KR20210051966A - Method for preparing graft polymer - Google Patents

Abstract

The present invention relates to a method for preparing a graft polymer, which comprises the following steps of: preparing a second diene-based rubbery polymer by enlarging a first diene-based rubbery polymer into a first acid group-containing polymer; preparing a composite rubbery polymer by enlarging a second diene-based rubbery polymer and an acrylic rubbery polymer into a second acid group-containing polymer; and preparing a graft polymer by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to the composite rubbery polymer. An object of the present invention is to provide the method for preparing the graft polymer, capable of implementing excellent impact strength, weather resistance, workability and tensile strength.

Description

Manufacturing method of graft polymer {METHOD FOR PREPARING GRAFT POLYMER}

The present invention relates to a method for producing a graft polymer, and to a method for producing a graft polymer using a composite rubber polymer prepared by simultaneously enlarging a diene rubber polymer and an acrylic rubber polymer as an acid group-containing polymer.

The graft polymer is largely a diene-based graft polymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide monomer to a diene-based rubber polymer, and an acrylic-based graft polymer obtained by graft-polymerizing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to an acrylic rubber polymer. It can be divided into two polymers.

Since the acrylic graft polymer has superior weather resistance compared to the diene graft polymer, it can be directly applied as an exterior material without post-processing such as painting. However, since the acrylic graft polymer has a lower impact strength than the diene-based graft polymer, the impact resistance is deteriorated, and the flow index is low, so that the processability is deteriorated. In order to overcome these drawbacks, a thermoplastic resin composition including both a diene-based graft polymer and an acrylic-based graft polymer has been proposed, but there is a problem in that weather resistance is remarkably deteriorated.

Accordingly, studies on graft polymers having both the advantages of diene-based graft polymers and acrylic graft polymers are continuing, but are currently insufficient.

An object of the present invention is to provide a method for producing a graft polymer capable of realizing excellent impact strength, weather resistance, workability and tensile strength.

In addition, an object of the present invention is to provide a method for producing a graft polymer capable of implementing excellent coloring properties.

In order to solve the above problems, the present invention comprises the steps of preparing a second diene-based rubbery polymer by enlarging the first diene-based rubbery polymer with a first acid group-containing polymer; Preparing a composite rubbery polymer by enlarging the second diene-based rubbery polymer and an acrylic rubbery polymer with a second acid group-containing polymer; And graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to the composite rubbery polymer to prepare a graft polymer.

According to the method for producing a graft polymer of the present invention, a graft polymer having excellent impact strength, weather resistance, workability, and tensile strength can be prepared. In addition, since it is possible to easily prepare a composite rubbery polymer in which an acrylic rubbery polymer is located on a diene rubbery polymer, weather resistance can be particularly improved. In addition, since the acrylic rubber polymer is enlarged to the acid group-containing polymer, the manufacturing time is significantly reduced compared to the case of manufacturing the composite rubber polymer by polymerization, and the generation of agglomerates is reduced, thereby improving the stability of the latex, thereby improving the manufacturing efficiency. I can.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In the present invention, the average particle diameter of a diene rubber polymer, an acrylic rubber polymer, or an acid group-containing polymer can be measured using dynamic light scattering, and in detail, it can be measured using Nicomp 380 HPL of Nicomp. I can. In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of an intensity distribution.

In the present invention, the carboxylic acid monomer unit may be a unit derived from a carboxylic acid monomer. The carboxylic acid monomer may be one or more from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, of which methacrylic acid is preferable.

In the present invention, the C ₁ to C ₃ alkyl (meth) acrylate monomer unit may be a unit derived from a _{C 1} to C _{3 alkyl (meth) acrylate monomer.} C ₁ to C ₃ alkyl (meth) acrylate monomer may be one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate, among which At least one selected from the group consisting of methyl acrylate and ethyl acrylate is preferred.

In the present invention, the aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferable.

In the present invention, the first diene-based rubber polymer may be prepared by polymerizing a diene-based monomer. The diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, of which 1,3-butadiene is preferable.

In the present invention, the acrylic rubber polymer _{may be prepared by crosslinking polymerization of a C 1} to C ₄ alkyl (meth) acrylate monomer. C ₁ to C ₃ alkyl (meth) acrylate monomer is one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate It may be more than one, of which butyl acrylate is preferred.

In the present invention, the vinyl cyanide monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is preferable.

One. Graft Method for producing polymer

A method for producing a graft polymer according to an embodiment of the present invention includes: 1) preparing a second diene-based rubbery polymer by enlarging a first diene-based rubbery polymer with a first acid group-containing polymer; 2) preparing a composite rubbery polymer by enlarging the second diene-based rubbery polymer and an acrylic rubbery polymer with a second acid group-containing polymer; And 3) graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer on the composite rubbery polymer to prepare a graft polymer.

Hereinafter, a method for preparing a graft polymer according to an embodiment of the present invention will be described in detail.

