KR102361451B1 - Method for preparing large particle sized rubber latex, and method for preparing abs graft copolymer - Google Patents

Abstract

The present disclosure relates to a method for producing a large-diameter rubber latex and a method for producing an ABS-based graft copolymer, and more particularly, 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å, and a core-shell structure polymer coagulant 1 to 3 parts by weight to prepare a large-diameter rubber latex, wherein the polymer coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of a core to a shell of 40 to 60: 40 to 60 of a large-diameter rubber latex It relates to a manufacturing method and a manufacturing method of an ABS-based graft copolymer.
According to the present disclosure, when manufactured by the above method, the stability of the large-diameter rubber latex is excellent, the formation of coagulation is reduced, and the ABS-based graft copolymer containing the large-diameter rubber latex has impact strength, fluidity and balance of physical properties. It has an excellent effect.

Description

Manufacturing method of large-diameter rubber latex and ABS-based graft copolymer

The present invention relates to a method for producing a large-diameter rubber latex and a method for producing an ABS-based graft copolymer, and more particularly, to 100 parts by weight of a rubber latex having an average particle diameter of 500 to 1,500 Å and a core-shell structure polymer coagulant 1 to 3 Including the step of preparing a large-diameter rubber latex by adding parts by weight, wherein the weight average molecular weight of the polymer coagulant is 130,000 to 200,000 g/mol and the weight ratio of the core to the shell is 40 to 60: 40 to 60, of the prepared latex Excellent stability and reduced coagulation, and furthermore, when preparing an ABS-based graft copolymer including this, the prepared copolymer has excellent impact strength, fluidity and physical property balance, a method for producing a large-diameter rubber latex and an ABS-based graft It relates to a method for preparing the copolymer.

ABS-based copolymer represented by acrylonitrile-butadiene-styrene has good physical properties such as impact resistance, mechanical strength, moldability, and gloss, and is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts. have.

The ABS-based copolymer is usually prepared by preparing butadiene rubber latex, and then grafting styrene and acrylonitrile thereto. At this time, physical properties such as impact resistance, mechanical strength, and gloss of the graft copolymer are greatly affected by the average particle size, particle size distribution, dispersion state, and coagulant content of the rubber latex.

In particular, the core technology of the high-impact ABS-based copolymer is the average particle diameter of polybutadiene latex (PBL) of the core, and the appropriate particle diameter of the rubber latex required for this is about 3,000 to 3,500 Å. . In general, PBL is produced by emulsion polymerization, which is advantageous for particle size control, and the large-diameter PBL as described above can be prepared by, for example, emulsion polymerization of small-diameter (about 1,000 to 1,500 Å) PBL, and then enlarging it, and emulsification. Direct preparation through polymerization is also possible.

Large-diameter PBL produced directly through emulsion polymerization has a narrow particle size distribution and low coagulant content, which is advantageous in terms of impact resistance.

Accordingly, a method of reducing the reaction time by adding an additive such as vinyl cyan monomer or continuously adding an emulsifier during emulsion polymerization has been proposed, but the effect is insignificant, and when the polymerization reaction temperature is increased to increase the reaction rate, the latex particle size This resulted in another problem, such as becoming smaller and the content of coagulated matter increased.

On the other hand, the method of producing large-diameter PBL by enlarging small-diameter PBL can shorten the reaction time by half, which is advantageous in terms of productivity, but uses an acid such as acetic acid as a conventional coagulant (particle thickening agent). The method is complicated, and since it is necessary to use soap for coagulation in the water treatment process, there was a problem of excessive coagulation.

Korean Patent No. 384375

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing a large-diameter rubber latex in which coagulation is reduced while ensuring excellent latex stability.

In addition, an object of the present invention is to provide a method for producing an ABS graft copolymer having excellent impact strength and fluidity, including a large-diameter rubber latex according to the above-mentioned manufacturing method.

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 substrate prepares an enlarged conjugated diene rubber latex by adding 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure. However, the polymer flocculant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60. Provides a method for producing a large-diameter rubber latex.

The polymer coagulant may have, for example, an average particle diameter of 1,300 to 1,600 Å.

The enlarged conjugated diene rubber latex may have, for example, an average particle diameter of 2,800 to 4,000 Å.

The polymer coagulant may be prepared by, for example, polymerizing 100 parts by weight of a total of 100 parts by weight of a monomer constituting the polymer flocculant in 0.05 to 0.15 parts by weight of a thermal decomposition initiator.

The thermal decomposition initiator may be, for example, at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.

The method for preparing the polymer coagulant comprises, for example, polymerizing 40 to 60 parts by weight of (meth)acrylic acid alkyl ester monomer and 0 to 5 parts by weight of an unsaturated acid monomer, 0.012 to 0.040 parts by weight of a thermal decomposition initiator to prepare a core; And in the presence of the polymerized core, 31 to 53 parts by weight of (meth)acrylic acid alkyl ester monomer, 7 to 11 parts by weight of an unsaturated acid monomer, and the remaining balance of the thermal decomposition initiator by graft polymerization to prepare a shell; can do.

