KR20220054176A - Method for preparing vinylcyan compound-conjugated dien rubber-aromatic vinyl compound graft copolymer and method for preparing thermoplastic resin composition containing the same - Google Patents

Abstract

The present disclosure relates to a method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and a method for preparing a thermoplastic resin composition including the same, and more specifically, to a method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer by preparing a bimodal conjugated diene rubber by adding a conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å to an enlarged conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å with a polymer coagulant, and carrying out graft-polymerization including the same, and a method for preparing a thermoplastic resin composition including the same. According to the present invention, the time for preparing an enlarged conjugated diene rubber is shortened and graft efficiency is increased, thereby having a synergistic effect of improving both impact resistance and fluidity.

Description

Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and method for producing a thermoplastic resin composition comprising the same COMPOSITION CONTAINING THE SAME}

The present invention relates to a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and a method for producing a thermoplastic resin composition comprising the same, and more particularly, to a conjugated diene rubber latex and a polymer coagulant Vinyl cyanide compound-conjugated diene rubber having a synergistic effect with improved both impact resistance and fluidity by shortening the production time of hypertrophic conjugated diene rubber and increasing grafting efficiency by producing bimodal conjugated diene rubber containing hypertrophic conjugated diene rubber latex - It relates to a method for producing an aromatic vinyl compound graft copolymer and a method for producing a thermoplastic resin composition comprising the same.

Conjugated diene rubber polymers represented by polybutadiene are acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') resin and methyl methacrylate-butadiene-styrene (hereinafter referred to as 'MBS') resin due to their excellent rubber properties. It is widely used as an impact modifier for various thermoplastic resins.

In order to secure the impact resistance of the ABS resin, the average particle diameter of polybutadiene latex (hereinafter referred to as 'PBL') should be 3000 to 3600 Å. However, in order to obtain such a large diameter rubber, polymerization time is usually Since it takes more than 30 hours, the production efficiency is low, and when the polymerization conversion rate is 90% or more, the polymerization conversion rate is rapidly decreased, so that even if more time is consumed, the polymerization conversion rate is not significantly improved.

In order to solve this problem, polymerization was carried out by increasing the reaction temperature and reducing the reaction time, but there is a disadvantage that the particle size is small and the reaction solids are increased, and the reaction pressure is increased due to excessive heat of reaction, which is a risk factor to the safety of the on-site process. It is not commercially easy to obtain high conversion rate and large diameter PBL in a short reaction time.

In addition, in order to shorten the reaction time, there is a method of polymerizing small-diameter PBL in a short time and then adding acid or salt to make large-diameter PBL through an enlargement process. There is a limit in manufacturing the above large-diameter PBL.

Therefore, there is a need to develop a manufacturing method capable of securing impact resistance and fluidity while safely manufacturing large-diameter conjugated diene rubber latex with an average particle diameter of 4,000 Å or more within a short time.

Korean Patent No. 384375

In order to solve the problems of the prior art as described above, the present substrate prepares a bimodal conjugated diene rubber comprising a conjugated diene rubber latex and an enlarged conjugated diene rubber latex that is enlarged with a polymer coagulant, thereby shortening polymerization time and process safety An object of the present invention is to provide a method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer excellent in both impact resistance and fluidity.

In addition, an object of the present disclosure is to provide a method for manufacturing a thermoplastic resin composition having excellent impact resistance and fluidity, including the graft copolymer according to the above manufacturing method.

In addition, the present substrate includes a bimodal conjugated diene rubber, a graft copolymer including an aromatic vinyl compound and a vinyl cyan compound, and an aromatic vinyl compound-vinyl cyan compound copolymer, and the bimodal conjugated diene rubber has a total weight thereof 85 to 97% by weight of a conjugated diene rubber having an average particle diameter of 2,400 to 2,800 Å, 1 to 14% by weight of a conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å, and 0.1 to 2% by weight of a polymer coagulant, according to ASTM D256 An object of the present invention is to provide a thermoplastic resin composition, characterized in that the Izod impact strength measured with a specimen thickness of 1/4" is 32 kgf·cm/cm or more.

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

In order to achieve the above object, the present a) preparing a large-diameter conjugated diene rubber latex step having an average particle diameter of 5,800 to 8,500 Å by adding a polymer coagulant to medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å; b) preparing a bimodal conjugated diene rubber latex by adding a medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å to the prepared large-diameter conjugated diene rubber latex; c) including the prepared bimodal conjugated diene rubber latex, aromatic vinyl compound, and vinyl cyan compound by graft polymerization to obtain a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer; It provides a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, characterized in that.

In addition, the present substrate comprises the steps of preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the manufacturing method; 15 to 40 wt% of the prepared graft copolymer and 60 to 85 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded, and then extruded; Thermoplastic resin composition comprising a It provides a manufacturing method of

In addition, the present substrate contains 15 to 40 wt% of a graft copolymer comprising a bimodal conjugated diene rubber, an aromatic vinyl compound and a vinyl cyan compound and 60 to 85 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, The bimodal conjugated diene rubber is 85 to 97% by weight of a medium-diameter conjugated diene rubber having an average particle diameter of 2,400 to 2,800 Å, 1 to 14% by weight of a large-diameter conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å, and a polymer coagulant 0.1, based on the total weight thereof to 2% by weight, and provides a thermoplastic resin composition, characterized in that the Izod impact strength measured with a specimen thickness of 1/4″ according to ASTM D256 is 32 kgf·cm/cm or more.

According to the present disclosure, the production time of large-diameter conjugated diene rubber latex having an average particle diameter of 5,800 to 8,500 Å is shortened by thickening the conjugated diene rubber latex with a polymer coagulant, and bimodal conjugated diene rubber latex mixed with non-enlarged conjugated diene rubber The graft-polymerized vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer including

1 is a photograph taken by TEM of a large-diameter rubbery polymer enlarged with a polymer coagulant according to Preparation C1 of the present invention (magnification: 25k)
2 is a photograph taken by TEM of a large-diameter rubber polymer polymerized by direct polymerization according to Preparation C6 of the present invention (magnification: 25k)
3 is a photograph taken by TEM of a large-diameter rubbery polymer enlarged with acetic acid according to Preparation C7 of the present invention (magnification: 25k)

The present inventors shortened the manufacturing time of large-diameter conjugated diene rubber latex having an average particle diameter of 5,800 to 8,500 Å required to improve the impact resistance of the ABS graft copolymer and to improve impact resistance and fluidity As a result, conjugated diene rubber latex was produced When an enlarged conjugated diene rubber latex that is enlarged with a polymer coagulant is prepared and it is added to the non-enlarged conjugated diene rubber latex in a predetermined amount to produce a bimodal conjugated diene rubber latex, the effect of greatly improving the impact strength while providing excellent fluidity was confirmed, and based on this, further intensive research was completed to complete the present invention.