1) second Diene Rubbery Preparation of polymer

First, a first diene-based rubbery polymer is enlarged to a first acid group-containing polymer to prepare a second diene-based rubbery polymer.

Even if the second diene-based rubbery polymer is made to be enlarged, all of the first diene-based rubbery polymers cannot be enlarged, so that a part of the first diene-based rubbery polymer can be maintained in its original state. The first diene-based rubber polymer having a small average particle diameter can improve the colorability and weather resistance of the graft polymer, and the second diene-based rubber polymer having a large average particle diameter can improve the impact strength of the graft polymer. The physical properties of the graft polymer can be improved overall. However, when the second diene-based rubbery polymer is prepared by polymerization, it is difficult to produce a diene-based rubbery polymer having a small average particle size in an appropriate amount at the same time, so it is very difficult to improve the colorability and weather resistance of the graft polymer with a diene-based rubbery polymer. I can.

The first diene-based rubber polymer may have an average particle diameter of 30 to 70 nm, preferably 40 to 60 nm. In the present invention, since the enlargement is performed two or more times, a first diene-based rubbery polymer having a smaller average particle diameter than the conventional one can be used. In addition, if the above-described range is satisfied, the polymerization time may be shortened during the production of the first diene-based rubber polymer, thereby improving manufacturing efficiency. In addition, the colorability and weather resistance of the graft polymer may be further improved due to the first diene-based rubber polymer.

The second diene-based rubbery polymer may have an average particle diameter of 80 to 130 ㎚, and preferably 90 to 120 ㎚. If the above-described range is satisfied, it is possible to maintain a balance between the impact strength and tensile strength of the graft polymer. In addition, since the average particle diameter of the acrylic rubber polymer to be described later is at the same level, if the weight ratio of the second diene rubber polymer and the acrylic rubber polymer is properly adjusted, the composite rubber polymer is a structure in which the acrylic rubber polymer is located on the second diene rubber polymer. Polymers can be prepared easily.

On the other hand, the first acid group-containing polymer can easily enlarge the first diene-based rubbery polymer and maintain latex stability.

The first acid group-containing polymer may include a carboxylic acid-based monomer unit and a C ₁ to C ₃ alkyl (meth) acrylate-based monomer unit. If the C ₁ to C ₃ alkyl (meth) acrylate monomer unit is included, the input amount of the first acid group-containing polymer is significantly reduced at the time of hypertrophy than when the _{C 4 or higher alkyl (meth) acrylate monomer unit is included.} In addition, the use of expensive carboxylic acid monomers can be significantly reduced.

In addition, the first acid group-containing polymer may contain a small amount of carboxylic acid monomer units compared to the second acid group-containing polymer described below, and may contain 2 to 5% by weight of carboxylic acid monomer units, and preferably 2.5 to 4% by weight. It can be included in %. If the above-described conditions are satisfied, the first diene-based rubbery polymer can be prevented from being excessively enlarged, and a second diene-based rubbery polymer having a desired average particle diameter can be prepared.

The first acid group-containing polymer is a copolymer of a carboxylic acid monomer and a C ₁ to C ₃ alkyl (meth) acrylate monomer, or a core phase prepared by polymerizing a _{C 1} to C _{3 alkyl (meth) acrylate monomer.} It may be a graft copolymer obtained by graft polymerization of a carboxylic acid monomer and a C ₁ to C _{3 alkyl (meth)acrylic monomer.}

The first acid group-containing polymer may enlarge the first diene-based rubber polymer in an amount of 3 to 7 parts by weight, and preferably, in an amount of 4 to 6 parts by weight, based on 100 parts by weight of the first diene-based rubber polymer. The first diene-based rubbery polymer may be enlarged. If the above-described range is satisfied, it is possible to easily prepare a second diene-based rubbery polymer having a desired average particle diameter of the first diene-based rubbery polymer.

The first acid group-containing polymer may have an average particle diameter of 30 to 70 nm, preferably 40 to 60 nm. If the above-described range is satisfied, the first diene-based rubbery polymer may have an average particle diameter equivalent to that of the first diene-based rubbery polymer, and thus the first diene-based rubbery polymer may be more easily enlarged.

2) compound Rubbery Preparation of polymer

Subsequently, the second diene rubber polymer and the acrylic rubber polymer are enlarged with a second acid group-containing polymer to prepare a composite rubber polymer.

The acrylic rubber polymer may have an average particle diameter of 80 to 130 nm, preferably 90 to 120 nm. If the above-described range is satisfied, the specific surface area of the acrylic rubber polymer increases, so that the weather resistance of the graft polymer can be improved. In addition, since the second diene-based rubber polymer and the average particle diameter are at the same level, if the weight ratio of the second diene-based rubber polymer and the acrylic rubber polymer is properly adjusted, the composite structure in which the acrylic rubber polymer is located on the second diene-based rubber polymer. It is possible to easily prepare a rubbery polymer.

