(4) Graft copolymer preparation

The acidity (pH) was maintained at 11.0 by administering 0.6 parts by weight of potassium chloride to 50 parts by weight of the multilayered rubbery polymer prepared in step (3) for 1 hour. 0.25 parts by weight of an activator composed of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate was administered in a batch, and the temperature was raised to 65°C and then maintained for 30 minutes. A monomer mixture consisting of 35 parts by weight of styrene (SM) and 15 parts by weight of acrylonitrile (AN), 0.2 parts by weight of cumene hydroperoxide as a polymerization initiator, and 1.5 parts by weight of fatty acid soap as an emulsifier were continuously administered for 4 hours to react, 99% In order to obtain the above monomer conversion rate, the graft copolymer latex was prepared by aging for 60 minutes. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and then dried to obtain a powdery graft copolymer resin.

Example 3

(1) Preparation of polymer seed

100 parts by weight of ion-exchanged water in a reactor substituted with nitrogen, 5 parts by weight of styrene (SM) as an aromatic vinyl monomer, 1.0 part by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an emulsifier, 3.0 parts by weight of fatty acid soap as an emulsifier Batch administration and reaction for 2 hours at 50 ℃ to prepare a polymer seed.

(2) Preparation of the first rubber layer

In the polymer seed prepared in step (1), 30 parts by weight of 1,3-butadiene (BD) as a monomer, 0.1 parts by weight of tert-dodecyl mercaptan as a molecular weight control agent, and 2.0 parts by weight of sodium sulfate (Na ₂ SO ₄ ) as an electrolyte Batch administration and reaction at a temperature of 75 ℃ to prepare a rubbery polymer.

(3) Preparation of the second rubber layer

65 parts by weight of butyl acrylate (BA) as a monomer in the rubber polymer prepared in step (2), 0.01 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator, 1.0 part by weight of an alkali alkyl sulfosuccinate as an emulsifier Part by weight, 1.0 part by weight of triallyl cyanurate as a polyfunctional compound was collectively administered and reacted at a temperature of 45°C to prepare a multilayered rubbery polymer.

(4) Graft copolymer preparation

The acidity (pH) was maintained at 11.3 by administering 0.5 parts by weight of potassium chloride to 30 parts by weight of the multilayered rubbery polymer prepared in step (3) for 1 hour. 0.25 parts by weight of an activator composed of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate was administered in a batch, and the temperature was raised to 65°C and then maintained for 30 minutes. A monomer mixture consisting of 49 parts by weight of styrene (SM) and 21 parts by weight of acrylonitrile (AN), 0.2 parts by weight of cumene hydroperoxide as a polymerization initiator, and 1.5 parts by weight of fatty acid soap as an emulsifier were continuously administered for 6 hours to react, 99% In order to obtain the above monomer conversion rate, it was aged for 60 minutes to prepare a graft copolymer latex. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Example 4

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1.

(3) Preparation of the second rubber layer

A multilayer rubbery polymer was prepared in the same manner as in Example 1, except that the reaction was performed at a temperature of 60°C.

(4) Graft copolymer preparation

The acidity (pH) was maintained at 11.2 by administering 1.0 part by weight of potassium chloride to 70 parts by weight of the multilayered rubbery polymer prepared in step (3) for 1 hour. 0.25 parts by weight of an activator composed of sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, and ferrous sulfate was administered in a batch, and the temperature was raised to 65°C and then maintained for 30 minutes. A monomer mixture consisting of 21 parts by weight of styrene (SM) and 9 parts by weight of acrylonitrile (AN), 0.2 parts by weight of cumene hydroperoxide as a polymerization initiator, and 1.5 parts by weight of fatty acid soap as an emulsifier were continuously administered for 4 hours to react, and 99% In order to obtain the above monomer conversion rate, the graft copolymer latex was prepared by aging for 60 minutes. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and then dried to obtain a powdery graft copolymer resin.