The manufacturing method of the graft copolymer and the manufacturing method of the thermoplastic resin composition according to the present disclosure will be described in detail separately as follows.

Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer manufacturing method

The method for producing the vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present disclosure is a) a medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å, by adding a polymer coagulant to enlarge it to increase the average particle diameter from 5,800 to Preparing a large-diameter conjugated diene rubber latex step of 8,500 Å; b) preparing a bimodal conjugated diene rubber latex by adding a medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å to the prepared large-diameter conjugated diene rubber latex; c) The prepared bimodal conjugated diene rubber latex 40 to 70% by weight (based on solid content), 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound by graft polymerization reaction to the vinyl cyan compound- Conjugated diene rubber - obtaining an aromatic vinyl compound graft copolymer; characterized in that it comprises. In this case, large-diameter conjugated diene rubber latex can be produced in a short time, and the graft copolymer including this has excellent grafting efficiency and has a synergistic effect with improved impact resistance and fluidity.

a) non-dialog phase

Step a) is a step of preparing a large-diameter conjugated diene rubber latex having an average particle diameter of 5,800 to 8,500 Å by adding a polymer coagulant to medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å, for example, to enlarge it.

Step a) is, for example, 0.3 to 1.6 parts by weight (based on solids) of the polymer flocculant, preferably 0.4 to 1.5 parts by weight (based on solids), more preferably based on 100 parts by weight (based on solids) of medium-diameter conjugated diene rubber latex is 0.5 to 1 part by weight (based on solids), most preferably 0.5 to 0.8 parts by weight (based on solids) may be a step of thickening, and the hypertrophic rubber latex can be prepared within a short time within this range and coagulated There is an advantage that water production is reduced.

in this article The average particle diameter may specifically be a weight average particle diameter, and may be measured using a dynamic light scattering method, and the average particle diameter is specifically measured using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). It can be measured as an intensity value in a Gaussian mode. At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50wt%) 1,000 to 5,000 times with deionized or distilled water, that is, diluting it appropriately so as not to significantly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and prepare and measure The method is auto-dilution and measured with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting value is temperature 23℃, measuring wavelength 632.8nm, channel width It can measure as 10 microseconds.

The medium-diameter conjugated diene rubber latex may preferably have an average particle diameter of 2,500 to 2,700 Å, and within this range, it can be efficiently enlarged with a large-diameter conjugated diene rubber latex within a short time, so there is an advantage in excellent productivity.

The large-diameter conjugated diene rubber latex may preferably have an average particle diameter of 6,000 to 8,200 Å, more preferably 6,100 to 8,000 Å, even more preferably 6,100 to 7,500 Å, and both impact resistance and fluidity within this range It has an excellent effect.

The polymer coagulant may have, for example, an average particle diameter of 700 to 1,700 Å, preferably 900 to 1,600 Å, more preferably 1,000 to 1,500 Å, more preferably 1,100 to 1,400 Å, and conjugated diene rubber within this range. It has the effect of uniformly thickening the latex.

The polymer coagulant may be, for example, a graft copolymer obtained by graft polymerization of an alkyl acrylate compound and a carboxylic acid compound to a polymerized core including at least one selected from the group consisting of an alkyl acrylate compound and a carboxylic acid compound, Preferably, it may be a graft copolymer obtained by graft polymerization of an alkyl acrylate compound and a carboxylic acid-based compound to a core polymerized with an alkyl acrylate compound. there is.

The polymer coagulant may be, for example, in the form of latex, and in this case, the conjugated diene rubber latex can be uniformly enlarged, and the coagulation product is reduced.

The method for preparing the polymer coagulant may include, for example, adding 35 to 45 parts by weight of an alkyl acrylate compound, 0 to 10 parts by weight of a carboxylic acid-based compound, an emulsifier and an initiator, and performing primary polymerization; After the first polymerization step, when the polymerization conversion rate is 85 to 93%, 40 to 60 parts by weight of an alkyl acrylate compound, 5 to 15 parts by weight of a carboxylic acid-based compound, and an initiator are added, followed by secondary graft polymerization; After the second graft polymerization step, the step of terminating the polymerization at a polymerization conversion rate of 95 to 99%; may include; in this case, there is an effect in that the hypertrophy effect is excellent and the coagulant content is reduced.

Preferably, the method for preparing the polymer coagulant comprises: adding 37 to 43 parts by weight of an alkyl acrylate compound, 0 to 5 parts by weight of a carboxylic acid-based compound, an emulsifier and an initiator, and performing primary polymerization; After the first polymerization step, 45 to 55 parts by weight of an alkyl acrylate compound, 7 to 12 parts by weight of a carboxylic acid-based compound, and an initiator are added at a polymerization conversion rate of 85 to 93%, followed by secondary graft polymerization; After the second graft polymerization step, the step of terminating the polymerization at a polymerization conversion rate of 95 to 99%; may include; in this case, there is an effect in that the hypertrophy effect is excellent and the coagulant content is reduced.

As a specific example, the method for preparing the polymer flocculant includes adding 130 to 200 parts by weight of ion-exchanged water and 0.1 to 1 parts by weight of an emulsifier to a nitrogen-substituted polymerization reactor, and stirring while raising the internal temperature of the polymerization reactor to 65 to 75° C. Next, adding 0.01 to 0.5 parts by weight of an initiator, 35 to 45 parts by weight of an alkyl acrylate compound, and 0 to 10 parts by weight of a carboxylic acid-based compound and performing primary polymerization; After the first polymerization step, when the polymerization conversion rate is 85 to 93% (based on the batch monomer conversion rate), 40 to 60 parts by weight of the alkyl acrylate compound, 5 to 15 parts by weight of the carboxylic acid-based compound, and 1 to 5 parts by weight of the initiator are continuous at a constant rate. input and secondary graft polymerization; After the second graft polymerization step, the step of terminating the polymerization at a polymerization conversion rate of 95 to 99%; may include; in this case, there is an effect in that the hypertrophy effect is excellent and the coagulant content is reduced.

The alkyl acrylate compound of the present disclosure is, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylic It may be at least one member selected from the group consisting of acrylate, n-pentyl acrylate and lauryl acrylate, and preferably at least one member selected from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate, in this case It has the advantage of excellent latex stability and thickening effect, and improved fluidity and impact resistance.

The carboxylic acid-based compound of the present disclosure may be, for example, at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumiric acid, and maleic acid, preferably methacrylic acid, in this case It has an excellent thickening effect and has the effect of reducing the coagulant content.

In the present description, the emulsifier is, for example, from the group consisting of alkyl sulfosuccinate metal salts and derivatives thereof having 12 to 18 carbon atoms, alkyl sulfate esters and derivatives thereof having 12 to 20 carbon atoms, and alkyl sulfonic acid metal salts having 12 to 20 carbon atoms and derivatives thereof. It may be one or more selected.