The second diene rubber polymer and the acrylic rubber polymer may have a weight ratio of 5:95 to 20:80, preferably 10:90 to 15:85. If the above-described conditions are satisfied, a composite rubber polymer having a structure in which an acrylic rubber polymer is located on the second diene rubber polymer can be easily prepared, so that a graft polymer having excellent impact strength and remarkably improved weather resistance can be obtained. Can be manufactured.

On the other hand, the second acid group-containing polymer can easily enlarge the second diene-based rubber polymer and the acrylic rubber-based polymer at the same time and maintain latex stability.

The second acid group-containing polymer may include a carboxylic acid-based monomer unit and a C ₁ to C ₃ alkyl (meth) acrylate-based monomer unit. If the C ₁ to C ₃ alkyl (meth) acrylate monomer unit is included, the input amount of the first acid group-containing polymer is significantly reduced at the time of hypertrophy than when the _{C 4 or higher alkyl (meth) acrylate monomer unit is included.} In addition, the use of expensive carboxylic acid monomers can be significantly reduced.

In addition, the second acid group-containing polymer may contain an excess of carboxylic acid monomer units compared to the first acid group-containing polymer, and may contain 3 to 9% by weight of carboxylic acid monomer units, and preferably 4 to 8% by weight. Can include. If the above-described conditions are satisfied, the second diene-based rubbery polymer and the acrylic-based rubbery polymer can be easily enlarged, and a composite rubbery polymer having a desired average particle diameter can be prepared.

The second acid group-containing polymer is a copolymer of a carboxylic acid monomer and a C ₁ to C ₃ alkyl (meth) acrylate monomer, or a core phase prepared by polymerizing a _{C 1} to C _{3 alkyl (meth) acrylate monomer.} It may be a graft copolymer obtained by graft polymerization of a carboxylic acid monomer and a C ₁ to C _{3 alkyl (meth)acrylic monomer.}

The second acid group-containing polymer may have an average particle diameter of 80 to 130 nm, and preferably 90 to 120 nm. If the above-described range is satisfied, the average particle diameter of the second diene-based rubber polymer and the acrylic rubber-like polymer are at the same level, so that these can be easily enlarged.

The second acid group-containing polymer may enlarge the second diene-based rubber polymer and the acrylic rubber polymer in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the sum of the second diene-based rubber polymer and the acrylic rubber polymer, Preferably, the 2 diene rubber polymer and the acrylic rubber polymer may be enlarged in an amount of 1 to 4 parts by weight. If the above-described range is satisfied, a composite rubber polymer having a desired average particle diameter of the 2 diene rubber polymer and the acrylic rubber polymer can be easily prepared.

The composite rubbery polymer may have an average particle diameter of 250 ㎚ to 400 ㎚, preferably 280 to 350 ㎚. If the above-described range is satisfied, a graft polymer having excellent weather resistance as well as impact resistance and processability can be prepared.

3) Graft Preparation of polymer

Subsequently, an aromatic vinyl-based monomer and a vinyl cyanide-based monomer are graft-polymerized on the composite rubbery polymer to prepare a graft polymer.

The composite rubbery polymer may be 40 to 70 parts by weight, preferably 45 to 65 parts by weight, based on 100 parts by weight of the total of the composite rubbery polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer. If the above-described range is satisfied, impact resistance, weather resistance, and processability of the graft polymer may be improved.

The aromatic vinyl-based monomer may be 10 to 54 parts by weight, and preferably 24 to 44 parts by weight, based on 100 parts by weight of the total of the composite rubbery polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer. If the above-described range is satisfied, the processability of the graft polymer can be improved.

The vinyl cyanide-based monomer may be 6 to 20 parts by weight, and preferably 7 to 18 parts by weight, based on 100 parts by weight of the total of the composite rubbery polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer. If the above-described range is satisfied, processability and chemical resistance of the graft polymer may be improved.

In the step of preparing the graft polymer, at least one selected from the group consisting of an initiator, an oxidation-reduction catalyst, and water may be further added.

The initiator is sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-menthanhydroperoxide, di-t-butyl peroxide, t-butylcumyl per Oxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyronitrile, azo It may be one or more selected from the group consisting of bis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) methyl, of which cumene hydroperoxide is preferable.

The initiator may be added in an amount of 0.01 to 0.5 parts by weight or 0.03 to 0.4 parts by weight based on 100 parts by weight of the sum of the composite rubbery polymer, the aromatic vinyl monomer and the vinyl cyanide monomer, of which 0.03 to 0.4 parts by weight. It is desirable. If the above-described range is satisfied, while the emulsion polymerization is easily performed, the residual amount in the graft polymer can be minimized.

The oxidation-reduction catalyst is 1 selected from the group consisting of sodium formaldehyde sulfoxylate, disodium dihydrogen ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate, and sodium sulfate. It may be more than one species, of which it is preferably at least one selected from the group consisting of dextrose, sodium pyrophosphate, and ferrous sulfate.

