KR20200036507A - In-situ bimodal acrylonitrile-conjugated diene rubber-aromatic vinyl copolymer, method for preparing thereof and thermoplastic resin composition comprising thereof - Google Patents

Abstract

The present invention relates to an in-situ bimodal vinylcyan compound-conjugated diene rubber-aromatic vinyl compound copolymer, a method for preparing the same, and a method for preparing a thermoplastic resin composition comprising the same, and more particularly to an in-situ bimodal vinylcyan compound-conjugated diene rubber-aromatic vinyl compound copolymer which is prepared by inputting a part of a grafted monomer first into a conjugated diene rubber latex, inputting a copolymer with a low content of acid group-containing monomer within a predetermined content range to carry out enlargement, and inputting a residual amount of grafted monomer to carry out graft polymerization. According to the present invention, the in-situ bimodal vinylcyan compound-conjugated diene rubber-aromatic vinyl compound copolymer can provide advantages of excellent formability, impact strength, etc., while achieving excellent polymerization stability compared to a conventional one.

Description

IN-SITU BIMODAL ACRYLONITRILE-CONJUGATED DIENE RUBBER-AROMATIC VINYL COPOLYMER, METHOD FOR PREPARING THEREOF AND THERMOPLASTIC RESIN COMPOSITION COMPRISING THEREOF}

The present invention relates to an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer, a method of manufacturing the same, and a method of manufacturing a thermoplastic resin composition comprising the same, more specifically, superior in polymerization stability compared to the prior art It relates to an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer that can provide excellent advantages such as moldability and impact strength.

The vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer represented by acrylonitrile-butadiene-styrene (ABS resin) has good physical properties such as impact resistance, mechanical strength, moldability, and glossiness, making it an electrical component and electronic component. It is widely used in various fields, such as office equipment and automobile parts.

In general, ABS resin is prepared by preparing butadiene rubber latex, followed by grafting styrene and acrylonitrile. At this time, physical properties such as impact resistance, mechanical strength, and glossiness of the graft copolymer are greatly affected by the average particle diameter, particle size distribution, dispersion state, and coagulation content of the rubber polymer latex.

In the case of a typical ABS product, the optimum rubber particle size excellent in both impact resistance and fluidity is 3000 to 5000 ,, and the optimum rubber particle size capable of improving colorability and surface gloss characteristics is known to be around 1000 ,, and for this reason, many ABS Resin manufacturers are manufacturing ABS products by applying bimodal rubber particles having the above two types of particle size distribution.

However, the large-diameter rubber having a particle diameter of 3000 to 5000 이 has a problem of low productivity because the polymerization time is significantly longer than that of the small-diameter rubber, and manufacturing and management problems occur when mixing and applying large-diameter and small-diameter rubber particles respectively. There was a problem of lowering productivity.

Accordingly, there is a need to develop a technology capable of providing ABS powder having excellent polymerization stability and processability, while having excellent impact resistance and appearance quality, as compared to the prior art.

Korean Patent Registration 10-0591039 B1

In order to solve the problems of the prior art as described above, the present invention aims to provide a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer having superior impact resistance and processability, and has excellent process efficiency compared to the prior art. An object of the present invention is to provide a production method capable of providing the copolymer with high productivity.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having a particle diameter of 800 to 1500 mm 2; And a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2, wherein the second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprises An acid group-containing copolymer, wherein the acid group-containing copolymer comprises 1 to 8% by weight of an acid group-containing monomer based on 100% by weight of the copolymer, and the acid group-containing copolymer is 0.5 based on 100 parts by weight of the conjugated diene rubber In-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl, which is contained in 5 parts by weight and characterized in that the coagulant content is 500 ppm or less (based on the total weight of the conjugated diene rubber, aromatic vinyl compound, and vinyl cyan compound). Provided is a compound copolymer.

In addition, the present invention is the first to pre-inject 5 to 20% by weight of 100% by weight of the vinyl cyan compound and aromatic vinyl compound used in 100 parts by weight of the conjugated diene rubber latex having an average particle diameter of 800 to 1500 mm 3 (based on solid content). step; A second step of partially enlarging the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 2 by adding 0.5 to 5 parts by weight of an acid group-containing copolymer to the mixture of the first step; And a residual amount of a vinyl cyan compound and an aromatic vinyl compound in the mixture of the second step; And an initiator; a third step of injecting and graft polymerizing; wherein the acid group-containing copolymer contains 1 to 8 wt% of an acid group-containing monomer based on 100 wt% of the copolymer, and is obtained after the graft polymerization. The vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer is an in-situ bimodal rubber polymer comprising a conjugated diene rubber having a particle diameter of 800 to 1500 mm 3 and a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2 Provided is a method for preparing an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer.