The metal salt of alkyl sulfosuccinate having 12 to 18 carbon atoms or a derivative thereof is, for example, dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethyl hexyl sulfosuccinate sodium salt, di-2- It may be at least one selected from the group consisting of ethyl hexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt and dioctyl sulfosuccinate potassium salt.

The alkyl sulfuric acid ester or derivative thereof having 12 to 20 carbon atoms, an alkyl sulfonic acid metal salt having 12 to 20 carbon atoms or a derivative thereof is, for example, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium It may be at least one selected from the group consisting of oleic sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate.

In the present description, the initiator is, for example, sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t -Butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobuty It may be at least one selected from the group consisting of ronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) methyl, preferably potassium persulfate; t-butyl hydroperoxide or a mixture thereof.

In the present description, the polymerization conversion rate can be measured by a measurement method commonly used in the technical field to which the present invention belongs, and as a specific example, the amount of the monomer converted into a polymer until measured based on 100% of the total weight of the monomers input until the end of polymerization It can be defined as weight %, and the method for measuring the polymerization conversion is not particularly limited if it is a method for measuring the polymerization conversion measured according to this definition, and as a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150° C. for 15 minutes. Then, by measuring the weight, the total solid content (TSC) can be obtained using Equation 1 below, and it can be calculated using Equation 2 below. Equation 2 is based on the total weight of the added monomer being 100 parts by weight.

[Equation 1]

[Equation 2]

Polymerization conversion (%) = [Total solid content (TSC) * (Total weight of the added monomer, ion-exchanged water, and auxiliary materials) / 100] - (The weight of the added additives other than the monomer and ion-exchanged water)

In Equation 2, the auxiliary material refers to an initiator, an emulsifier, an electrolyte, and a molecular weight regulator.

The input monomer refers to an alkyl acrylate compound and a carboxylic acid-based compound in the case of the polymer coagulant, and refers to a conjugated diene compound in the case of conjugated diene rubber latex polymerization, vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft air In the case of copolymer latex polymerization, it refers to a conjugated diene compound, a vinyl cyan compound, and an aromatic vinyl compound.

In step a), the medium-diameter conjugated diene rubber latex is stirred at 200 to 300 rpm, for example, while the polymer coagulant is continuously added at a constant speed for 5 to 20 minutes, and then aged for 10 to 30 minutes, preferably 220 While stirring at 270 rpm, the polymer coagulant may be continuously input at a constant speed for 7 to 17 minutes, and then aged for 15 to 25 minutes, and uniformly enlarged within this range to reduce coagulant formation.

Step a) may include stabilizing the large-diameter conjugated diene rubber latex by injecting an adsorption type emulsifier as an example, and in this case, latex stability is excellent and coagulation is reduced.

In step a), the adsorption type emulsifier may be added, for example, in an amount of 0.05 to 0.7 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight (based on solid content) of the large-diameter conjugated diene rubber latex, and latex stability within this range This is excellent and has the effect of reducing the formation of clots.

The adsorption type emulsifier may be, for example, at least one selected from among alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, oleic acid soaps, and rosin acid alkali salts, preferably rosin acid alkali salts. In this case, the latex stability is excellent and the coagulation is reduced.

The medium-diameter conjugated diene rubber latex may include, for example, adding an emulsifier, an electrolyte, a molecular weight regulator and an initiator to 60 to 80 parts by weight of 100 parts by weight of the conjugated diene compound and performing primary polymerization; After the first polymerization step, 20 to 40 parts by weight of the conjugated diene compound is added at a time when the polymerization conversion rate is 30 to 40% and secondary polymerization is performed; adding an initiator and a molecular weight regulator at a time when the polymerization conversion rate is 55 to 65% after the second polymerization step and performing a third polymerization; adding an initiator at a polymerization conversion rate of 75 to 85% after the third polymerization step and performing a fourth polymerization; and terminating the polymerization at a polymerization conversion rate of 93 to 99% after the fourth polymerization step; in this case, it is stably enlarged within a short time by a polymer coagulant, and is enlarged together with the conjugated diene rubber latex By forming a bimodal conjugated diene rubber latex, impact resistance and fluidity are improved.

As a specific example, the medium-diameter conjugated diene rubber latex is used in 60 to 80 parts by weight of 100 parts by weight of the conjugated diene compound in the polymerization reactor, 50 to 100 parts by weight of ion-exchanged water, 0.1 to 5 parts by weight of an adsorption type emulsifier, 0.1 to 3 parts by weight of an electrolyte , 0.1 to 1 parts by weight of a molecular weight modifier and 0.1 to 3 parts by weight of an initiator, and primary polymerization at 70 to 80 ℃; After the first polymerization step, at a time when the polymerization conversion rate is 30 to 40%, 20 to 40 parts by weight of the conjugated diene compound is continuously added for 3 to 7 hours, followed by secondary polymerization; After the second polymerization step, at a time when the polymerization conversion rate is 55 to 65%, 0.01 to 2 parts by weight of an initiator and 0.01 to 1 parts by weight of a molecular weight regulator are batched in, and the temperature is raised by 4 to 10° C. to perform a third polymerization; After the third polymerization step, at a polymerization conversion rate of 75 to 85%, adding 0.01 to 3 parts by weight of a redox initiator and performing a fourth polymerization; and terminating the polymerization at a polymerization conversion rate of 93 to 99% after the fourth polymerization step; in this case, it is stably enlarged within a short time by a polymer coagulant, and is enlarged together with the conjugated diene rubber latex By forming a bimodal conjugated diene rubber latex, impact resistance and fluidity are improved.

The polymerization time of the medium-diameter conjugated diene rubber latex may be, for example, 15 to 20 hours, preferably 16 to 18 hours, and in this case, there is an effect of preparing a latex having a uniform particle size.

The emulsifier used in preparing the medium-diameter conjugated diene rubber latex may be, for example, at least one selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt. , In this case, it is possible to prepare a rubber latex having excellent stability of the polymerization reaction and having a desired particle size.

The electrolyte used in preparing the medium-diameter conjugated diene rubber latex is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , K ₂ SO ₄ , NaHSO ₃ , K ₂ P ₂ O ₇ , Na ₂ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ and K ₂ HPO ₄ may be at least one selected from the group consisting of, in this case, the stability of the latex is excellent.

The molecular weight modifier used in preparing the medium-diameter conjugated diene rubber latex may be, for example, at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and carbon tetrachloride, preferably is t-dodecyl mercaptan.

The initiator used in the preparation of the medium-diameter conjugated diene rubber latex is, for example, cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, benzoyl peroxide fat-soluble persulfates such as oxides; peroxy monomers; And redox initiator; may be at least one selected from the group consisting of, in this case, emulsion polymerization can be performed efficiently.

b) preparing a bimodal conjugated diene rubber latex

Step b) is a step of preparing a bimodal conjugated diene rubber latex by adding the medium-diameter conjugated diene rubber latex to the prepared large-diameter conjugated diene rubber latex.