Comparative Example 1

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1, except that 2 parts by weight of styrene (SM) was added as an aromatic vinyl monomer.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1.

(3) Preparation of the second rubber layer

A multilayered rubbery polymer was prepared in the same manner as in Example 1, except that 68 parts by weight of butyl acrylate (BA) as a monomer was administered at once.

(4) Graft copolymer preparation

Graft copolymer latex was prepared in the same manner as in Example 1. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Comparative Example 2

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1, except that 65 parts by weight of 1,3-butadiene (BD) was administered as a monomer.

(3) Preparation of the second rubber layer

A multilayered rubbery polymer was prepared in the same manner as in Example 1, except that 25 parts by weight of butyl acrylate (BA) as a monomer was administered at once.

(4) Graft copolymer preparation

Graft copolymer latex was prepared in the same manner as in Example 1. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Comparative Example 3

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1, except that 5 parts by weight of 1,3-butadiene (BD) was administered as a monomer.

(3) Preparation of the second rubber layer

A multilayered rubbery polymer was prepared in the same manner as in Example 1, except that 85 parts by weight of butyl acrylate (BA) as a monomer was administered at once.

(4) Graft copolymer preparation

Graft copolymer latex was prepared in the same manner as in Example 1. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Comparative Example 4

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1.

(3) Preparation of the second rubber layer

A multilayer rubbery polymer was prepared in the same manner as in Example 1.

(4) Graft copolymer preparation

A graft copolymer latex was prepared in the same manner as in Example 1, except for the step of correcting the acidity (pH) by administering potassium chloride to the multilayer rubbery polymer prepared in step (3). The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Comparative Example 5

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1, except that 20 parts by weight of styrene (SM) was collectively administered as an aromatic vinyl monomer.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1.

(3) Preparation of the second rubber layer

A multilayered rubbery polymer was prepared in the same manner as in Example 1, except that 50 parts by weight of butyl acrylate (BA) as a monomer was administered at once.

(4) Graft copolymer preparation

Graft copolymer latex was prepared in the same manner as in Example 1. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Comparative Example 6

(1) Preparation of polymer seed

A polymer seed was prepared in the same manner as in Example 1.

(2) Preparation of the first rubber layer

A rubbery polymer was prepared in the same manner as in Example 1.

(3) Preparation of the second rubber layer

A multilayer rubbery polymer was prepared in the same manner as in Example 1, except that the reaction was performed at a temperature of 70°C.

(4) Graft copolymer preparation

Graft copolymer latex was prepared in the same manner as in Example 1. The obtained graft copolymer latex was aggregated with magnesium sulfate (MgSO ₄ ) and dried to obtain a powdery graft copolymer resin.

Experimental example

The dosage of each component according to Examples 1 to 4 and Comparative Examples 1 to 6, the average particle diameter, gel content, polymerization temperature, graft rate, and coagulation content of the polymer seed and the polymer in each step were measured and shown in Table 1 below. . The unit of dosage of each component is parts by weight unless otherwise specified.

step division Example Comparative example One 2 3 4 One 2 3 4 5 6 (One) SM 10 15 5 10 2 10 10 10 20 10 (One) Average particle diameter (Å) 900 1,450 550 900 450 900 900 900 1,350 900 (2) BD 30 50 30 30 30 65 5 30 30 30 (2) Gel content (%) 84 77 89 84 83 85 86 84 85 84 (2) Average particle diameter (Å) 3,000 3,250 2,750 3,000 2,600 3,200 1,500 3,000 3,200 3,000 (3) BA 60 35 65 60 68 25 85 60 50 60 (3) Polymerization temperature (℃) 50 50 45 60 50 50 50 50 50 70 (3) Acidity (pH) 7.8 8.1 7.5 7.8 7.8 8.2 7.4 7.8 8.1 7.8 (3) Average particle diameter (Å) 3,550 3,980 3,250 3,550 3,000 3,500 3,400 3,550 3,800 3,550 (4) Polymer(3) 50 50 30 70 50 50 50 50 50 50 (4) KCl 0.6 0.6 0.5 1.0 0.6 0.6 0.6 - 0.6 0.6 (4) Acidity (pH) 11.0 11.0 11.3 11.2 11.0 11.0 11.0 - 11.0 11.0 (4) SM 35 35 49 21 35 35 35 35 35 35 (4) AN 15 15 21 9 15 15 15 15 15 15 (4) Continuous dosing time (hr) 4 4 6 4 4 4 4 4 4 4 (4) Graft rate (%) 50 60 70 30 50 65 35 45 50 50 (4) Coagulation (%) 0.01 0.01 0.02 0.01 0.01 0.01 0.03 3 0.01 0.01