The (meth)acrylic acid alkyl ester monomer is, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid propyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid tert- It may be at least one selected from the group consisting of butyl and (meth)acrylic acid 2-ethylhexyl.

The unsaturated acid monomer may be, for example, at least one selected from the group consisting of (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, and anhydrides thereof.

In the step of preparing the shell, the remaining amount of the thermal decomposition initiator may be added in the form of a stock solution prepared, for example, in a concentration of 1 to 5% by weight of the thermal decomposition initiator with water.

The method for producing the large-diameter rubber latex may include, for example, adding a polymer coagulant to the conjugated diene rubber latex and stirring at 45 to 75° C. for 10 to 40 minutes to enlarge it.

In addition, the present substrate includes the steps of preparing an enlarged conjugated diene rubber latex by adding 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure; and adding 15 to 40 wt% of an aromatic vinyl monomer and 3 to 25 wt% of a vinyl cyan monomer to 45 to 80 wt% of the enlarged conjugated diene rubber latex (based on solid content) to perform graft polymerization; including, the polymer The coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60. Provides a method for producing an ABS-based graft copolymer.

In addition, the present substrate contains 100 parts by weight of a conjugated diene rubber and 1 to 3 parts by weight of a polymer flocculant having a core-shell structure, and is a large-diameter rubber latex having an average particle diameter of 2,800 to 4,000 Å, wherein the polymer flocculant has a weight average molecular weight of 130,000 to 130,000 It provides a large diameter rubber latex, characterized in that 200,000 g / mol and the weight ratio of the core to the shell is 40 to 60: 40 to 60.

According to the present disclosure, a polymer coagulant having a core-shell structure as a rubber particle thickening agent for manufacturing large-diameter rubber latex, a polymer coagulant having a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60 In the case of adding , the stability of the prepared latex is excellent and the formation of coagulation is reduced, and when an ABS-based graft copolymer is prepared including the prepared latex, the impact strength, fluidity and physical property balance of the prepared copolymer has an excellent effect.

Hereinafter, a method for producing a large-diameter rubber latex of the present invention will be described in detail.

The present inventors use a polymer coagulant having a core-shell structure, which is input to enlarge the small-diameter conjugated diene rubber latex into a large-diameter conjugated diene rubber latex, with a specific molecular weight and a specific core-shell weight ratio. Conjugated diene rubber latex has excellent stability and reduced coagulation, and when it is used in the manufacture of ABS graft copolymer, it is confirmed that mechanical properties and fluidity such as impact strength are improved, and based on this, further research The present invention has been completed.

Manufacturing method of large diameter rubber latex

The method for producing a large-diameter rubber latex of the present disclosure includes 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å (hereinafter referred to as 'small-diameter rubber latex') and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure. to prepare an enlarged conjugated diene rubber latex, wherein the polymer coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60, In this case, the stability of the polymer latex is excellent and the formation of coagulation is reduced, and when it is used in the manufacture of the ABS graft copolymer, there is an excellent effect in impact strength, fluidity and balance of properties.

The method for producing the large-diameter rubber latex may include, for example, 1-3 parts by weight, 1 to 2.5 parts by weight, 1.5 to 2.5 parts by weight, or 1.9 to 2.5 parts by weight of the polymer coagulant based on 100 parts by weight of the small-diameter rubber latex, Within this range, it is possible to enlarge in a short time while suppressing the formation of clots.

The polymer coagulant may have, for example, a weight average molecular weight of 130,000 to 200,000 g/mol, 140,000 to 190,000 g/mol, or 160,000 to 180,000 g/mol, and within this range, the small-diameter rubber latex is enlarged within a short time and the coagulated product While reducing the production, there is an effect of improving the stability of the produced large-diameter rubber latex.

In the present description, the weight average molecular weight is measured using GPC by dissolving a sample in THF (tetrahydrofuran).

The polymer coagulant, for example, the weight ratio of the core and the shell may be 40 to 60: 40 to 60, 45 to 60: 40 to 55, or 45 to 55: 45 to 55, and the latex stability is excellent and coagulation within this range. As water production is reduced, when it is used in the manufacture of the ABS graft copolymer, mechanical properties such as impact strength and fluidity are improved.

The polymer coagulant may have, for example, an average particle diameter of 1,300 to 1,600 Å, 1,350 to 1,550 Å, or 1,350 to 1,490 Å.

The core-shell structure polymer coagulant, for example, the core may include 90 to 100% by weight of a (meth)acrylic acid alkyl ester monomer and 0 to 10% by weight of an unsaturated acid monomer, and the shell is an alkyl (meth)acrylic acid 80 to 90% by weight of an ester monomer and 10 to 20% by weight of an unsaturated acid monomer.