In the present description, the bimodal conjugated diene rubber latex refers to a conjugated diene rubber latex in which two or more types of conjugated diene rubber latex having different average particle diameters are mixed. It is a mixture, and in this case, when the particle size distribution is measured, it can be displayed as a graph of a bimodal shape.

Preferably, step b) comprises 85 to 96 wt% (based on solids) of the medium-diameter conjugated diene rubber latex to 4 to 15 wt% (based on solid content) of the large-diameter conjugated diene rubber latex, More preferably, the large-diameter conjugated diene rubber latex 6 Bimodal conjugated diene rubber latex can be prepared by adding 87 to 94% by weight (based on solids) of the medium-diameter conjugated diene rubber latex to 13% by weight (based on solids), and in this case, grafting efficiency is excellent It has excellent impact properties and fluidity.

In step b), the bimodal conjugated diene rubber latex may have, for example, an average particle diameter of 3,000 to 3,800 Å, preferably 3,100 to 3,700 Å, more preferably 3,200 to 3,600 Å, more preferably 3,200 to 3,500 Å, Due to the presence of the large-diameter conjugated diene rubber latex within this range, the grafting efficiency is excellent and the impact resistance is improved.

c) obtaining a graft copolymer

Step c) is a step of obtaining a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer by graft polymerization including the prepared bimodal conjugated diene rubber latex, aromatic vinyl compound and vinyl cyan compound. can

Preferably, step c) comprises 40 to 70 wt% of the prepared bimodal conjugated diene rubber latex (based on solid content), 15 to 45 wt% of an aromatic vinyl compound, and 5 to 25 wt% of a vinyl cyanide compound. It can be reacted, and more preferably, the prepared bimodal conjugated diene rubber latex comprises 55 to 65 wt% (based on solid content), 25 to 35 wt% of an aromatic vinyl compound, and 7 to 20 wt% of a vinyl cyanide compound. It can be polymerized, more preferably 57 to 62% by weight of the prepared bimodal conjugated diene rubber latex (based on solid content), 27 to 32% by weight of an aromatic vinyl compound, and 7 to 15% by weight of a vinyl cyan compound Graf It can be polymerized, and in this case, the grafting efficiency is excellent, so that both the impact resistance and the fluidity are improved.

In step c), 0.01 to 1 part by weight of an initiator may be added during the graft polymerization reaction, and within the above range, the stability of the polymerization reaction is excellent and the polymerization efficiency is improved.

The initiator may include, for example, oil-soluble persulfates such as cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, and benzoyl peroxide; peroxy monomers; and a redox initiator; may be at least one selected from the group consisting of, and in this case, polymerization may be efficiently performed.

The redox initiator may, for example, be a combination of a catalyst, an oxidizing agent and a reducing agent, the catalyst may be, for example, ferrous sulfate, and the oxidizing agent may be, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroper It may be at least one selected from the group consisting of oxide, benzoyl peroxide, cumene hydropaokiside and p-menthane hydroperoxide, and the reducing agent is, for example, sodium sulfite, acid sodium sulfite, rongalit, dextrose, pyrrole It may be at least one selected from the group consisting of sodium phosphate and ascorbic acid.

The redox initiator may preferably be a mixture of ferrous sulfate, t-butyl hydroperoxide, dextrose and sodium pyrrolate, in which case radicals are generated faster than thermal initiators such as potassium persulfate, thereby speeding up the polymerization reaction is increased to shorten the polymerization time.

The graft copolymer obtained in step c) may be, for example, in the form of a latex and may include a step of agglomeration thereof, and preferably may include the steps of agglomeration, aging, dehydration and drying, and the step of The graft copolymer prepared by including it may be provided in powder form. The coagulation, aging, dehydration and drying steps are not particularly limited if the methods are generally used in the art.

The agglomeration step in the manufacturing method of the graft copolymer may include, for example, an acid coagulant such as sulfuric acid, phosphoric acid, hydrochloric acid, or the like, or a salt coagulant such as magnesium sulfate, aluminum sulfate, calcium chloride, and the like, alone or mixed.

Other reaction conditions, such as reaction time, reaction temperature, pressure, time of input of reactants, etc. in the method for preparing the graft copolymer other than the above-described description, are not particularly limited as long as they are within the range commonly used in the art to which the present invention belongs, and necessary It can be appropriately selected and implemented according to the

In the present description, the conjugated diene compound is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene and piperine. It may be at least one selected from the group consisting of ren.

In the present description, the aromatic vinyl monomer is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ -bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene may be at least one selected from the group consisting of.

In the present description, the vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.

Method for producing a thermoplastic resin composition

The method for producing the thermoplastic resin composition of the present invention comprises the steps of: preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the method; and 15 to 40% by weight of the prepared graft copolymer and 60 to 85% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer in an extruder, melt-kneading, and then extruding; may include, in this case The graft copolymer has excellent effects in both impact resistance and fluidity due to excellent grafting efficiency.

Preferably, the method for preparing the thermoplastic resin composition may include 20 to 35 wt% of the graft copolymer and 65 to 80 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer, and more preferably 25 to 30 wt% of the graft copolymer. Weight % and aromatic vinyl compound-vinyl cyan compound copolymer may be 70 to 75 weight %, and in this case, both impact resistance and fluidity have excellent effects.

The aromatic vinyl compound-vinyl cyan compound copolymer may include, for example, 60 to 95% by weight of an aromatic vinyl compound, preferably 65 to 90% by weight, more preferably 70 to 85% by weight; and 5 to 40% by weight of the vinyl cyanide compound, preferably 10 to 35% by weight, more preferably 15 to 30% by weight; may be a polymerized copolymer.

The melt-kneading may be carried out, for example, at 200 to 280°C, preferably at 220 to 260°C.

The melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader reactor, and the like, and is not particularly limited.

During the melt-kneading, one or more additives selected from the group consisting of colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids may be optionally added as needed.

In the method for producing the thermoplastic resin composition, content overlapping with the step of preparing the above-described graft copolymer was omitted.

Thermoplastic resin composition

The thermoplastic resin composition of the present disclosure contains 15 to 40 wt% of a graft copolymer comprising bimodal conjugated diene rubber, an aromatic vinyl compound and a vinyl cyan compound, and 60 to 85 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer And, the bimodal conjugated diene rubber is 85 to 97% by weight of a conjugated diene rubber having an average particle diameter of 2,400 to 2,800 Å, 1 to 14% by weight of a conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å, and a polymer coagulant 0.1, based on the total weight thereof to 2% by weight, and characterized in that the Izod impact strength measured with a specimen thickness of 1/4" according to ASTM D256 is 32 kgf cm/cm or more. In this case, the effect of excellent fluidity while excellent balance of physical properties there is

Preferably, the bimodal conjugated diene rubber is 88 to 95% by weight of a conjugated diene rubber having an average particle diameter of 2,400 to 2,800 Å, 4 to 11% by weight of a conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å, and a polymer coagulant based on the total weight thereof It may contain 0.2 to 1.5% by weight, and graft efficiency is improved and impact resistance is improved due to the conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å within this range.