In addition, the present invention 20-80% by weight of the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and 20-80% by weight of aromatic vinyl compound-vinyl cyan compound copolymer prepared according to the above production method After preparing a mixture comprising a step, melt-kneading the mixture; And extruding; provides a method for producing a thermoplastic resin composition comprising a.

According to the present invention, it is possible to provide an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer having a low coagulant content and excellent processability and impact resistance.

In addition, according to the present invention, it is possible to provide a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer with high productivity due to excellent process efficiency as compared to the prior art and low content of coagulum.

1 is a schematic view showing an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer prepared by a production method according to an embodiment of the present invention.
2 is a particle size distribution curve of a rubber polymer prepared according to an embodiment of the present invention.
3 is a particle size distribution curve of a rubber polymer not according to the present invention.
(In FIG. 2 and FIG. 3, the x-axis represents the particle diameter (unit: nm) of the polymer, and the y-axis represents the relative intensity (REL.).)

Hereinafter, the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer of the present disclosure and a method for manufacturing the same will be described in detail.

As used herein, the term "in-situ bimodal" is not a mixture of two rubber latexes having different average particle diameters prepared separately, but is polymerized simultaneously or continuously in one reactor and having two different particle sizes. It means that a rubber polymer was formed.

The particle diameter of the polymer in the present description indicates a value measured by a dynamic light scattering method using a particle size distribution analyzer (Nicomp 380), unless otherwise specified. In addition, in the present description, the average particle size means a particle size whose light intensity corresponds to 50% in the particle size distribution curve.

The in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer of the present disclosure is, for example, a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound containing a conjugated diene rubber having a particle diameter of 800 to 1500 mm 3 coalescence; And a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2, wherein the second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprises An acid group-containing copolymer, wherein the acid group-containing copolymer comprises 1 to 8% by weight of an acid group-containing monomer based on 100% by weight of the copolymer, and the acid group-containing copolymer is 0.5 based on 100 parts by weight of the conjugated diene rubber It contains from 5 parts by weight, characterized in that the content of coagulation is less than or equal to 500ppm, in this case, the content of coagulation is small, so that productivity is excellent and impact resistance and workability are both excellent.

In the present description, unless otherwise specified, the content of the coagulation product is in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer weight of the coagulum produced in the reaction tank, rubber added during the copolymer production (solid content) It is a value calculated by measuring the weight and the weight of the monomer and using the following equation (1).

[Equation 1]

Coagulant content [ppm] = weight of coagulum produced inside the reactor / (total rubber weight + monomer weight)

The conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2 may be characterized as a non-conjugated conjugated diene rubber containing the acid group-containing copolymer.

The method for preparing the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer of the present disclosure is, for example, vinyl used in 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 800 to 1500 mm 3 (based on solid content). A first step of pre-injecting 5 to 20% by weight of the total of 100% by weight of the cyan compound and the aromatic vinyl compound; A second step of partially enlarging the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 2 by adding 0.5 to 5 parts by weight of an acid group-containing copolymer to the mixture of the first step; And a residual amount of a vinyl cyan compound and an aromatic vinyl compound in the mixture of the second step; And an initiator; a third step of injecting and graft polymerizing; wherein the acid group-containing copolymer contains 1 to 8 wt% of an acid group-containing monomer based on 100 wt% of the copolymer, and is obtained after the graft polymerization. The vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer is characterized in that it is an in-situ bimodal rubber polymer comprising a conjugated diene rubber having a particle diameter of 800 to 1500 mm 3 and a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2. , In this case, a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer having excellent polymerization stability, low coagulation content, and excellent impact resistance and processability can be provided with high productivity.

Hereinafter, the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and its preparation method will be described in detail for each configuration.

Graft  Monomer Pre-input First step

The preparation method of the present substrate is a preparation for pre-injecting 5 to 20% by weight of 100% by weight of the vinyl cyan compound and aromatic vinyl compound used in 100 parts by weight of the conjugated diene rubber latex having an average particle diameter of 800 to 1500 Å (based on solid content). Step 1 is included.

In the first step, 5 to 20% by weight, 8 to 20% by weight, 8 to 16% by weight of the vinyl cyan compound and the aromatic vinyl compound based on 100% by weight of the total amount of the vinyl cyan compound and the aromatic vinyl compound used in the reaction. This can be introduced, and in this case, a coagulant formation is controlled during the non-dialysis process, so that a copolymer having excellent polymerization stability and excellent physical properties such as impact resistance can be obtained.

In the first step, only some of the vinyl cyan compound and the aromatic vinyl compound are pre-injected, and polymerization is not initiated. In this case, the formation of a coagulation product is controlled during the non-conversation process, thereby contributing to an improvement in polymerization stability and productivity, and finally A bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer having different rubber particle diameters is obtained, which has the advantage of improving physical properties.