The oxidation-reduction catalyst may be added in an amount of 0.01 to 0.5 parts by weight or 0.03 to 0.3 parts by weight, of which 0.03 to 0.3 parts by weight, based on 100 parts by weight of the sum of the composite rubbery polymer, aromatic vinyl monomer and vinyl cyanide monomer. It is preferable to add in parts by weight. If the above-described range is satisfied, polymerization can be easily initiated at a relatively low temperature.

The water may be ion-exchanged water.

When the polymerization of the graft polymer is completed, coagulation, aging, washing and drying processes are further performed to obtain a graft polymer in powder form.

Hereinafter, a preferred embodiment is presented to aid in the understanding of the present invention, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea, but the following examples are only illustrative of the present invention, It is natural that such modifications and modifications fall within the scope of the appended claims.

Manufacturing example One

75 parts by weight of deionized water, 100 parts by weight of 1,3-butadiene, 4 parts by weight of an unsaturated fatty acid emulsifier, _{0.1 parts by weight of K 2} CO _3, 0.1 parts by weight of t-dodecyl mercaptan, 0.15 parts by weight of t-butyl hydroperoxide , 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrophosphate, and 00025 parts by weight of ferrous sulfate were added to the reactor at once, and the reactor was heated to 55°C to initiate polymerization. When the polymerization conversion rate reached 35%, 0.03 parts by weight of potassium persulfate was added, and the temperature was raised to 72°C, followed by polymerization. When the polymerization conversion rate reached 95%, polymerization was terminated. The obtained first diene-based rubbery polymer latex had an average particle diameter of 60 nm.

Manufacturing example 2

75 parts by weight of deionized water, 100 parts by weight of 1,3-butadiene, 5 parts by weight of an unsaturated fatty acid emulsifier, _{0.1 parts by weight of K 2} CO _3, 0.1 parts by weight of t-dodecyl mercaptan, 0.15 parts by weight of t-butyl hydroperoxide , 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrophosphate, and 00025 parts by weight of ferrous sulfate were added to the reactor at once, and the reactor was heated to 55°C to initiate polymerization. When the polymerization conversion rate reached 35%, 0.03 parts by weight of potassium persulfate was added, and the temperature was raised to 72°C, followed by polymerization. When the polymerization conversion rate reached 95%, polymerization was terminated. The obtained first diene-based rubbery polymer latex had an average particle diameter of 50 nm.

Manufacturing example 3

90 parts by weight of deionized water, 12 parts by weight of butyl acrylate, 0.08 parts by weight of ethylene glycol dimethacrylate, 0.04 parts by weight of allyl methacrylate, 1.5 parts by weight of sodium dodecyl persulfate were added to the reactor at once, and polymerized for 1 hour. The seed was prepared. In the presence of the seed, 60 parts by weight of deionized water, 88 parts by weight of butyl acrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, 0.4 parts by weight of allyl methacrylate were continuously added for 3 hours to perform polymerization, and then polymerization was terminated. I did. The obtained acrylic rubbery polymer latex had an average particle diameter of 100 nm.

Manufacturing example 4

90 parts by weight of deionized water, 15 parts by weight of butyl acrylate, 0.08 parts by weight of ethylene glycol dimethacrylate, 0.04 parts by weight of allyl methacrylate, and 1.5 parts by weight of sodium dodecylpersulfate were added to the reactor at once, and the seeds were polymerized for 1 hour. Was prepared. In the presence of the seed, polymerization was terminated after polymerization was performed while continuously adding 60 parts by weight of deionized water, 85 parts by weight of butyl acrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, and 0.4 parts by weight of allyl methacrylate for 3 hours. . The obtained acrylic rubbery polymer latex had an average particle diameter of 110 nm.

Manufacturing example 5

220 parts by weight of deionized water and 1 part by weight of sodium dioctyl sulfosuccinate were added to the reactor, and the internal temperature of the reactor was maintained at 70° C., and then 0.04 parts by weight of potassium persulfate and 50 parts by weight of ethyl acrylate 2 at a constant rate. The core was prepared by polymerization while continuously added for a period of time. In the presence of the core, 47 parts by weight of ethyl acrylate and 3 parts by weight of methacrylic acid were continuously added at a constant rate for 2 hours to perform graft polymerization. When the polymerization conversion rate reached 90%, polymerization was terminated. The obtained acid group-containing polymer latex had an average particle diameter of 48 nm.

Manufacturing example 6

208 parts by weight of deionized water and 0.4 parts by weight of sodium dioctyl sulfosuccinate were added to the reactor, and the internal temperature of the reactor was maintained at 70° C., and then 0.04 parts by weight of potassium persulfate and 50 parts by weight of ethyl acrylate at a constant rate. The core was prepared by polymerization while continuously added for a period of time. In the presence of the core, 43 parts by weight of ethyl acrylate and 6 parts by weight of methacrylic acid were continuously added at a constant rate for 2 hours to perform graft polymerization. When the polymerization conversion rate reached 90%, polymerization was terminated. The obtained acid group-containing polymer latex had an average particle diameter of 98 nm.