The polymer coagulant may have, for example, an average particle diameter of 700 to 1,700 Å, preferably 900 to 1,600 Å, more preferably 1,000 to 1,500 Å, more preferably 1,100 to 1,400 Å, and impact resistance and All of the fluidity has an excellent effect.

The bimodal conjugated diene rubber may have, for example, an average particle diameter of 3,000 to 3,800 Å, preferably 3,100 to 3,700 Å, more preferably 3,200 to 3,600 Å, within this range, the impact resistance is improved.

The graft copolymer may have, for example, a graft rate of 30 to 45%, preferably 30 to 37%, and both have excellent impact resistance and fluidity within this range.

In the present description, the graft rate can be calculated using Equation 3 below after adding a certain amount of the graft copolymer to a solvent, dissolving it using a vibrator, centrifuging with a centrifugal separator, and drying to obtain an insoluble content .

In detail, 2 g of the dry graft copolymer powder was added to 100 ml of acetone and vibrated with a vibrator (product name: SI-600R, manufacturer: Lab. companion) for 24 hours to dissolve the free graft copolymer, followed by a centrifugal separator. After centrifugation at 14,000 rpm for 1 hour, and drying at 140° C. for 2 hours with a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) to obtain an insoluble content, it can be calculated using Equation 3 below.

[Equation 3]

Graft rate (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] * 100

(The weight (g) of the grafted monomer in Equation 3 is the weight obtained by subtracting the rubber weight (g) from the weight of the insoluble material (gel) after dissolving the graft copolymer in acetone and centrifuging, and the rubber weight ( g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

The thermoplastic resin composition preferably has an Izod impact strength of 32 kgf·cm/cm or more, more preferably 33 to 37 kgf·cm/cm, and in this case, it has excellent fluidity while excellent balance of physical properties. .

The thermoplastic resin composition has a flow index of 20 g/10min or more, more preferably 21 g/10min or more, more preferably 21 to 28 g/10min or more, measured under the conditions of 220°C and 10 kg according to ASTM D1238, for example. may be, and it has excellent fluidity within this range and has the advantage of easy molding into various shapes.

Hereinafter, the present invention will be described with reference to the drawings.

1 is a TEM photograph of Preparation Example C1, which is a large-diameter rubbery polymer enlarged with a polymer flocculant according to the present invention.

In addition, the following FIG. 2 is a TEM photograph of Preparation C6, in which a large-diameter rubbery polymer was prepared by direct polymerization, in which soft spherical shapes exist individually and do not aggregate.

In addition, the following FIG. 3 is a TEM photograph of C7 made of large-diameter rubber by being enlarged with acetic acid, in which small spherical particles are aggregated to form large and small lumps, and the rim of the lump is a shape in which small circles are overlapped.

Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

<Preparation Example A: Preparation of polymer flocculant>

160 parts by weight of ion-exchanged water and 0.5 parts by weight of sodium dioctyl sulfosuccinate as an emulsifier were added to a nitrogen-substituted polymerization reactor, and after stirring while raising the internal temperature of the polymerization reactor to 70° C., 0.1 potassium persulfate as an initiator Weight parts and 40 parts by weight of butyl acrylate were added and polymerization was carried out for 90 minutes. At a polymerization conversion rate of 90% (based on batch monomer conversion), 50 parts by weight of butyl acrylate, 10 parts by weight of methacrylic acid, and 3.0 parts by weight of an aqueous solution of potassium persulfate (concentration of 3% by weight) as an initiator (concentration 3% by weight) were continuously introduced at a constant rate while graft polymerization was carried out. , the polymerization was terminated when the polymerization conversion rate was 98%, and the obtained polymer flocculant had a core-shell structure and an average particle diameter of 1,300 Å.

<Preparation Example B1: Medium-diameter conjugated diene rubber latex production>

70 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 70 parts by weight of 1,3-butadiene as a monomer, 1 part by weight of potassium rosin acid as an emulsifier and 0.8 parts by weight of a fatty acid soap, and 1 part by weight of potassium carbonate as an electrolyte Part, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were put together and polymerization was carried out at a reaction temperature of 74°C. Then, when the polymerization conversion was 30 to 40%, 30 parts by weight of the remaining 1,3-butadiene was continuously added for 5 hours. After that, at a polymerization conversion rate of 60%, 0.15 parts by weight of potassium persulfate and 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) were batch-injected, and then the temperature was raised to 80° C. for polymerization. Then, at a polymerization conversion rate of 80%, 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrophosphate, and 0.002 parts by weight of ferrous sulfate were added, and then the polymerization conversion rate was 95%. to prepare a conjugated diene rubber latex having an average particle diameter of 2,700 Å by terminating the reaction. At this time, the polymerization time was 17 hours.

<Preparation Example B2: Medium-diameter conjugated diene rubber latex production>

70 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 70 parts by weight of 1,3-butadiene as a monomer, 1 part by weight of potassium rosin acid as an emulsifier and 0.8 parts by weight of a fatty acid soap, and 0.9 parts by weight of potassium carbonate as an electrolyte Part, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were put together and polymerization was carried out at a reaction temperature of 74°C. Then, when the polymerization conversion was 30 to 40%, 30 parts by weight of the remaining 1,3-butadiene was continuously added for 5 hours. After that, at a polymerization conversion rate of 60%, 0.15 parts by weight of potassium persulfate and 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) were batch-injected, and then the temperature was raised to 80° C. for polymerization. Then, at a polymerization conversion rate of 80%, 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrophosphate, and 0.002 parts by weight of ferrous sulfate were added, and then the polymerization conversion rate was 95%. to prepare a conjugated diene rubber latex having an average particle diameter of 2,600 Å by terminating the reaction. At this time, the polymerization time was 16 hours.

<Preparation Example B3: Medium-diameter conjugated diene rubber latex production>

70 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 70 parts by weight of 1,3-butadiene as a monomer, 1 part by weight of potassium rosin acid salt as an emulsifier and 0.9 parts by weight of a fatty acid soap, and 0.85 parts by weight of potassium carbonate as an electrolyte Part, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were put together and polymerization was carried out at a reaction temperature of 74°C. Then, when the polymerization conversion was 30 to 40%, 30 parts by weight of the remaining 1,3-butadiene was continuously added for 5 hours. After that, at a polymerization conversion rate of 60%, 0.15 parts by weight of potassium persulfate and 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) were batch-injected, and then the temperature was raised to 80° C. for polymerization. Then, at a polymerization conversion rate of 80%, 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrophosphate, and 0.002 parts by weight of ferrous sulfate were added, and then the polymerization conversion rate was 95%. to prepare a conjugated diene rubber latex having an average particle diameter of 2,500 Å by terminating the reaction. At this time, the polymerization time was 15 hours.