That is, the first step is characterized in that it is initiator-free (free) containing no initiator.

The vinyl cyan compound and the aromatic vinyl compound introduced in the first step may be characterized in that they are mixed in a weight ratio of 10:90 to 40:60, 20:80 to 40:60 or 30:70 to 40:60, Within this range, the balance of physical properties such as processability and impact resistance of the copolymer finally obtained is excellent.

The vinyl cyan compound may be, for example, one or more selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably acrylonitrile.

The aromatic vinyl compound may be, for example, one or more selected from styrene, alpha-methyl styrene, vinyl toluene, and chloro styrene, and preferably styrene.

In the first step, the conjugated diene rubber latex to be added may have an average particle diameter of 800 to 1500 mm 2, 900 to 1300 mm 2 or 950 to 1200 mm 1, for example, excellent fluidity and impact resistance of the copolymer finally obtained within this range. This is excellent, and has the advantage of excellent appearance quality.

The conjugated diene rubber latex may be, for example, a polymer latex containing one or more conjugated diene-based compounds selected from 1,3-butadiene, isoprene, chloroprene, and piperylene, and optionally further polymerized by including styrene and the like. Copolymer latex, preferably butadiene rubber latex or butadiene-styrene rubber latex.

Conjugate Dien  Rubberized Stage 2

The manufacturing method of the present invention includes a second step of partially enlarging the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 2 by adding an acid group-containing copolymer to the mixture of the first step.

In the present description, "partially enlarged" means that a part of the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 3 dispersed in the latex chemically interacts with the acid group-containing copolymer to aggregate while decreasing the dispersion stability of the latex. Part of the relatively excess conjugated diene rubber is dispersed in the latex while maintaining the original average particle size of 800 to 1500 mm 3 without agglomeration due to the chemical interaction as described above, and thus the partially enlarged latex has a particle size of 800 to Conjugated diene rubber, which is 1500 mm3, and hyper-sized rubber coexist.

The second step may be performed at a temperature of 25 to 70 ° C for 10 minutes to 120 minutes, and preferably at a temperature of 50 to 70 ° C for 20 minutes to 100 minutes.

The acid group-containing copolymer introduced in the second step is, for example, based on 100 parts by weight of the conjugated diene rubber latex having an average particle size of 800 to 1500 mm 3 (based on solid content), 0.5 to 5 parts by weight, 0.7 to 4.5 parts by weight, or Bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound having an average particle diameter in a desired range while maintaining a high polymerization stability within this range can be obtained in 1.5 to 4 parts by weight.

The acid group-containing copolymer may have, for example, an average particle diameter of 800 to 1500 mm 2 or 800 to 1400 mm 2, and has a high polymerization stability within this range and a reduced coagulation content.

The acid group-containing copolymer comprises 1 to 8% by weight or 1.5 to 6% by weight of an acid group-containing monomer as an example based on 100% by weight of the copolymer, and within this range, the polymerization stability is excellent and the content of the coagulated product is reduced. to provide.

The acid group-containing monomers are, for example, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, crotonic acid, crotonic anhydride , Fumaric acid, maleic acid, maleic anhydride, citraconic acid, and citraconic anhydride. , Preferably acrylic acid or methacrylic acid, more preferably methacrylic acid.

As a specific example, the acid group-containing copolymer may be a copolymer that contains 1 to 8% by weight of an acid group-containing monomer and 92 to 99% by weight of a (meth) acrylic acid alkyl ester compound, and maintains high polymerization stability within this range. And there is an advantage that the content of coagulation is reduced.

For example, the (meth) acrylic acid alkyl ester may preferably have 1 to 20 carbon atoms in alkyl, and specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid n-. Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, and the like, preferably ethyl acrylate or butyl acrylate, and more preferably ethyl Acrylate.

For example, the acid group-containing copolymer may be spherical particles having a homogeneous structure in which the (meth) acrylic acid alkyl ester and the acid group-containing monomer are uniformly mixed, and in another example, the acid group-containing copolymer is (meth) acrylic acid alkyl Polymerized cores including esters; And a shell surrounding the core, and polymerized shell including a (meth) acrylic acid alkyl ester and an acid group-containing monomer; and a core-shell structured copolymer.

The acid group-containing copolymer may optionally further include an aromatic vinyl compound, a vinyl cyan compound, or both.

The monomer component in rubber Graft  Polymerized Stage 3

The production method of the present disclosure includes a mixture of the second step, that is, a residual amount of vinyl cyan compound and aromatic vinyl compound in the partially enlarged rubber latex; And an initiator; a third step of initiating graft polymerization by introducing the graft copolymer.