-Gel content (%): The rubbery polymer latex was coagulated using 1% sulfuric acid solution, washed, dried in a vacuum oven at 50° C. for 24 hours, and then 1 g of the obtained coagulum was added to 100 g of toluene for 48 hours. After storage in a dark room at room temperature, it was separated into a sol and a gel, and the gel content of the rubbery polymer latex was calculated according to Equation 1 below.

[Equation 1]

Gel content (%) = [(weight of insoluble matter (gel))/(weight of sample)]×100

-Average particle diameter (Å): The average particle diameter of the rubbery polymer latex was measured using Nanotrac 150 by a dynamic laser light scattering method.

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

[Equation 2]

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

30 parts by weight of each graft copolymer prepared according to Examples 1 to 4 and Comparative Examples 1 to 6, 70 parts by weight of a SAN resin having a weight average molecular weight (M _w ) of 100,000 and an acrylonitrile content of 25%, After 0.75 parts by weight of a lubricant and 0.25 parts by weight of a heat stabilizer were added and mixed, extrusion, injection, and molding were performed to prepare respective thermoplastic resin specimens having a rubber content of 20% by weight.

Izod impact strength, surface gloss, colorability (L) and weather resistance (ΔE) were measured using the specimen, and the results are shown in Table 2 below.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 Izod impact strength
(1/4”Kg·cm/cm) 30 28 32 32 24 35 18 - 22 20 Surface gloss (60°) 96 95 95 94 92 92 92 - 96 95 Coloring (L) 26.8 26.7 26.9 26.8 28 26.5 28.2 - 26.5 26.8 Weather resistance (△E) 7 7 6 6 6 10 6 - 6 7

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

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

-Coloring (L): 0.5 parts by weight of a black colorant for easy identification was added and injected with respect to 100 parts by weight of a thermoplastic resin, and each L value was measured using a spectrophotometer (Datacolor 650). When the L value was low, the colorability was judged to be good.

-Weather resistance (ΔE): After exposure to 4,500KJ/m ² with a weatherometer according to SAEJ2527, the degree of discoloration (ΔE) was measured using a spectrochromometer, and ΔE is the CIE Lab value before and after exposure. It is an arithmetic average value of, and the closer the value is to 0, the better the stability.

Referring to Tables 1 and 2, the graft copolymers of Examples 1 to 4 prepared according to an aspect of the present invention have excellent polymerization stability unlike Comparative Example 4 in which a separate acidity correction is not performed, so that the content of the coagulum Is significantly reduced.

In addition, the graft copolymers of Examples 1 to 4 have significantly superior impact strength compared to Comparative Examples 1, 3, 5 and 6, and the butadiene ratio is excessively high, so that the first rubber layer cannot be sufficiently covered with the second rubber layer. Compared to the graft copolymer of 2, excellent weather resistance was implemented.