<Preparation Example B4: Preparation of small-diameter conjugated diene rubber latex>

130 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 80 parts by weight of 1,3-butadiene as a monomer, 2.5 parts by weight of a fatty acid soap as an emulsifier, 0.3 parts by weight of potassium carbonate as an electrolyte, tertiary dode as a molecular weight regulator 0.3 parts by weight of syl mercaptan (TDDM), 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrophosphate, and 0.002 parts by weight of ferrous sulfate were added together and polymerized at a reaction temperature of 60° C. reacted Then, when the polymerization conversion rate was 40%, 20 parts by weight of the remaining 1,3-butadiene was continuously added for 5 hours. After that, at a polymerization conversion rate of 60%, 0.15 parts by weight of potassium persulfate and 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) were batch-injected, and then the temperature was raised to 80° C. for polymerization. Then, the reaction was terminated when the polymerization conversion rate was 95% to prepare a conjugated diene rubber latex having an average particle diameter of 1,200 Å. At this time, the polymerization time was 13 hours.

<Production Example C1: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2700 Å prepared in Preparation Example B1 at a speed of 250 rpm, 0.5 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) was added for 7 minutes. After continuous input at a constant speed for 30 minutes and thickening while stirring for 30 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize it, and a large diameter rubber latex (C1) having an average particle diameter of 6,100 Å was obtained.

<Production Example C2: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2700 Å prepared in Preparation Example B1 at a speed of 250 rpm, 0.7 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) for 10 minutes After continuous input at a constant speed for 20 minutes and thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize it, and a large-diameter rubber latex (C2) having an average particle diameter of 7,000 Å was obtained.

<Production Example C3: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2700 Å prepared in Preparation Example B1 at a speed of 250 rpm, 0.9 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) for 10 minutes After continuous input at a constant speed for 20 minutes and thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize it, and a large-diameter rubber latex (C3) having an average particle diameter of 7,900 Å was obtained.

<Production Example C4: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2600 Å prepared in Preparation Example B2 at a speed of 250 rpm, 1.2 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) was added for 10 minutes. After continuous input at a constant speed for 20 minutes, and after thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid was added to stabilize it, and a large-diameter rubber latex (C4) having an average particle diameter of 8,000 Å was obtained.

<Production Example C5: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2500 Å prepared in Preparation Example B3 at a speed of 250 rpm, 1.5 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) was added for 10 minutes. After continuous input at a constant speed for 20 minutes and thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize it, and a large-diameter rubber latex (C5) having an average particle diameter of 8,200 Å was obtained.

<Production Example C6: Large-diameter conjugated diene rubber latex production: Direct polymerization >

70 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 70 parts by weight of 1,3-butadiene as a monomer, 1 part by weight of potassium rosin acid as an emulsifier and 0.8 parts by weight of a fatty acid soap, and 1.4 parts by weight of potassium carbonate as an electrolyte Part, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were put in a batch, and polymerization was carried out at a reaction temperature of 74°C. Then, at a polymerization conversion of 30 to 40%, 30 parts by weight of the remaining 1,3-butadiene was continuously added for 5 hours, and at a polymerization conversion of 60%, 0.15 parts by weight of potassium persulfate, 0.1 tertiary dodecyl mercaptan (TDDM) After batching in parts by weight, the temperature was raised to 80° C. for polymerization. Then, at the polymerization conversion rate of 80%, 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrophosphate and 0.002 parts by weight of ferrous sulfate were added, and then, the polymerization conversion rate was 93%. The reaction was terminated in , to prepare a rubbery polymer with an average particle diameter of 3,300 Å. At this time, the polymerization time was 32 hours.

<Production Example C7: Large-diameter conjugated diene rubber latex production - Acetic acid hypertrophy >

100 parts by weight (based on solid content) of the small-diameter rubber latex prepared in Preparation Example B4 with an average particle diameter of 1200 Å was added to another reaction tank, the stirring speed was adjusted to 60 rpm, and then 2.0 parts by weight of a concentration of 5% by weight aqueous acetic acid solution was slowly added for 30 minutes A rubbery polymer (C7) having an average particle diameter of 3,450 Å was prepared through an acid treatment process in which 1.9 parts by weight of a 7 wt% KOH aqueous solution was added while stirring for 30 minutes while stirring and stabilizing.

<Production Example C8: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2700 Å prepared in Preparation Example B1 at a speed of 250 rpm, 0.1 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) was added to 10 After continuous input at a constant rate for minutes, and after thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize it, and a large-diameter rubber latex (C8) having an average particle diameter of 3,000 Å was obtained.

<Production Example C9: Large diameter conjugated diene rubber latex production >

While stirring 100 parts by weight (based on solid content) of the medium-diameter rubber latex prepared in Preparation Example B1 at a speed of 250 rpm, 1.7 parts by weight of the polymer flocculant prepared in Preparation Example A (based on solid content) was continuously added at a constant rate for 10 minutes. After adding and thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize the resulting large-diameter rubber latex (C9) having an average particle diameter of 9,000 Å.

<Preparation Example C10: Enlarged small-diameter conjugated diene rubber latex with a polymer coagulant to produce medium-diameter conjugated diene rubber latex>

0.7 parts by weight of the polymer coagulant prepared in Preparation Example A while stirring 100 parts by weight (based on solid content) of the small-diameter conjugated diene rubber latex having an average particle diameter of 1200 Å prepared in Preparation Example B4 at a speed of 250 rpm (based on solid content) 10 After continuous input at a constant rate for minutes, and after thickening while stirring for 20 minutes, 0.2 parts by weight of potassium rosin acid salt was added to stabilize the mixture, and a medium-diameter rubber latex (C10) having an average particle diameter of 2,800 Å was obtained.

< Preparation C11: Large-diameter Conjugated Diene Rubber Latex Preparation - Acetic Acid Hypertrophy >

100 parts by weight (based on solid content) of medium-diameter rubber latex having an average particle diameter of 2,700 Å prepared in Preparation Example B1 was added to another reaction tank, the stirring speed was adjusted to 60 rpm, and then 2.0 parts by weight of a concentration of 5% by weight aqueous acetic acid solution was slowly added for 30 minutes After stirring while stirring, 1.9 parts by weight of a 7 wt% KOH aqueous solution was added while stirring for 30 minutes to prepare a rubbery polymer (C11) having an average particle diameter of 6100 Å through an acid treatment process for stabilization.