The vinyl cyan compound and the aromatic vinyl compound input in the third step may be characterized in that they are mixed in a weight ratio of 10:90 to 40:60, 20:80 to 40:60 or 30:70 to 40:60 as an example. There is an excellent balance of physical properties such as processability and impact resistance of the copolymer finally obtained within this range.

The initiator injected in the third step is not particularly limited as long as it is an initiator commonly used in the art, and is preferably cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and p -mentan hydride. It may be one or more selected from loper oxide, benzoyl peroxide, sodium persulfate, and potassium persulfate.

In another example, the third step may optionally be further performed by further including an oxidation-reduction catalyst, and the oxidation-reduction catalyst may be a combination of ferrous sulfate, dextrose, and sodium pyrophosphate. However, the present invention is not limited thereto, and any type commonly used in the art may be appropriately selected without limitation.

In the third step, it may be preferable to further emulsify graft polymerization by further including an emulsifier, and the emulsifier is not particularly limited as long as it is a type commonly used in the art, preferably alkyl aryl sulfonate and alkali methyl alkyl sulfate. , Sulfonated alkyl ester, a metal salt of an unsaturated fatty acid, a metal salt of a dimer acid or a trimer acid, but may be one or more selected, but is not limited thereto.

The graft copolymer latex obtained in the third step has a coagulant content of 500 ppm or less, 250 ppm or less, 150 ppm or less, or 100 ppm or less, thereby providing the graft copolymer with high productivity.

The graft copolymer obtained in the third step may be characterized in that it is an in-situ bimodal rubber polymer comprising a conjugated diene rubber having an average particle diameter of 800 to 1500 mm 2 and a conjugated diene rubber having an average particle diameter of 3000 to 5000 mm 2. In this case, the impact resistance, processability, and appearance quality of the final product are all excellent, so that a high-quality molded product can be provided.

In another example, the graft copolymer obtained in the third step may be characterized in that it is an in-situ bimodal rubber polymer comprising a conjugated diene rubber having an average particle diameter of 900 to 1300 mm 3 and a conjugated diene rubber having an average particle diameter of 3000 to 3500 mm 3. In this range, the impact resistance, processability, and appearance quality of the final product are more excellent.

Graft  To obtain a copolymer powder 4th step

After the third step, the step of agglomerating and drying the graft copolymer latex to obtain an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer in a powder form.

As a specific example, after the third step, the graft copolymer latex is agglomerated by adding a metal salt or an acid coagulant, and then aged, washed, dehydrated and dried to obtain a powdery vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer. Can be obtained.

The metal salt or acid coagulant may be, for example, magnesium sulfate, aluminum sulfate, calcium chloride, calcium acetate, acetic acid, hydrochloric acid, but is not limited thereto.

As described above, the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer according to the present disclosure is an in-situ bimodal rubber polymer containing conjugated diene rubbers having different particle sizes, and the specific structure thereof will be described with reference to the drawings.

1 is a schematic view of an in-situ bimodal rubber polymer prepared by the production method according to the present disclosure. Referring to this, the copolymer prepared according to the production method of the present disclosure is a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl in which a vinyl aromatic compound and a vinyl cyan compound are grafted to a conjugated diene rubber having a particle diameter in the range of 800 to 1500 mm 2 The compound copolymer (A) and the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 2 injected at the beginning of the reaction are enlarged, and a vinyl aromatic compound and a vinyl cyan compound are grafted to the conjugated diene rubber having a particle size of 3000 to 5000 mm 2. 2 vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymers (B1, B2).

1, the rubber is enlarged by interaction with an acid group-containing copolymer, and the conjugated diene rubber aggregates on the periphery of the acid group-containing copolymer to form an enlarged rubber, and the enlarged rubber (core) The vinyl aromatic compound and the vinyl cyan compound may have a form (B1) including a graft copolymerized shell and another core-shell form (B2).

In another form (B2), the aromatic vinyl compound and the vinyl cyan compound pre-injected into a conjugated diene rubber having an average particle diameter of 800 to 1500 mm 3, which are partially unagglomerated after the introduction of the initiator, are grafted to form a shell, and at the same time, they are enlarged by aggregation. The formed rubber is formed, and the residual amount of the vinyl cyan compound and the aromatic vinyl compound added with the initiator to the enlarged rubber is graft polymerized to form a shell, whereby graft polymerization proceeds both inside and outside the enlarged rubber. will be.

The powdery vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer prepared according to the present disclosure may be provided as a thermoplastic resin composition by mixing with a matrix resin, and further may be provided as a molded product through a molding process.