As another example, the core-shell structure polymer coagulant may include 90 to 99.9% by weight of a (meth)acrylic acid alkyl ester monomer and 0.1 to 10% by weight of an unsaturated acid monomer, and the shell is (meth) 80 to 90% by weight of an acrylic acid alkyl ester monomer and 10 to 20% by weight of an unsaturated acid monomer.

The small-diameter rubber latex may have, for example, an average particle diameter of 700 to 1,200 Å or 900 to 1,100 Å.

The enlarged conjugated diene rubber latex may have, for example, an average particle diameter of 2,800 to 4,000 Å, 3,000 to 3,700 Å, or 3,300 to 3,500 Å, and an ABS-based graft copolymer including the prepared latex within this range. In the case of manufacturing, the prepared copolymer has an excellent effect in terms of impact strength, fluidity, and balance of physical properties.

In the present description, the average particle diameter is measured using an intensity Gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.

The method for producing the large-diameter rubber latex may include, for example, adding a polymer coagulant to the small-diameter latex, and stirring at 45 to 75 ° C., or 50 to 65 ° C. for 10 to 40 minutes or 15 to 30 minutes to enlarge. There is, in this case, the stability of the latex is excellent and has the effect of reducing the formation of coagulation.

Method for manufacturing polymer flocculant

The polymer coagulant may be prepared by, for example, polymerizing 100 parts by weight of a total of 100 parts by weight of the monomer constituting the polymer flocculant, 0.05 to 0.15 parts by weight, 0.06 to 0.14 parts by weight, or 0.06 to 0.10 parts by weight of the thermal decomposition initiator, in this case the desired molecular weight And a polymer coagulant having an effect is prepared.

The thermal decomposition initiator may be, for example, at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate, and in this case, latex stability is excellent and coagulation is reduced.

The method for preparing the polymer coagulant comprises, for example, polymerizing 40 to 60 parts by weight of (meth)acrylic acid alkyl ester monomer and 0 to 5 parts by weight of an unsaturated acid monomer, 0.012 to 0.040 parts by weight of a thermal decomposition initiator to prepare a core; And in the presence of the polymerized core, 31 to 53 parts by weight of (meth)acrylic acid alkyl ester monomer, 7 to 11 parts by weight of an unsaturated acid monomer, and the remaining balance of the thermal decomposition initiator by graft polymerization to prepare a shell; In this case, there is an effect of improving the stability of the large-diameter rubber latex produced while enlarging the small-diameter rubber latex into a large-diameter within a short time and reducing the formation of coagulation.

As another example, the method for producing the polymer coagulant comprises 45 to 55 parts by weight of a (meth)acrylic acid alkyl ester monomer and 0 to 5 parts by weight of an unsaturated acid monomer, and 0.015 to 0.037 parts by weight of a thermal decomposition initiator to prepare a core. step; And in the presence of the polymerized core, (meth) acrylic acid alkyl ester monomer 35 to 45 parts by weight, 8 to 10 parts by weight of an unsaturated acid monomer, and the remaining amount of the thermal decomposition initiator graft polymerization to prepare a shell; In this case, there is an effect of improving the stability of the large-diameter rubber latex produced while enlarging the small-diameter rubber latex into a large-diameter within a short time and reducing the formation of coagulation.

The (meth)acrylic acid alkyl ester monomer is, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid propyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid tert- It may be at least one selected from the group consisting of butyl and 2-ethyl hexyl (meth)acrylate, preferably ethyl acrylate, n-butyl acrylate, or a mixture thereof.

In the present description, (meth)acrylic acid alkyl ester includes both methacrylic acid alkyl ester and acrylic acid alkyl ester.

The unsaturated acid monomer may include, for example, at least one selected from the group consisting of (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, and anhydrides thereof, preferably (meth) It contains acrylic acid, and more preferably contains methacrylic acid, and in this case, the coagulation effect is excellent, and the formation of a coagulate is reduced, thereby contributing to productivity improvement.

The remaining residual amount of the thermal decomposition initiator input in the step of preparing the shell may be, for example, batch input or continuous input while the shell is polymerized.

The continuous input may be, for example, continuously added by drop by drop or continuously introduced as a stream.

The remaining amount of the thermal decomposition initiator added in the step of preparing the shell may be added in the form of a stock solution prepared, for example, in a concentration of 1 to 5 wt% or 2 to 4 wt% of the pyrolysis initiator with water, In this case, there is an effect that the thermal decomposition initiator is uniformly dispersed and the polymerization reaction proceeds smoothly.

In the step of preparing the core, for example, 0.1 to 2 parts by weight, 0.5 to 1.5 parts by weight, or 0.5 to 1 parts by weight of an emulsifier may be added to perform polymerization.