Example 1

< Preparation of graft copolymer >

55 parts by weight (based on solid content) of the medium-diameter rubbery polymer (B1) prepared in Preparation Example B1, 5 parts by weight of the large-diameter rubbery polymer (C1) prepared in Preparation Example C1, 90 parts by weight of polymerized ion-exchanged water, fatty acid salt After adding 1.0 parts by weight of potassium oleic, 7.5 parts by weight of styrene as a monomer, and 2.5 parts by weight of acrylonitrile as a monomer, maintaining the reactor temperature at 50° C., 0.05 parts by weight of cumene hydroperoxide and 0.09 parts by weight of sodium pyrrolate; 0.12 parts by weight of textrose and 0.015 parts by weight of ferrous sulfide were batched in to initiate the reaction. Simultaneously with the start of polymerization, a mixed solution of 22.5 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, and 0.12 parts by weight of cumene hydroperoxide was continuously introduced into the reactor for 2 hours while the temperature was raised to 75°C. After the continuous input, 0.06 parts by weight of cumene hydroperoxide, 0.04 parts by weight of sodium pyrophosphate, 0.06 parts by weight of dextrose and 0.001 parts by weight of ferrous sulfide were added, and the temperature was raised to 80° C. and the reaction was performed at a polymerization conversion rate of 98%. was terminated. After adding 0.1 parts by weight of silicone oil and 0.5 parts by weight of an antioxidant (winstay-L/IR1076=0.8/0.2) emulsion to 100 parts by weight of the reaction-finished latex (based on solid content), an aqueous solution of magnesium sulfate was added to solidify, and then dehydrated , washed and dried to obtain a graft copolymer powder.

<Preparation of thermoplastic resin composition>

에서 펠렛 형태의 수지 조성물을 제조한 뒤, 210℃ 및 550 bar 하에서 사출하여 물성 측정을 위한 시편을 제조하였다27 parts by weight of the prepared graft copolymer powder, 73 parts by weight of SAN resin (92HR of LG Chem), and 1.2 parts by weight of lubricant were put in a mixer and mixed, followed by mixing with an extruder at a temperature of 210

After preparing a resin composition in the form of pellets, it was injected under 210° C. and 550 bar to prepare a specimen for measuring physical properties.

Example 2

Example 1 was carried out in the same manner as in Example 1, except that the large-diameter rubber latex (C1) was changed to that prepared in Preparation Example C2.

Example 3

Example 1 was carried out in the same manner as in Example 1, except that the large-diameter rubber latex (C1) was changed to that prepared in Preparation Example C3.

Example 4

The medium-diameter rubber latex (B1) and the large-diameter rubber latex (C1) in Example 1 were changed to the medium-diameter rubbery polymer (B2) prepared in Preparation Example B2 and the large-diameter rubbery polymer (C4) prepared in Preparation Example C4, respectively. Except that, it was carried out in the same manner as in Example 1.

Example 5

Medium-diameter rubber latex (B1) and large-diameter rubber latex (C1) in Example 1 were changed to medium-diameter rubbery polymer (B3) prepared in Preparation Example B3 and large-diameter rubbery polymer (C5) prepared in Preparation Example C5, respectively Except that, it was carried out in the same manner as in Example 1.

Comparative Example 1

Example 1 was carried out in the same manner as in Example 1, except that the medium-diameter rubber latex (B1) and the large-diameter rubber latex (C1) were changed to those prepared in Preparation Example C6.

Comparative Example 2

Medium-diameter rubber latex (B1) and large-diameter rubber latex (C1) in Example 1 were changed to small-diameter rubber latex (B4) prepared in Preparation Example B4 and large-diameter rubber latex (C7) prepared in Preparation Example C7, respectively Except for the above, it was carried out in the same manner as in Example 1.

Comparative Example 3

Example 1 was carried out in the same manner as in Example 1, except that the large-diameter rubber latex (C1) was changed to that prepared in Preparation Example C8.

Comparative Example 4

Example 1 was carried out in the same manner as in Example 1, except that the large-diameter rubber latex (C1) was changed to the one prepared in Preparation Example C9.

Comparative Example 5

Medium-diameter rubber latex (B1) and large-diameter rubber latex (C1) in Example 1 were changed to small-diameter rubber latex (B4) prepared in Preparation Example B4 and medium-diameter rubber latex (C10) prepared in Preparation Example C10, respectively Except for the above, it was carried out in the same manner as in Example 1.

Comparative Example 6

Example 1 was carried out in the same manner as in Example 1, except that the large-diameter rubber latex (C1) was changed to the large-diameter rubber latex (C11) prepared in Preparation Example C11.

[Test Example]

The properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Tables 1 and 2 below.

How to measure

* Measurement of average particle diameter (Å): The average particle diameter of each of the small-diameter rubbery polymer, medium-diameter rubbery polymer, large-diameter rubbery polymer and bimodal rubbery polymer was measured with a particle size analyzer (NICOMP 380 HPL).

* Graft rate (%): 2 g of the graft copolymer powder was added to 100 ml of acetone and vibrated with a vibrator (product name: SI-600R, manufacturer: Lab. companion) for 24 hours to dissolve the free graft copolymer and centrifuged After centrifugation at 14,000 rpm with a separator for 1 hour, and drying at 140° C. for 2 hours with a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) to obtain an insoluble content, it was calculated using Equation 3 below.

[Equation 3]

Graft rate (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] * 100

(The weight (g) of the grafted monomer in Equation 3 is the weight obtained by subtracting the rubber weight (g) from the weight of the insoluble material (gel) after dissolving the graft copolymer in acetone and centrifuging, and the rubber weight ( g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

* Izod impact strength (kgf·cm/cm): It was measured according to ASTM D256 with a specimen thickness of 1/4”.

* Flow index (MI; g/10 min): Measured according to ASTM D1238 under the conditions of 220 °C and 10 kg.

division Example 1 Example 2 Example 3 Example 4 Example 5 rubbery
polymer Medium diameter rubbery polymer
polymerization time (HR) 17 17 17 16 15 Medium diameter rubbery polymer
Average particle diameter (Å) 2700
(Preparation Example B1) 2700
(Preparation Example B1) 2700
(Preparation Example B1) 2600
(Production Example B2) 2500
(Production Example B3) polymer flocculant
(parts by weight) 0.5 0.7 0.9 1.2 1.5 Large diameter rubbery polymer average particle diameter (Å) 6100
(Production Example C1) 7000
(Production Example C2) 7900
(Production Example C3) 8000
(Production Example C4) 8200
(Production Example C5) graft copolymer bimodal rubber
Polymer average particle diameter
(Å) 3210 3460 3570 3600 3420 Graft rate (%) 37 32 30 30 36 thermoplastic resin
composition impact strength 33 34 36 32 34 flow index 22 23 20 23 21

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 rubbery
polymer medium caliber rubber
polymer
polymerization time (HR) 32 ^* 13 17 17 13 17 medium caliber rubber
polymer
Average particle diameter (Å) - 1200
(Production Example B4) 2700
(Preparation Example B1) 2700
(Preparation Example B1) 1200
(Production Example B4) 2700
(Preparation Example B1) polymer flocculant
(parts by weight) directly
polymerization acetic acid
agglomeration 0.1 1.7 0.7 acetic acid
agglomeration large diameter rubber
polymer
Average particle diameter (Å) 3300
(Production Example C6) 3450
(Production Example C7) 3000
(Production Example C8) 9000
(Production Example C9) 2800
(Production Example C10) 6100
(Production Example C11) graft copolymer bimodal rubber
polymer
Average particle diameter (Å) 3300 3450 2900 3800 2700 3200 Graft rate (%) 47 29 39 27 49 32 thermoplastic resin
composition impact strength 30 30 29 31 23 28 flow index 18 20 17 20 16 17

In Comparative Example 1, * denotes the time required for polymerization into a large-diameter rubbery polymer.