Manufacturing example 7

170 parts by weight of deionized water and 0.09 parts by weight of sodium dioctyl sulfosuccinate were added to the reactor, followed by stirring while raising the temperature to 80° C., 0.1 parts by weight of potassium persulfate, and left for 5 minutes.

Meanwhile, 3 parts by weight of methacrylic acid, 97 parts by weight of methyl acrylate, 0.41 parts by weight of sodium dioctyl sulfosuccinate, and 0.5 parts by weight of potassium persulfate were uniformly mixed to prepare a reaction solution.

In the reactor, the reaction solution was continuously added for 5 hours for polymerization, and polymerization was terminated when the polymerization conversion rate was 98%. The obtained acid group-containing polymer latex had an average particle diameter of 75 nm.

Example 1 to Example 4

<Production of the second diene rubber polymer>

100 parts by weight of the first diene-based rubbery polymer latex A of Preparation Example 1 (based on solid content) and the acid group-containing polymer latex of Preparation Example 5 were added to the reactor in the amount shown in Table 1 (based on solid content), and stirred for 30 minutes. And a second diene-based rubbery polymer latex having an average particle diameter shown in Table 1 below by enlarging.

<Production of composite rubber polymer>

Into the reactor, 0.4 parts by weight of NaOH and the acrylic rubbery polymer latex of Preparation Example 3 were added in the amount (based on solid content) shown in Table 1 below, and stirred for 10 minutes. Thereafter, the second diene-based rubbery polymer latex was added to the reactor in the amount (based on solid content) shown in Table 1 below, and then stirred for 10 minutes. Thereafter, the acid group-containing polymer latex of Preparation Example 6 was added to the reactor at the content (based on solid content) shown in Table 1 below, and stirred and enlarged for 30 minutes to prepare a composite rubbery polymer having the average particle diameter shown in Table 1 below. .

<Preparation of composite rubber graft polymer>

In a nitrogen-substituted reactor, after adding 100 parts by weight of deionized water to 50 parts by weight of the obtained composite rubbery polymer latex (based on solid content), 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate It was put in at once. A mixed solution of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 0.2 parts by weight of cumene hydroperoxide was continuously added at a constant rate for 2.5 hours while polymerization at 70° C. for 2.5 hours, and then additional cumene hydroperoxide 0.05 After the polymerization was completed for 1 hour by adding parts by weight, a composite rubber-like graft polymer latex was prepared. The composite rubbery graft polymer latex _{was agglomerated with MgSO 4} , aged, washed, dehydrated and dried to prepare a composite rubbery graft polymer powder.

<Production of thermoplastic resin composition>

A thermoplastic resin composition was prepared by mixing 35 parts by weight of the composite rubbery graft polymer powder and 65 parts by weight of 92HR (styrene/acrylonitrile polymer (SAN polymer)) manufactured by LG Chem.

Comparative example One

<Production of the second diene rubber polymer>

100 parts by weight of the first diene-based rubbery polymer latex of Preparation Example 2 (based on solid content) and 2 parts by weight of phosphoric acid were added to the reactor, and stirred and enlarged to prepare a second diene-based rubbery polymer latex having an average particle diameter of 100 nm.

<Production of composite rubber polymer>

Into a reactor, 10 parts by weight of the second butadiene rubbery polymer latex (based on solid content) and 90 parts by weight of the acrylic rubbery polymer latex B of Preparation Example 4 were added and mixed. Then, 3 parts by weight of phosphoric acid was added to the reactor, and stirred and enlarged to prepare a composite rubbery polymer having an average particle diameter of 350 nm.

<Preparation of composite rubber graft polymer>

In a nitrogen-substituted reactor, after adding 100 parts by weight of deionized water to 50 parts by weight of the composite rubbery polymer latex (based on solid content), 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate at a time Was put in. A mixed solution of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 0.2 parts by weight of cumene hydroperoxide was continuously added at a constant rate for 2.5 hours while polymerization at 70° C. for 2.5 hours, and then additional cumene hydroperoxide 0.05 After the polymerization was completed for 1 hour by adding parts by weight, a composite rubber-like graft polymer latex was prepared. The composite rubbery graft polymer latex _{was agglomerated with MgSO 4} , aged, washed, dehydrated and dried to prepare a composite rubbery graft polymer powder.

<Production of thermoplastic resin composition>

A thermoplastic resin composition was prepared by mixing 35 parts by weight of the composite rubber graft polymer powder and 65 parts by weight of 92HR (styrene/acrylonitrile polymer, SAN polymer) manufactured by LG Chem.

Comparative example 2

<Production of the second diene rubber polymer>

100 parts by weight of the first diene-based rubbery polymer latex of Preparation Example 2 (based on solid content) and 2 parts by weight of phosphoric acid were added to the reactor, and stirred and enlarged to prepare a second diene-based rubbery polymer latex having an average particle diameter of 100 nm.