The graft copolymers of Examples 1 to 4 are effective in improving the appearance quality due to the higher content of the aromatic vinyl monomer having a high refractive index in the seed polymer compared to Comparative Example 1, and the first rubber layer composed of the conjugated diene-based monomer was formed, compared to Comparative Example 3. It was excellent in colorability.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to 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 limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (20)

(a) reacting 5 to 15 parts by weight of an aromatic vinyl monomer, 0.2 to 1.0 parts by weight of a polymerization initiator, and 1.0 to 3.0 parts by weight of an emulsifier;
(b) reacting 30 to 50 parts by weight of a conjugated diene-based monomer with the product of step (a) in the presence of 0.1 to 0.5 parts by weight of a molecular weight control agent and 0.5 to 2.0 parts by weight of an electrolyte;
(c) reacting 35 to 65 parts by weight of an acrylic monomer with the product of step (b) in the presence of 0.01 to 0.1 parts by weight of a polymerization initiator, 0.2 to 1.0 parts by weight of an emulsifier, and 0.1 to 1.0 parts by weight of a polyfunctional compound; And
(d) reacting 30 to 70 parts by weight of an aromatic vinyl monomer and an unsaturated nitrile monomer mixture with 30 to 70 parts by weight of the product of step (c) under conditions of an acidity of 10.0 to 12.0; including,
The reaction of step (c) is carried out at 45 ~ 60 ℃, the method of producing a graft copolymer. The method of claim 1,
The reaction of step (a) is carried out under the conditions of 40 ~ 70 ℃, the method of producing a graft copolymer. The method of claim 1,
The product of the step (a) has an average particle diameter of 500 to 1500 Å, a method for producing a graft copolymer. The method of claim 1,
The reaction of step (b) is carried out at 60 ~ 80 ℃, the method of producing a graft copolymer. The method of claim 1,
The product of step (b) has an average particle diameter of 2,700 to 3,300 Å, a method for producing a graft copolymer. The method of claim 1,
The product of step (b) has a gel content of 75 to 90%, a method for producing a graft copolymer. delete The method of claim 1,
The product of step (c) has an average particle diameter of 3,200 to 4,000 Å, a method for producing a graft copolymer. The method of claim 1,
The product of step (d) has a graft rate of 30 to 70%, a method for producing a graft copolymer. The method of claim 1,
In steps (a) to (d), a method for producing a graft copolymer is subjected to a polymerization reaction by batch or continuous administration of the reactants, respectively. Seeds composed of aromatic vinyl monomers;
A first rubber layer composed of a conjugated diene-based monomer and surrounding at least a portion of the seed surface;
A second rubber layer composed of a polyfunctional compound and an acrylic monomer and covering the entire surface of the first rubber layer; And
Containing, a graft copolymer consisting of an aromatic vinyl monomer and an unsaturated nitrile monomer, and a matrix grafted with the second rubber layer. The method of claim 11,
The average particle diameter of the seed is 500 ~ 1500 Å, the graft copolymer. The method of claim 11,
The seed, based on 100 parts by weight of the monomer constituting the first rubber layer and the second rubber layer, the content of the monomer constituting the seed is 5 to 15 parts by weight, a graft copolymer. The method of claim 11,
The average particle diameter of the first rubber layer is 2,700 ~ 3,300 Å, the graft copolymer. The method of claim 11,
The seed, based on 100 parts by weight of monomers constituting the first rubber layer and the second rubber layer, the content of the monomer constituting the first rubber layer is 30 to 50 parts by weight, a graft copolymer. The method of claim 11,
The average particle diameter of the second rubber layer is 3,200 ~ 4,000 Å, the graft copolymer. The method of claim 11,
The seed, based on 100 parts by weight of monomers constituting the first rubber layer and the second rubber layer, the content of the monomer constituting the second rubber layer is 35 to 65 parts by weight, the graft copolymer. The method of claim 11,
The graft copolymer of the matrix has a graft ratio of 30 to 70%. The method of claim 11,
Based on 100 parts by weight of the monomer constituting the graft copolymer, the content of the monomer constituting the matrix is 30 to 70 parts by weight, the graft copolymer. The graft copolymer according to any one of claims 11 to 19; And
A thermoplastic resin composition comprising; a copolymer prepared by bulk or solution polymerization and composed of an aromatic vinyl monomer and an unsaturated nitrile monomer.