For example, the thermoplastic resin composition is 20-80% by weight of the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and 20-80% by weight aromatic vinyl compound-vinyl cyan compound copolymer prepared according to the above-mentioned manufacturing method. After preparing a mixture containing%, melt-kneading the mixture; And extruding; can be prepared including.

In another example, the mixture may include 20 to 40% by weight of an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and 60 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, Within this range, the composition has an excellent melt index, and thus has excellent processability and excellent impact resistance.

When preparing the mixture or when melt-kneading the mixture, an additive may be optionally included as necessary, and the additives include, for example, antioxidants, heat stabilizers, lubricants, dyes, pigments, colorants, mold release agents, antistatic agents, antibacterial agents, and processing. It may be one or more selected from auxiliaries, metal deactivators, flame retardants, flame retardants, anti-dropping agents, anti-friction agents, and anti-wear agents, but is not limited thereto.

The additive may be included, for example, 0.01 to 5% by weight, 0.05 to 3% by weight, 0.1 to 2% by weight, or 0.5 to 1% by weight based on the total weight of the composition, and within this range, the inherent physical properties of the thermoplastic resin composition The effect of adding the additive can be realized without lowering.

The kneading and extrusion are, for example, 190 to 260 ° C and 100 to 400 rpm; Or 200 to 250 ℃ and 150 to 350rpm; may be performed under conditions that are not limited thereto, and may be carried out by appropriately selecting within a range commonly practiced in the art.

After the melting and kneading, the composition may be provided in pellet form through extrusion, and the extrusion is not particularly limited when using an extruder conventionally used in the art, and preferably performed using a twin-screw extrusion kneader Can be.

Furthermore, the composition of the present base material prepared as described above may be provided as a molded product for various purposes through molding processes such as injection and blow molding.

In describing the in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer of the present disclosure, a method of manufacturing the same, and a method of manufacturing the thermoplastic resin composition, other conditions or equipment not explicitly described are sugar It is noted that it can be appropriately selected within a range that is generally practiced in the industry, and is not particularly limited.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

Materials used in the following Examples and Comparative Examples are prepared as follows.

[Production Example-Preparation of acid group-containing copolymer]

In the following preparation examples, the weight parts of each component are based on a total of 100 parts by weight of monomers used in preparing the acid group-containing copolymer, that is, ethyl acrylate and methacrylic acid.

Manufacturing example  One

Into the reactor, 208 parts by weight of distilled water and 0.5 parts by weight of dioctyl sulfosuccinate sodium as an emulsifier were added and stirred while heating to 70 ° C., and 0.034 parts by weight of potassium persulfate and 50 parts by weight of ethyl acrylate were added to initiate the reaction. After that, polymerization was performed for 90 minutes to prepare a core. Then, in the presence of the core, a mixture containing 48.5 parts by weight of ethyl acrylate, 1.5 parts by weight of methacrylic acid, and 0.25 parts by weight of dioctyl sulfosuccinate sodium, prepared in a separate container, was continuously added and reacted for 90 minutes to react the shell. Formed. Finally, a core-shell structured ethyl acrylate-methacrylic acid copolymer having an average particle diameter of 1100 mm 3 (methacrylic acid content in the copolymer was 1.5% by weight) was obtained.

Manufacturing example  2

In Preparation Example 1, dioctyl sulfosuccinate sodium was added at 0.75 parts by weight instead of 0.5 parts by weight to prepare a core, and when preparing the shell, 48.5 parts by weight of ethyl acrylate and 1.5 parts by weight of ethyl acrylate instead of 1.5 parts by weight of methacrylic acid And ethyl acrylate-methacrylic acid copolymer having a core-shell structure (3% by weight of methacrylic acid in the copolymer) in the same manner as in Preparation Example 1, except that 3 parts by weight of methacrylic acid was added. At this time, the prepared copolymer had an average particle diameter of 920 MPa.

Manufacturing example  3

To the reactor, 208 parts by weight of distilled water, 0.25 parts by weight of dioctyl sulfosuccinate sodium and 0.034 parts by weight of potassium persulfate as an initiator were added, followed by 0.25 parts by weight of dioctyl sulfosuccinate sodium, 94 parts by weight of ethyl acrylate and methacryl Reaction was performed by continuously adding 6 parts by weight of acid for 4 hours, and finally, an ethyl acrylate-methacrylic acid copolymer having an average particle diameter of 1100 MPa (methacrylic acid content in the copolymer was 6% by weight) was obtained. At this time, the prepared copolymer has a homogeneous structure in which monomer components used in the reaction are mixed uniformly, not in a core-shell structure.

Manufacturing example  4

Ethyl acrylate-methacrylic acid copolymer having an average particle diameter of 1100 ((methacrylic acid content 18% by weight) in the same manner as in Preparation Example 3, except that 82 parts by weight of ethyl acrylate and 18 parts by weight of methacrylic acid were added. Was obtained.