<Production of composite rubber polymer>

10 parts by weight (based on solid content) of the second butadiene rubbery polymer latex was added to the reactor, followed by nitrogen substitution. After heating the reactor to 70°C, 90 parts by weight of butyl acrylate, 0.4 parts by weight of allyl methacrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, 2 parts by weight of dipotassium alkenyl succinate salt, 50 parts by weight of deionized water The mixed solution was polymerized while continuously being added to the reactor for 4 hours at a constant rate. At the same time, 0.3 parts by weight of potassium persulfate was polymerized while continuously being added to the reactor for 4 hours at a constant rate to prepare a composite rubbery polymer having an average particle diameter of 290 nm.

<Preparation of composite rubber graft polymer>

In a nitrogen-substituted reactor, after adding 100 parts by weight of deionized water to 50 parts by weight of the composite rubbery polymer latex (based on solid content), 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate at a time Was put in. A mixed solution of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 0.2 parts by weight of cumene hydroperoxide was continuously added at a constant rate for 2.5 hours while polymerization at 70° C. for 2.5 hours, and then additional cumene hydroperoxide 0.05 After the polymerization was completed for 1 hour by adding parts by weight, a composite rubber-like graft polymer latex was prepared. The composite rubbery graft polymer latex _{was agglomerated with MgSO 4} , aged, washed, dehydrated and dried to prepare a composite rubbery graft polymer powder.

<Production of thermoplastic resin composition>

A thermoplastic resin composition was prepared by mixing 35 parts by weight of the composite rubbery graft polymer powder and 65 parts by weight of 92HR (styrene/acrylonitrile polymer (SAN polymer)) manufactured by LG Chem.

Comparative example 3

<Production of the second diene rubber polymer>

100 parts by weight of the first diene-based rubbery polymer latex (based on solid content) of Preparation Example 2 and 2.5 parts by weight of the acid group-containing polymer latex of Preparation Example 7 were added to the reactor, stirred and enlarged, and the second diene-based rubbery substance having an average particle diameter of 150 nm A polymer latex was prepared.

<Production of composite rubber polymer>

10 parts by weight (based on solid content) of the second butadiene rubbery polymer latex was added to the reactor, followed by nitrogen substitution. After heating the reactor to 70°C, 90 parts by weight of butyl acrylate, 0.4 parts by weight of allyl methacrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, 2 parts by weight of dipotassium alkenyl succinate salt, 50 parts by weight of deionized water The mixed solution was polymerized while continuously being added to the reactor for 4 hours at a constant rate. At the same time, 0.3 parts by weight of potassium persulfate was polymerized while continuously added to the reactor for 4 hours at a constant rate to prepare a composite rubbery polymer latex having an average particle diameter of 340 nm.

<Preparation of composite rubber graft polymer>

In a nitrogen-substituted reactor, after adding 100 parts by weight of deionized water to 50 parts by weight of the composite rubbery polymer latex (based on solid content), 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate at a time Was put in. A mixed solution of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 0.2 parts by weight of cumene hydroperoxide was continuously added at a constant rate for 2.5 hours while polymerization at 70° C. for 2.5 hours, and then additional cumene hydroperoxide 0.05 After the polymerization was completed for 1 hour by adding parts by weight, a composite rubber-like graft polymer latex was prepared. The composite rubbery graft polymer latex _{was agglomerated with MgSO 4} , aged, washed, dehydrated and dried to prepare a composite rubbery graft polymer powder.

<Production of thermoplastic resin composition>

A thermoplastic resin composition was prepared by mixing 35 parts by weight of the graft polymer powder and 65 parts by weight of 92HR (styrene/acrylonitrile polymer (SAN polymer)) manufactured by LG Chem.

Comparative example 4

<Production of the second diene rubber polymer>

100 parts by weight of the first diene-based rubbery polymer latex A of Preparation Example 1 (based on solid content) and 5 parts by weight of the acid group-containing polymer latex (based on solid content) of Preparation Example 5 were added to the reactor, and stirred and enlarged for 30 minutes, averaged A second diene-based rubbery polymer latex having a particle diameter of 100 nm was prepared.

<Production of composite rubber polymer>

10 parts by weight (based on solid content) of the second butadiene rubbery polymer latex was added to the reactor, followed by nitrogen substitution. After heating the reactor to 70°C, 90 parts by weight of butyl acrylate, 0.4 parts by weight of allyl methacrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, 2 parts by weight of dipotassium alkenyl succinate salt, 50 parts by weight of deionized water The mixed solution was polymerized while continuously being added to the reactor for 4 hours at a constant rate. At the same time, 0.3 parts by weight of potassium persulfate was polymerized while continuously added to the reactor for 4 hours at a constant rate to prepare a composite rubbery polymer latex having an average particle diameter of 100 nm.