The emulsifier is, for example, an alkyl sulfosuccinate metal salt and derivatives thereof having 12 to 18 carbon atoms, an alkyl sulfate ester and derivatives thereof having 12 to 20 carbon atoms, an alkyl sulfonic acid metal salt having 12 to 20 carbon atoms, and derivatives thereof 1 selected from the group consisting of may be more than one species.

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.

The method for preparing the polymer coagulant may be carried out at a polymerization temperature of 70 to 90°C, or 75 to 85°C, for example, and within this range, the grafting efficiency is excellent.

Method for producing small diameter rubber latex

The small-diameter rubber latex is, for example, 85 to 95 parts by weight of a total of 100 parts by weight of the conjugated diene monomer, 1 to 4 parts by weight of an emulsifier, 0.1 to 0.6 parts by weight of a polymerization initiator, 0.1 to 1 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight regulator Polymerizing at 50 to 60 ℃ by adding 70 to 130 parts by weight of ion-exchanged water in a batch; adding 0.05 to 1.2 parts by weight of an initiator at a polymerization conversion rate of 30 to 40%, and raising the temperature to 65 to 75° C. to perform polymerization; polymerizing by adding 5 to 15 parts by weight of a conjugated diene monomer at a polymerization conversion rate of 60 to 70%; and terminating the polymerization at a polymerization conversion rate of 93 to 98%.

The conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene and pyrerylene. It may be at least one selected from the group consisting of.

The emulsifier used in preparing the small-diameter 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, the stability of the polymerization reaction is excellent, and rubber latex having a desired particle size can be prepared.

The electrolyte 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 , It may be at least one selected from the group consisting of K ₃ PO ₄ , Na ₃ PO ₄ and K ₂ HPO ₄ , and in this case, the stability of the latex is excellent.

The molecular weight modifier 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, and is preferably t-dodecyl mercaptan.

The initiator used in the preparation of the small-diameter rubber latex is, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, benzoyl peroxide, etc. of fat-soluble persulfate; peroxy monomers; and a redox-based polymerization initiator combining a reducing agent and an oxidizing agent.

ABS system graft Method for preparing copolymer

In the method for preparing the ABS-based graft copolymer of the present invention, 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure are added to prepare an enlarged conjugated diene rubber latex to do; and adding 15 to 40 wt% of an aromatic vinyl monomer and 3 to 25 wt% of a vinyl cyan monomer to 45 to 80 wt% of the enlarged conjugated diene rubber latex (based on solid content) to perform graft polymerization; including, the polymer The coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of core and shell of 40 to 60: 40 to 60, and in this case, impact strength, fluidity and physical properties of the prepared ABS-based graft copolymer There is an excellent effect of balance.

The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, vinyltoluene, and chlorostyrene, and the vinyl cyan compound is, for example, acrylonitrile, methacrylonitrile, or a mixture thereof. can

The method for preparing the ABS-based graft copolymer may include, for example, agglomeration, aging, dehydration and drying of the latex prepared after the graft polymerization, and the graft copolymer prepared including the above steps is a powder may be provided in the form. The coagulation, aging, dehydration and drying steps are not particularly limited if the methods are generally used in the art.

The step of agglomeration in the manufacturing method of the ABS-based graft copolymer may be carried out either alone or by mixing an acid coagulant such as sulfuric acid, phosphoric acid and hydrochloric acid, or a salt coagulant such as magnesium sulfate, aluminum sulfate and calcium chloride.

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

The large-diameter rubber latex of the present disclosure includes 100 parts by weight of a conjugated diene rubber and 1 to 3 parts by weight of a polymer flocculant having a core-shell structure, and a large-diameter rubber latex having an average particle diameter of 2,800 to 4,000 Å, wherein the polymer flocculant has a weight average molecular weight It is characterized in that 130,000 to 200,000 g/mol, and the weight ratio of the core to the shell is 40 to 60: 40 to 60, and in this case, the impact strength, fluidity, and physical property balance of the ABS-based graft copolymer are excellent.

As another example, the large-diameter rubber latex contains 100 parts by weight of a conjugated diene rubber and 1 to 2.5 parts by weight, 1.5 to 2.5 parts by weight, or 1.9 to 2.5 parts by weight of a polymer coagulant having a core-shell structure, and an average particle diameter of 3,000 to 3,700 Å or 3,300 to 3,500 Å of large-diameter rubber latex, wherein the polymer coagulant has a weight average molecular weight of 140,000 to 190,000 g/mol or 160,000 to 180,000 g/mol, and a weight ratio of core and shell of 45 to 60: 40 to 55 or 45 to 55 : It may be 45 to 55, and in this case, the impact strength, fluidity, and physical property balance of the ABS-based graft copolymer are excellent.