Manufacturing example  5

Ethyl acrylate-methacrylic acid copolymer having an average particle diameter of 1500 Å (methacrylic acid content 12% by weight) in the same manner as in Preparation Example 3, except that 88 parts by weight of ethyl acrylate and 12 parts by weight of methacrylic acid were added. Was obtained.

Manufacturing example  6

A core was prepared as in Preparation Example 1, and a shell was formed in the following manner in the presence of the core. In preparing the shell, first, a mixture containing 40 parts by weight of ethyl acrylate and 0.5 part by weight of dioctyl sulfosuccinate is continuously added and 0.08 parts by weight of potassium persulfate is continuously added for 90 minutes to polymerize, followed by ethyl acrylate. 9.1 parts by weight, 0.9 parts by weight of methacrylic acid, and 0.02 parts by weight of potassium persulfate were continuously reacted for 1 hour. Finally, an ethyl acrylate-methacrylic acid copolymer having an average particle diameter of 1100 mm 3 (methacrylic acid content in this copolymer was 0.9% by weight) was obtained.

[Examples and Comparative Examples]

In the following examples and comparative examples, the weight parts of each component are based on 100 parts by weight of butadiene rubber latex (based on solid content).

Example  One

100 parts by weight of butadiene rubber latex having an average particle diameter of 1000 MPa in the reactor (based on solid content), 5 parts by weight of styrene, and 1.5 parts by weight of acrylonitrile (based on total 100% by weight of styrene and acrylonitrile grafted to rubber) The amount corresponding to%) was pre-injected, and 4 parts by weight of the ethyl acrylate-methacrylic acid copolymer of Preparation Example 1 was added, followed by stirring for 30 minutes to partially enlarge the butadiene rubber. Subsequently, 44 parts by weight of styrene, 14.5 parts by weight of acrylonitrile, and 0.15 parts by weight of cumene hydroperoxide were continuously or dividedly added to perform graft polymerization.

After the graft polymerization was completed, the obtained ABS graft copolymer latex was agglomerated with magnesium sulfate (MgSO ₄ ), and then ABS graft copolymer powder was obtained including washing, dehydrating and drying steps.

23% by weight of the powder obtained as described above and 77% by weight of a styrene-acrylonitrile copolymer (acrylonitrile content in this copolymer) was mixed and pelletized using an extruder, and then injected into it to physical properties Measurement specimens were prepared.

Example  2 to 3

Grafting in the same conditions and methods as in Example 1, except that the type and content of the ethyl acrylate-methacrylic acid copolymer and the ratio of styrene and acrylonitrile to be pre-injected were changed as shown in Table 1 below. Polymerization was carried out to obtain ABS graft copolymer powder.

23% by weight of the powder obtained as described above and 77% by weight of a styrene-acrylonitrile copolymer (acrylonitrile content of 27% by weight) were mixed and pelletized using an extruder, thereby extruding the sample for measuring physical properties. It was produced.

Comparative example  1 to 6

Grafting in the same conditions and methods as in Example 1, except that the type and content of the ethyl acrylate-methacrylic acid copolymer and the ratio of styrene and acrylonitrile to be pre-injected were changed as shown in Table 2 below. Polymerization was carried out to obtain ABS graft copolymer powder.

23% by weight of the powder obtained as described above and 77% by weight of a styrene-acrylonitrile copolymer (acrylonitrile content of 27% by weight) were mixed and pelleted using an extruder, thereby extruding the sample for measuring physical properties. It was produced.

Comparative example  7

When the styrene and acrylonitrile were pre-injected in Example 1, 0.02 parts by weight of cumene hydroperoxide as an initiator was added together, and the same procedure as in Example 1 was performed, except that graft polymerization was initiated.

[Test Example]

The physical properties of the injection molded products prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 to 2 and FIGS. 2 to 3 below.

Table 1 shows the measurement results of the properties of Examples 1 to 3, Table 2 shows the measurement results of the properties of Comparative Examples 1 to 7, and FIG. 2 shows the particle size distribution of the rubber polymers prepared according to an embodiment of the present invention. 3 is a particle size distribution curve of a rubber polymer prepared according to a comparative example.

* Flow index (Melt Index, MI): measured in accordance with ASTM D1238 under the conditions of 220 ℃, load 10kg.

* Notched Izod Impact Strength: Izod impact strength was measured by notching the specimen according to ASTM D256. The thickness of the measurement specimen was 6.4 mm (1/4 inch).

* Average particle size and particle size distribution of rubber: After the prepared ABS graft copolymer latex was diluted with distilled water, it was measured using a Nicomp 380HPL equipment.