<Preparation of composite rubber graft polymer>

In a nitrogen-substituted reactor, after adding 100 parts by weight of deionized water to 50 parts by weight of the composite rubbery polymer latex (based on solid content), 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate at a time Was put in. A mixed solution of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 0.2 parts by weight of cumene hydroperoxide was continuously added at a constant rate for 2.5 hours while polymerization at 70° C. for 2.5 hours, and then additional cumene hydroperoxide 0.05 After the polymerization was completed for 1 hour by adding parts by weight, a composite rubber-like graft polymer latex was prepared. The composite rubbery graft polymer latex _{was agglomerated with MgSO 4} , aged, washed, dehydrated and dried to prepare a composite rubbery graft polymer powder.

<Production of thermoplastic resin composition>

A thermoplastic resin composition was prepared by mixing 35 parts by weight of the composite rubbery graft polymer powder and 65 parts by weight of 92HR (styrene/acrylonitrile polymer (SAN polymer)) manufactured by LG Chem.

Comparative example 5

LG Chem's DP229M (small particle diameter ABS graft polymer, butadiene rubber polymer average particle diameter: 100 nm) 10 parts by weight, LG Chem's SA927 (large particle diameter ASA graft polymer, butyl acrylate rubber polymer average particle diameter: 300 nm) ) 20 parts by weight, and 70 parts by weight of LG Chem's 92HR (styrene/acrylonitrile polymer (SAN polymer)) were mixed to prepare a thermoplastic resin composition.

Comparative example 6

SA100 (small particle diameter ASA graft polymer, average particle diameter of butyl acrylate rubber polymer: 100 nm) 20 parts by weight of LG Chem, SA927 (large particle diameter ASA graft polymer, average particle diameter of butyl acrylate rubber polymer) : 300 nm) 20 parts by weight and 60 parts by weight of 92HR (styrene/acrylonitrile polymer (SAN polymer)) manufactured by LG Chemical Co., Ltd. were mixed to prepare a thermoplastic resin composition.

Experimental example One

The thermoplastic resin compositions of Examples and Comparative Examples were extruded to produce pellets. The physical properties of the pellets were measured as follows, and the results are shown in Tables 1 and 2 below.

① Flow index (g/10 min): In accordance with ASTM D1238, it was measured under the condition of 220° C. and 10 kg.

Experimental example 2

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

② Impact strength (kg·m/m, 1/4 In): It was measured according to ASTM D256.

③ Tensile strength (kg/㎠): It was measured according to ASTM D638.

④ Weather resistance: It was measured according to SAE J2527.

division Example 1 Example 2 Example 3 Example 4 Preparation of the second diene rubber polymer First diene system
Rubbery
polymer
Latex Kinds Manufacturing Example 1 Manufacturing Example 1 Manufacturing Example 1 Manufacturing Example 1 Average particle diameter
(Nm) 60 60 50 50 input
(Part by weight) 100 100 100 100 First acid group-containing polymer
Latex Kinds Manufacturing Example 5 Manufacturing Example 5 Manufacturing Example 5 Manufacturing Example 5 Methacrylic acid unit
(weight%) 3 3 3 3 Average particle diameter (nm) 48 48 48 48 input
(Part by weight) 5 3.5 4 5 Second rubbery
polymer
Latex Average particle diameter
(Nm) 100 100 110 115 Of composite rubbery polymer
Produce Second rubbery
polymer
Latex input
(Part by weight) 10 10 13 15 Acrylic
Rubbery
polymer
Latex Kinds Manufacturing Example 3 Manufacturing Example 3 Manufacturing Example 3 Manufacturing Example 3 Average particle diameter
(Nm) 100 100 100 110 input
(Part by weight) 90 90 87 85 Second acid group-containing polymer
Latex Kinds Manufacturing Example 6 Manufacturing Example 6 Manufacturing Example 6 Manufacturing Example 6 Methacrylic acid unit
(weight%) 6 6 6 6 Average particle diameter (nm) 98 98 98 98 Input amount (parts by weight) 2 3 3 3 Composite rubbery polymer Average particle diameter
(Nm) 300 300 330 330 Thermoplastic resin composition Compound rubbery
Graft polymer powder
(Part by weight) 35 35 35 35 SAN polymer
(Part by weight) 65 65 65 65 Flow index 20 18 19 21 Impact strength 20 19 19 18 The tensile strength 460 460 450 450 Weather resistance 3.5 class 3~3.5 grade 3~3.5 grade 3.5 class