인 대구경 고무 라텍스 45 내지 80 중량%(고형분 기준)에, 방향족 비닐 단량체 15 내지 40 중량% 및 비닐시안 단량체 3 내지 25 중량%가 그라프트 중합된 공중합체이되, 상기 고분자 응집제는 중량평균분자량이 130,000 내지 200,000 g/mol이고 코어와 쉘의 중량비가 40 내지 60 : 40 내지 60인 것을 특징으로 하고, 이 범위 내에서 충격강도, 유동성 및 물성 밸런스가 우수한 효과가 있다.The ABS-based graft copolymer of the present invention contains 100 parts by weight of a conjugated diene rubber and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure, and an average particle diameter of 2,800 to 4,000.

It is a copolymer obtained by graft polymerization of 45 to 80% by weight of phosphorus large-diameter rubber latex (based on solid content), 15 to 40% by weight of an aromatic vinyl monomer and 3 to 25% by weight of a vinyl cyanide monomer, wherein the polymer coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol, and the weight ratio of the core to the shell is 40 to 60: 40 to 60, and there is an excellent effect of impact strength, fluidity and physical property balance within this range.

The polymer coagulant, large-diameter rubber latex, and the like included in the ABS-based graft copolymer follow the above description, and thus description thereof will be omitted.

The thermoplastic resin composition of the present disclosure includes, for example, 20 to 80% by weight of the ABS-based graft copolymer and 20 to 80% by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer, but the Izod impact strength measured according to ASTM D256 (1/4˝, 23℃) is characterized by more than 21 kgf·cm/cm, and in this case, it has excellent balance of properties and can be applied to products requiring impact resistance.

As another example, the thermoplastic resin composition includes 40 to 60% by weight of the ABS-based graft copolymer and 40 to 60% by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer, but the Izod impact strength measured according to ASTM D256 (1/4˝, 23℃) has a characteristic of 21 to 30 kgf·cm/cm, or 22 to 25 kgf·cm/cm, and in this case, it is applied to products requiring excellent balance of properties and impact resistance can do.

In addition, the thermoplastic resin composition of the present disclosure contains 20 to 80% by weight or 40 to 60% by weight of the ABS-based graft copolymer, and 20 to 80% by weight or 40 to 60% by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer. Including, but is characterized in that the flow index (220 ℃, 10 kg) measured according to ASTM D1238 is 15 g/10 min or more, 15 to 20 g/10 min, or 15.8 to 18.5 g/10 min, in this case, the physical properties There is an excellent effect of balance.

The aromatic vinyl monomer-vinyl cyan monomer copolymer may be, for example, a copolymer of a vinyl aromatic monomer such as styrene or α-methylstyrene and a vinyl cyan monomer such as acrylonitrile or methacrylonitrile.

The method for preparing the thermoplastic resin composition of the present disclosure includes preparing an enlarged conjugated diene rubber latex by adding 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure; 15 to 40% by weight of an aromatic vinyl monomer and 3 to 25% by weight of a vinyl cyan monomer are added to 45 to 80% by weight of the enlarged conjugated diene rubber latex (based on solid content), and graft polymerization to prepare an ABS-based graft copolymer step; And mixing 20 to 80 parts by weight of the prepared ABS-based graft copolymer and 20 to 80 parts by weight of the aromatic vinyl monomer-vinyl cyan monomer copolymer, melt-kneading and extruding; including, wherein the polymer coagulant has a weight average molecular weight It is characterized in that 130,000 to 200,000 g/mol and the weight ratio of the core to the shell is 40 to 60: 40 to 60, and within the above range, it is possible to prepare a thermoplastic resin composition having excellent impact strength, fluidity and physical property balance.

The melt-kneading may be carried out at 200 to 280 °C, or 220 to 260 °C in a twin-screw extruder, for example.

In the method for producing the thermoplastic resin composition, content overlapping with the above-described thermoplastic resin composition was omitted.

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.

[Production Example]

<Preparation of polymer flocculant>

production example One

208 parts by weight of distilled water and 0.75 parts by weight of dioctyl sulfosuccinate sodium (DOSS) as an emulsifier were added to the reactor and stirred while the temperature was raised to 80 ° C., and then potassium persulfate as a thermal decomposition initiator (Potassium persulfate, K ₂ S ₂ O ₈ ) After starting polymerization by adding 0.034 parts by weight and 50 parts by weight of butyl acrylate (BA), polymerization was carried out for 90 minutes to prepare a core part. Then, in the presence of the core, as a shell part, 41 parts by weight of butyl acrylate, 9 parts by weight of methacrylic acid (MAA) and potassium persulfate in the form of a stock solution prepared to a concentration of 3% by weight with distilled water, potassium persulfate 0.099 parts by weight were continuously added for 90 minutes to carry out a graft polymerization reaction, and the reaction was terminated at a polymerization conversion rate of 98%.