* Coagulant content: The weight of the coagulum produced in the reaction tank, the weight of the rubber (solid content) and the monomer added to the reaction were measured, and the content of the coagulum was calculated using Equation 1 below.

 [Equation 1]

Coagulant content [ppm] = weight of coagulum produced inside the reactor / (total rubber weight + monomer weight)

division Example 1 Example 2 Example 3 Pre-injection monomer ratio [% by weight] 10 8 16 Type of acid-containing copolymer (MA * content) Preparation Example 1 (1.5% by weight) Preparation Example 2
(3% by weight) Preparation Example 3
(6% by weight) Acid group-containing copolymer input
[Parts by weight] 4 3 1.5 Average particle diameter of rubber [Å] 3200 3300 3400 Rubber particle size distribution Bimodal Bimodal Bimodal Flow index [g / 10min] 20 20.3 21.3 Impact strength [kg · cm / cm] 22.5 25.0 26.5 Coagulant content [ppm] <100 200 500

* : Methacrylic acid

division Comparative example One 2 3 4 5 6 7 Pre-injection monomer ratio [% by weight] 0 15 25 16 8 8 10 ** Type of acid-containing copolymer (MA * content) Preparation Example 2
(3% by weight) Preparation Example 4
(18% by weight) Preparation Example 5
(12% by weight) Preparation Example 3
(6% by weight) Preparation Example 2
(3% by weight) Preparation Example 6
(0.9% by weight) Preparation Example 1
(1.5% by weight) Acid group-containing copolymer input [parts by weight] 3 One One 0.4 5.5 3 4 Average particle size of rubber
[Å] 3200 3300 2960 2200 4000 2850 3200 Rubber particle size distribution Bimodal Non-uniformity *** Bimodal *** *** Non-uniformity Flow index [g / 10min] 16.5 18 16 17 Impact strength
[kg · cm / cm] 26.0 26.5 15 23 Coagulant content [ppm] 4000 4000 <100 3000

* : Methacrylic acid ** : When the monomer is pre-injected, polymerization is initiated by adding an initiator together

*** : Coagulated during graft polymerization, and specimens for measuring properties are not produced

Referring to Table 1 above, it was confirmed that the specimens of Examples 1 to 3 according to the present invention were prepared with a rubber polymer having a desired size and had a bimodal distribution. Furthermore, the specimens of Examples 1 to 3 according to the present invention have significantly less coagulant content of 500 ppm or less, thereby contributing to productivity improvement of the ABS-based copolymer resin, and have excellent flow index and impact strength, thereby improving workability and product quality. It was confirmed that it can also contribute.

Next, referring to Table 2, in the case of Comparative Example 2, which was performed under the same conditions as Example 2, except that some monomers were not pre-injected, the object of the present invention is to determine the average particle size, particle size distribution, and impact strength of the final specimen. Although it was achieved, it can be seen that the coagulant content is increased by a factor of 20 to significantly lower the productivity.

In addition, even if some monomers are pre-injected and the acid group-containing copolymer is included within the scope of the present invention, in Comparative Example 2 in which the proportion of acid group-containing monomers in the acid group-containing copolymer is outside the scope of the present invention, the particle size distribution of the rubber polymer is It was confirmed that the non-uniformity and the coagulant content increased by at least 20 times compared to the examples, resulting in low productivity.

In addition, in the case of Comparative Example 3 in which the ratio of the monomer to be pre-injected and the ratio of the acid group-containing monomer in the acid group-containing copolymer is outside the scope of the present invention, excessive coagulation is formed during graft polymerization, and latex stability is considerably unstable. Measurement specimens could not be prepared. From this, the comparative example 3 is predicted to have a very low productivity at a level that cannot be industrially used.

In addition, except for applying a small amount of the acid group-containing copolymer, Comparative Example 4 carried out under the same conditions as in Example 3 finally has a bimodal particle size distribution, but the average particle size of the rubber is small, so it can be confirmed that the impact strength is significantly reduced. have.

In addition, in the case of Comparative Example 5, which was carried out under the same conditions as in Example 2, except that an excess of an acid group-containing copolymer was applied, an excessive amount of coagulation occurred during graft polymerization, so that a specimen for measuring physical properties could not be produced, and productivity was significantly I could confirm that it was falling.

In addition, in the case of Comparative Example 6 using an acid group-containing copolymer having a significantly low acid group-containing monomer ratio, as in Comparative Examples 3 and 5, it was confirmed that excessive coagulation was generated during graft polymerization, resulting in a significant drop in latex stability and productivity. .