As shown in Tables 1 and 2, in Examples 1 to 5 containing the bimodal conjugated diene rubber according to the present invention, the time for producing the large-diameter conjugated diene rubber was significantly reduced compared to Comparative Examples 1 to 6, and the graft rate was It was confirmed that both impact strength and fluidity were improved.

Specifically, Comparative Example 1, in which a large-diameter conjugated diene rubber was prepared by direct polymerization, had low production efficiency as it took 32 hours to polymerize, and a small-diameter conjugated diene rubber (Preparation Example B4) having an average particle diameter of 1200 Å was aggregated with acetic acid. In Comparative Example 2, both the graft rate and the impact strength were lowered.

In Comparative Example 3, in which the polymer coagulant was enlarged using 0.1 parts by weight, the average particle diameter of the enlarged conjugated diene rubber was only 3,000 Å, and Comparative Example 4 in which the polymer coagulant was enlarged using 1.7 parts by weight of the conjugated diene rubber was enlarged has a very large average particle diameter of 9,000 Å, and the graft rate and impact strength were lowered.

In addition, Comparative Example 5, in which a small-diameter conjugated diene rubber (Preparation Example B4) having an average particle diameter of 1200 Å was enlarged with a polymer coagulant, had an average particle diameter of only 2800 Å, and the graft rate was lowered, resulting in poor impact strength and fluidity.

In conclusion, an enlarged conjugated diene rubber latex in which the conjugated diene rubber latex according to the present invention is enlarged with a polymer coagulant is prepared, and this is added to the non-enlarged conjugated diene rubber latex in a predetermined amount to produce a bimodal conjugated diene rubber latex to produce vinyl It was confirmed that the method for preparing the cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer significantly shortened the production time of the enlarged conjugated diene rubber and increased the grafting efficiency to have a synergistic effect with improved both impact resistance and fluidity. .

Claims (13)

a) preparing a large-diameter conjugated diene rubber latex step having an average particle diameter of 5,800 to 8,500 Å by adding a polymer coagulant to medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å;
b) preparing a bimodal conjugated diene rubber latex by introducing a medium-diameter conjugated diene rubber latex having an average particle diameter of 2,400 to 2,800 Å to the prepared large-diameter conjugated diene rubber latex;
c) including the prepared bimodal conjugated diene rubber latex, aromatic vinyl compound and vinyl cyan compound to obtain a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer by graft polymerization; characterized by
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
In step a), the polymer coagulant is added in an amount of 0.3 to 1.5 parts by weight (based on solids) based on 100 parts by weight (based on solids) of the medium-diameter conjugated diene rubber latex.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The polymer coagulant is characterized in that the average particle diameter is 700 to 1,700 Å.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The polymer coagulant is a graft copolymer obtained by graft polymerization of an alkyl acrylate compound and a carboxylic acid compound to a polymerized core including at least one selected from the group consisting of an alkyl acrylate compound and a carboxylic acid compound.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The step a) is characterized in that while stirring the medium-diameter conjugated diene rubber latex at 200 to 300 rpm, the polymer coagulant is continuously added at a constant speed for 5 to 20 minutes, and then aged for 10 to 30 minutes
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
Step a) is characterized in that it comprises a step of stabilizing by adding an emulsifier after thickening with a large-diameter conjugated diene rubber latex
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
In step a), the medium-diameter conjugated diene rubber latex is prepared by adding an emulsifier, an electrolyte, a molecular weight regulator and an initiator to 60 to 80 parts by weight of 100 parts by weight of the conjugated diene compound and performing primary polymerization;
After the first polymerization step, 20 to 40 parts by weight of the conjugated diene compound is added at a time when the polymerization conversion rate is 30 to 40% and secondary polymerization is performed;
adding an initiator and a molecular weight regulator at a time when the polymerization conversion rate is 55 to 65% after the second polymerization step and performing a third polymerization;
adding a redox initiator at a time when the polymerization conversion rate is 75 to 85% after the third polymerization step and performing fourth polymerization; and
After the fourth polymerization step, terminating the polymerization at a polymerization conversion rate of 93 to 99%; characterized in that it is prepared including
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
Step b) is a bimodal conjugated diene rubber latex by adding 85 to 96 wt% (solid content) of medium-diameter conjugated diene rubber latex with an average particle diameter of 2,400 to 2,800 Å to 4 to 15 wt% (solid content) of large-diameter conjugated diene rubber latex characterized in that the step of manufacturing
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
Claims 1 to 8 of any one of the manufacturing method according to any one of the vinyl cyanide compound-conjugated diene rubber-preparing an aromatic vinyl compound graft copolymer; and
15 to 40 wt% of the prepared graft copolymer and 60 to 85 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded, and then extruded; characterized in that it comprises a
A method for producing a thermoplastic resin composition.
Bimodal conjugated diene rubber, 15 to 40% by weight of a graft copolymer comprising an aromatic vinyl compound and a vinyl cyan compound, and 60 to 85% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer,
The bimodal conjugated diene rubber is 85 to 97% by weight of a conjugated diene rubber having an average particle diameter of 2,400 to 2,800 Å, 1 to 14% by weight of a conjugated diene rubber having an average particle diameter of 5,800 to 8,500 Å, and 0.1 to 2% by weight of a polymer flocculant, based on the total weight thereof including %,
Characterized in that the Izod impact strength measured with a specimen thickness of 1/4" according to ASTM D256 is 32 kgf cm/cm or more
Thermoplastic resin composition.
11. The method of claim 10,
The bimodal conjugated diene rubber is characterized in that the average particle diameter is 3,000 to 3,800 Å.
Thermoplastic resin composition.
11. The method of claim 10,
The graft copolymer is characterized in that the graft ratio is 30 to 45%
Thermoplastic resin composition.
11. The method of claim 10,
The thermoplastic resin composition is characterized in that the flow index measured under the conditions of 220 °C and 10 kg in accordance with ASTM D1238 is 20 g/10 min or more
Thermoplastic resin composition.

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