Finally, a polymer coagulant having a core-shell structure having a core:shell weight ratio of 50:50 was obtained.

production example 2

In Preparation Example 1, 0.026 parts by weight of potassium persulfate was added at the start of core polymerization, and 0.074 weight of potassium persulfate in the form of a stock solution prepared so that the concentration of potassium persulfate was 3% by weight with distilled water during shell polymerization. It was carried out in the same manner as in Preparation Example 1, except that parts were continuously added.

production example 3

In Preparation Example 1, 0.017 parts by weight of potassium persulfate was added at the start of the core polymerization, and 0.05 weight of potassium persulfate was added in the form of a stock solution prepared so that the concentration of potassium persulfate was 3% by weight with distilled water during shell polymerization. It was carried out in the same manner as in Preparation Example 1, except that parts were continuously added.

production example 4

In Preparation Example 1, 0.006 parts by weight of potassium persulfate was added at the start of core polymerization, and 0.019 weight of potassium persulfate was added in the form of a stock solution prepared so that the concentration of potassium persulfate was 3% by weight with distilled water during shell polymerization. It was carried out in the same manner as in Preparation Example 1, except that parts were continuously added.

production example 5

In Preparation Example 1, 0.05 parts by weight of potassium persulfate was added at the start of core polymerization, and 0.15 weight of potassium persulfate was added in the form of a stock solution prepared so that the concentration of potassium persulfate was 3% by weight with distilled water during shell polymerization. It was carried out in the same manner as in Preparation Example 1, except that parts were continuously added.

production example 6

208 parts by weight of distilled water and 0.75 parts by weight of dioctyl sulfosuccinate sodium (DOSS) as an emulsifier were added to the reactor and stirred while the temperature was raised to 80° C., and then 0.05 parts by weight of potassium persulfate and butyl acrylate (BA) 75 as a thermal decomposition initiator After starting polymerization by adding parts by weight, the polymerization reaction was carried out for 120 minutes to prepare a core. Then, in the presence of the core, 20.5 parts by weight of shello butyl acrylate, 4.5 parts by weight of methacrylic acid (MAA), and potassium persulfate in the form of a stock solution prepared to a concentration of 3% by weight with distilled water, 0.15 weight of potassium persulfate The part was continuously added for 60 minutes to carry out a graft polymerization reaction, and the reaction was terminated at a polymerization conversion rate of 98%.

Finally, a core-shell polymer coagulant having a core-shell weight ratio of 75:25 was obtained.

production example 7

208 parts by weight of distilled water and 0.75 parts by weight of dioctyl sulfosuccinate sodium (DOSS) as an emulsifier were added to the reactor and stirred while the temperature was raised to 80° C., and then 0.05 parts by weight of potassium persulfate and butyl acrylate (BA) 60 as a thermal decomposition initiator After starting polymerization by adding parts by weight, the polymerization reaction was carried out for 90 minutes to prepare a core. Then, in the presence of the core, 32.8 parts by weight of shello butyl acrylate, 7.2 parts by weight of methacrylic acid (MAA) and potassium persulfate in the form of a stock solution prepared to a concentration of 3% by weight with distilled water, 0.15 weight of potassium persulfate The part was continuously added for 90 minutes to carry out a graft polymerization reaction, and the reaction was terminated at a polymerization conversion rate of 98%.

Finally, a polymer coagulant having a core-shell structure having a core:shell weight ratio of 60:40 was obtained.

production example 8

208 parts by weight of distilled water and 0.75 parts by weight of dioctyl sulfosuccinate sodium (DOSS) as an emulsifier were added to the reactor and stirred while the temperature was raised to 80° C., and then 0.034 parts by weight of potassium persulfate and butyl acrylate (BA) 20 as a thermal decomposition initiator After starting polymerization by adding parts by weight, it was reacted for 30 minutes to prepare a core. Then, in the presence of the core, 65.6 parts by weight of shello butyl acrylate, 14.4 parts by weight of methacrylic acid (MAA), and potassium persulfate in the form of a stock solution prepared to a concentration of 3% by weight with distilled water, 0.1 weight of potassium persulfate The part was continuously added for 150 minutes to carry out a graft polymerization reaction, and the reaction was terminated at a polymerization conversion rate of 98%.

Finally, a polymer coagulant having a core-shell structure having a core:shell weight ratio of 20:80 was obtained.

production example 9

208 parts by weight of distilled water and 0.75 parts by weight of dioctyl sulfosuccinate sodium (DOSS) as an emulsifier were added to the reactor and stirred while the temperature was raised to 80° C., and then 0.034 parts by weight of potassium persulfate and butyl acrylate (BA) 10 as a thermal decomposition initiator After starting polymerization by adding parts by weight, it was reacted for 10 minutes to prepare a core. Then, in the presence of the core, 73.8 parts by weight of shello butyl acrylate, 16.2 parts by weight of methacrylic acid (MAA), and potassium persulfate in the form of a stock solution prepared to a concentration of 3% by weight with distilled water, 0.1 weight of potassium persulfate The part was continuously added for 240 minutes to carry out a graft polymerization reaction, and the reaction was terminated at a polymerization conversion rate of 98%.