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Of the second diene rubber polymer
Produce First diene system
Rubbery polymer
Latex Kinds Manufacturing Example 2 Manufacturing Example 2 Manufacturing Example 2 Manufacturing Example 1 - Average particle diameter
(Nm) 50 50 50 60 - input
(Part by weight) 100 100 100 100 - Phosphoric acid input
(Part by weight) 2 2 - - Acid group-containing polymer
Latex Kinds - - Manufacturing Example 7 Manufacturing Example 5 - - Average particle diameter
(Nm) - - 75 48 - - input
(Part by weight) - - 2.5 5 - - 2nd diene rubber polymer
Latex Average particle diameter
(Nm) 100 100 150 100 - - Preparation of composite rubbery polymer Manufacturing method Hyperbolic polymerization polymerization polymerization - - Second diene rubber polymer latex input
(Part by weight) 10 10 10 10 - - Acrylic rubber
polymer
Latex Kinds Manufacturing Example 4 - - - - - Average particle diameter
(Nm) 110 - - - - input
(Part by weight) 90 - - - - - Phosphoric acid input
(Part by weight) 3 - - - - Butyl acrylate input
(Part by weight) - 90 90 90 - - Composite rubbery polymer Average particle diameter (nm) 350 290 340 290 - - Thermoplastic resin composition Compound rubbery
Graft
Polymer powder 35 35 35 35 - - Small particle diameter
ABS Graft Polymer Powder 10 - Small particle diameter ASA graft polymer powder - - - - 20 Large particle diameter ASA graft polymer powder - - - 20 20 SAN polymer 65 65 65 65 70 60 Flow index 23 18 20 19 20 15 Impact strength 17 17 20 18 15 15 The tensile strength 450 450 430 440 450 440 Weather resistance 2.5~3 grade 2.5~3 grade 2.5 class Level 3 Level 2 Level 4

Referring to the table, it was confirmed that the thermoplastic resin compositions of Examples 1 to 4 were excellent in impact strength, tensile strength, and weather resistance.

On the other hand, the thermoplastic resin composition of Comparative Example 1 using the graft polymer prepared by enlarging the second diene rubber polymer and the composite rubber polymer with phosphoric acid has impact strength and weather resistance compared to the thermoplastic resin compositions of Examples 1 to 4. It could be confirmed that it was degraded.

The thermoplastic resin composition of Comparative Example 2 using the graft polymer prepared by enlarging the second diene-based rubber polymer with phosphoric acid and polymerizing the composite rubber polymer was compared to the thermoplastic resin compositions of Examples 1 to 4 in impact strength and weather resistance. It was confirmed that this decreased.

Although the second diene-based rubber polymer was made of an acid group-containing polymer latex, the thermoplastic resin compositions of Comparative Examples 3 and 4 using the graft polymer prepared by polymerization of the composite rubber polymer were the thermoplastic resin compositions of Examples 1 to 4 In contrast, it was confirmed that the tensile strength and weather resistance were lowered.

It was confirmed that the thermoplastic resin composition of Comparative Example 5 using a mixture of a small-diameter ABS graft polymer and a large-diameter ASA graft polymer had lower impact strength and weather resistance compared to the thermoplastic resin compositions of Examples 1 to 4.

It can be seen that the thermoplastic resin composition of Comparative Example 5 using a mixture of a small-diameter ASA graft polymer and a large-diameter ASA graft polymer decreased the flow index, impact strength, and tensile strength compared to the thermoplastic resin compositions of Examples 1 to 4. there was.

From these results, it was confirmed that only when all the technical features of the present invention were satisfied, a thermoplastic resin composition having excellent flow index, impact strength, tensile strength, and weather resistance could be prepared.

Claims (9)

Preparing a second diene-based rubbery polymer by enlarging the first diene-based rubbery polymer with a first acid group-containing polymer;
Preparing a composite rubbery polymer by enlarging the second diene-based rubbery polymer and an acrylic rubbery polymer with a second acid group-containing polymer; And
A method for producing a graft polymer, comprising graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer on the composite rubbery polymer to prepare a graft polymer.
The method according to claim 1,
The second diene-based rubber polymer and the acrylic rubber polymer have a weight ratio of 5:95 to 20:80.
The method according to claim 1,
The first diene-based rubbery polymer is a method for producing a graft polymer having an average particle diameter of 30 to 70 nm.
The method according to claim 1,
The second diene-based rubbery polymer is a method for producing a graft polymer having an average particle diameter of 80 to 130 nm.
The method according to claim 1,
The method for producing a graft polymer wherein the acrylic rubber polymer has an average particle diameter of 80 to 130 nm.
The method according to claim 1,
The first acid group-containing polymer and the second acid group-containing polymer include a carboxylic acid-based monomer unit and a C ₁ to C ₃ alkyl (meth) acrylate-based monomer unit,
The method for producing a graft polymer, wherein the first acid group-containing polymer contains a small amount of carboxylic acid monomer units compared to the second acid group-containing polymer.
The method of claim 6,
The first acid group-containing polymer contains 2 to 5% by weight of a carboxylic acid monomer unit,
The second acid group-containing polymer is a method for producing a graft polymer comprising 3 to 9% by weight of a carboxylic acid-based monomer unit.
The method according to claim 1,
The method for producing a graft polymer wherein the first acid group-containing polymer has an average particle diameter of 30 to 70 nm.
The method according to claim 1,
The second acid group-containing polymer has an average particle diameter of 80 to 130 nm.