In addition, the same procedure as in Example 1 of the present application, in the case of initiating the graft polymerization at the initial stage of the reaction by injecting the initiator together in the monomer pre-injection step, the particle size distribution of the rubber polymer is non-uniform, the content of coagulation is at least 30 times It was confirmed that the amount was significantly increased compared to the examples in terms of latex stability and productivity.

On the other hand, referring to Figure 2, it can be seen that the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer prepared according to an embodiment of the present invention has a bimodal particle size distribution. Specifically, it can be confirmed that the copolymer prepared according to the embodiment of the present invention includes a polymer having a particle size of about 1000 mm 2 and a polymer having a particle size of about 3300 mm 2 or less by being partially enlarged.

Particularly, looking at the particle size distribution curve of FIG. 2, it can be confirmed that the particle size has a discontinuous distribution in the vicinity of about 2000Å, and it is clear that the butadiene rubber having an average particle size of 1000Å injected in the reaction is partially enlarged to have a bimodal particle size distribution. Can be confirmed.

However, referring to FIG. 3, which is a particle size distribution curve of Comparative Example 2 not according to the present invention, it can be confirmed that it has a continuous particle size distribution within a wide range of approximately 1300 mm 2 to 6500 mm 2, which partially enlarged. Rather, it is clearly distinguished from the particle size distribution curve of FIG. 2 having a bimodal particle size distribution as including an unevenly enlarged rubber as a whole.

Claims (11)

A first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having a particle diameter of 800 to 1500 mm 2; And
Containing; a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 3,
The second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer includes an acid group-containing copolymer,
The acid group-containing copolymer comprises 1 to 8% by weight of an acid group-containing monomer based on 100% by weight of the copolymer,
The acid group-containing copolymer is included in 0.5 to 5 parts by weight based on 100 parts by weight of the conjugated diene rubber,
Characterized in that the coagulum content is 500 ppm or less (based on the total weight of the conjugated diene rubber, aromatic vinyl compound, and vinyl cyan compound)
In-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer. According to claim 1,
The conjugated diene rubber having a particle diameter of 3000 to 5000 mm 3 is characterized by being a non-conjugated conjugated diene rubber containing the acid group-containing copolymer.
In-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer. A first step of pre-injecting 5 to 20% by weight of 100% by weight of the total vinyl cyan compound and aromatic vinyl compound used in 100 parts by weight of the conjugated diene rubber latex having an average particle diameter of 800 to 1500 mm 3 (based on solid content);
A second step in which 0.5 to 5 parts by weight of an acid group-containing copolymer is added to the mixture of the first step to partially enlarge a portion of the conjugated diene rubber having an average particle diameter of 800 to 1500 mm 3 with a conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2; And
In the in-situ bimodal rubber polymer comprising partially conjugated diene rubber having a particle diameter of 800 to 1500 mm 3 and conjugated diene rubber having a particle diameter of 3000 to 5000 mm 2 in the second step, a residual amount of vinyl cyan compound and aromatic vinyl compound; And an initiator; a third step of injecting and graft polymerization;
The acid group-containing copolymer is characterized in that it comprises an acid group-containing monomer of 1 to 8% by weight based on 100% by weight of the copolymer
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
The acid group-containing copolymer is characterized in that the average particle diameter of 800 to 1500 Å
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
The acid group-containing monomer is acrylic acid (acrylic acid), methacrylic acid (methacrylic acid), itaconic acid (itaconic acid), itaconic acid anhydride (itaconic anhydride), crotonic acid (crotonic acid), crotonic anhydride, fumaric acid (fumaric acid), maleic acid (maleic acid), maleic anhydride (maleic anhydride), citraconic acid (citraconic acid) and citraconic anhydride (citraconic anhydride) is at least one compound selected from the group consisting of
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
In each of the first and third steps, the vinyl cyan compound and the aromatic vinyl compound are mixed in a weight ratio of 10:90 to 40:60.
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
In the third step, further comprising an emulsifier, characterized in that the emulsion graft polymerization
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
The acid group-containing copolymer is characterized in that the polymerization comprises 1 to 8% by weight of the acid group-containing monomer and 92 to 99% by weight of the (meth) acrylic acid alkyl ester compound
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
After the third step, the graft copolymer latex is agglomerated and dried to obtain an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer in powder form.
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. According to claim 3,
The graft copolymer latex obtained in the third step is characterized in that the coagulum content is less than 500ppm
In-situ bimodal vinyl cyan compound-conjugated diene rubber-producing method of aromatic vinyl compound copolymer. 20 to 80% by weight of an in-situ bimodal vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer prepared according to any one of claims 3 to 10 and an aromatic vinyl compound-vinyl cyan compound copolymer 20 to After preparing a mixture containing 80% by weight, melt-kneading the mixture; And extruding;
Method for manufacturing a thermoplastic resin composition.

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