Finally, a core-shell polymer coagulant having a core-shell weight ratio of 10:90 was obtained.

<Preparation of small diameter rubber latex>

production example 10

75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 90 parts by weight of 1,3-butadiene as a monomer, 3 parts by weight of a dimer acid potassium salt (Cas No.67701-19-3) as an emulsifier, potassium carbonate ( K ₂ CO ₃ ) 0.1 parts by weight, 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.15 parts by weight of tertiary butyl hydroperoxide as an initiator, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrole phosphate and 0.0025 parts by weight of ferrous sulfate were added in a batch, and polymerization was initiated at 55°C. After adding 0.3 wt% of potassium persulfate at a polymerization conversion rate of 30 to 40%, the temperature was raised to 72° C. for polymerization reaction, and then 10 parts by weight of 1,3-butadiene was added at a polymerization conversion rate of 60 to 70%, followed by a polymerization conversion rate of 95 % to complete the reaction. At this time, the average particle diameter of the small-diameter rubber latex was 1,000 Å, and the solid content was 39% by weight.

[Example]

Example One

Based on 100 parts by weight of the small-diameter rubber latex prepared in Preparation Example 10 (based on solid content), 2.2 parts by weight of the polymer coagulant prepared in Preparation Example 1 was added and stirred at 50° C. The particle size was measured. 28.8% by weight of styrene and 11.2% by weight of acrylonitrile were added to 60% by weight of the prepared large-diameter rubber latex (based on solid content), and graft polymerization was performed to prepare an ABS graft copolymer latex. This was agglomerated with 2 parts by weight of magnesium sulfate, then aged, dehydrated and dried to obtain an ABS graft copolymer powder. 23% by weight of the ABS graft copolymer powder and 77% by weight of the acrylonitrile-styrene copolymer are mixed in a mixer, melt-kneaded at 220° C. using an extruder, and pelletized, and this is used for physical properties using an injection machine Specimens for measurement were prepared.

Example 2

Example 1 was carried out in the same manner as in Example 1, except that the polymer coagulant of Preparation Example 2 was used.

Example 3

Example 1 was carried out in the same manner as in Example 1, except that the polymer coagulant of Preparation Example 3 was used.

Example 4

Example 1 was carried out in the same manner as in Example 1, except that 1.9 parts by weight of the polymer coagulant of Preparation Example 2 was used.

Example 5

Example 1 was carried out in the same manner as in Example 1, except that 2.5 parts by weight of the polymer coagulant of Preparation Example 2 was used.

comparative example 1 to 7

Example 1 was carried out in the same manner as in Example 1, except that the type or content of the polymer coagulant was changed as in Tables 3 and 4 below.

[Test Example]

The properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Tables 1 to 4 below.

How to measure

) 측정: 소구경 고무 라텍스에 고분자 응집제를 투입 후 30분이 경과된 시점에 Nicomp 370HPL 기기를 사용하여 다이나믹 레이져 라이트 스케트링 방법으로 대구경 라텍스 내 고무의 평균입경을 측정하였다.* Average particle diameter of large diameter rubber latex (

) Measurement: At 30 minutes after adding the polymer coagulant to the small-diameter rubber latex, the average particle diameter of the rubber in the large-diameter latex was measured by using a Nicomp 370HPL device using the dynamic laser light skating method.

* Weight average molecular weight (g/mol): The sample was dissolved in THF (tetrahydrofuran) and measured using GPC.

* Izod impact strength (kgf·cm/cm): A specimen thickness of 1/4″ was measured at room temperature (23°C) according to ASTM D256.

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

* Polymerization conversion (%): After drying 1.5 g of the prepared latex in a hot air dryer at 150 ° C. for 15 minutes, the weight was measured to determine the total solid content (TSC), and then the polymerization conversion rate was calculated by Equation 1 below.

[Equation 1]

Polymerization conversion (%) = [(parts by weight of monomers and additives added) X (TSC) - (parts by weight of additives added other than monomers)] X 100

* Latex stability (%): After 30 minutes and 2 hours have elapsed after adding the polymer coagulant to the small-diameter rubber latex, the average particle diameter of the large-diameter rubber latex was measured by the dynamic laser light skating method using the Nicomp 370HPL instrument. , The rubber latex stability was calculated by Equation 2 below.

The lower the rubber latex stability value, the better the latex stability was evaluated.

[Equation 2]

* Coagulation content in latex (wt%): After filtering the enlarged large-diameter rubber latex using a wire mesh of 60 mesh, the unfiltered coagulation is dried and weighed, and its content is calculated as the total solid content It was calculated as a percentage of

division Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 potassium persulfate
Total input (parts by weight) 0.133 0.100 0.067 0.025 0.2 polymer coagulant
weight average molecular weight
(g/mol) 140,000 160,000 180,000 250,000 120,000 polymer flocculant
Average particle diameter (Å) 1510 1490 1350 1500 1230 Core:shell weight ratio 50:50 50:50 50:50 50:50 50:50

division Preparation 6 Preparation 7 Preparation 8 Preparation 9 potassium persulfate
Total input (parts by weight) 0.2 0.2 0.133 0.133 polymer coagulant
weight average molecular weight
(g/mol) 120,000 120,000 140,000 140,000 polymer flocculant
Average particle diameter (Å 1200 1250 1500 1520 Core:shell weight ratio 75:25 60:40 20:80 10:90

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 big
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La
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s polymer
flocculant
Kinds Preparation Example 1 Preparation 2 Preparation 3 Preparation 2 Preparation 2 Preparation 4 polymer flocculant
Content (parts by weight) 2.2 2.2 2.2 1.9 2.5 2.2 Large diameter rubber latex average particle diameter (Å) 3400 3500 3300 3350 3450 3400 Latex Stability
(%) 2.94 4.3 4.5 3.0 4.5 coagulation Coagulant content (wt%) <0.01 <0.01 <0.01 <0.01 <0.01 >0.1 heat
plastic resin MI 18.5 18.0 15.8 18.1 17.9 Solidification during SAN grafting Izod
impact strength 22.3 23.7 24.2 23.5 23.8

division Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 big
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s polymer
flocculant
Kinds Preparation 5 Preparation 6 Preparation 7 Preparation 8 Preparation 9 Preparation Example 2 polymer flocculant
Content (parts by weight) 2.2 2.2 2.2 2.2 2.2 4.0 Large diameter rubber latex average particle diameter (Å) 3400 3400 3300 3300 3400 3500 Latex Stability (%) 5.9 6.0 5.8 3.0 3.1 coagulation Coagulant content (wt%) 0.01 <0.01 <0.01 <0.01 <0.01 >0.1 heat
firing
Suzy MI 18.1 17.9 18.0 15.0 14.8 Solidification during SAN grafting Izod
impact strength 19.3 19.2 19.5 13.0 13.5

As shown in Tables 1 and 2 above, the polymer flocculant having a core-shell structure (Preparation Examples 1 to 3) according to the present invention has a weight average molecular weight of the polymer flocculant outside the range of the present invention (Preparation Examples 4 to 7). ), the latex stability was excellent and the coagulated product was reduced.

In addition, as shown in Tables 3 and 4, Examples 1 to 5 containing the large-diameter rubber latex enlarged with the polymer coagulant (Preparation Examples 1 to 3) of the core-shell structure according to the present invention, Preparation Examples 5 to 7 In comparison with Comparative Examples 2 to 4 including the large-diameter rubber latex, which was enlarged with a polymer coagulant of

In addition, as in Preparation Example 4, Comparative Example 1 including a large-diameter rubber latex enlarged with a polymer flocculant having a very large weight average molecular weight, and Comparative Example 7 containing an excess of the polymer flocculant of Preparation Example 2 was a SAN copolymer in a large-diameter rubber latex. It was coagulated during the graft polymerization, so the physical properties could not be measured.

In addition, the weight average molecular weight of the polymer flocculant is within the range of the present invention, but the weight ratio of the core and the shell is 40 to 60: Comparative Examples 5 and 6 including the large diameter rubber latex enlarged with the polymer flocculant of Preparation Examples 8 and 9 out of 40 to 60 In comparison with Examples 1 to 5, the melt index was lowered and the impact strength was very poor.

Claims (12)

A step of preparing an enlarged conjugated diene rubber latex by adding 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure,
The polymer coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60
Method for producing large diameter rubber latex.
The method of claim 1,
The polymer coagulant has an average particle diameter of 1,300 to 1,600 Å
Method for producing large diameter rubber latex.
The method of claim 1,
The enlarged conjugated diene rubber latex is characterized in that the average particle diameter is 2,800 to 4,000 Å.
Method for producing large diameter rubber latex.
The method of claim 1,
The polymer flocculant is prepared by polymerizing a total of 100 parts by weight of a monomer constituting the polymer flocculant in 0.05 to 0.15 parts by weight of a thermal decomposition initiator.
Method for producing large diameter rubber latex.
5. The method of claim 4,
The thermal decomposition initiator, characterized in that at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate
Method for producing large diameter rubber latex.
5. The method of claim 4,
The method for preparing the polymer coagulant comprises: preparing a core by polymerizing 40 to 60 parts by weight of a (meth)acrylic acid alkyl ester monomer and 0 to 5 parts by weight of an unsaturated acid monomer, 0.012 to 0.040 parts by weight of a thermal decomposition initiator; And in the presence of the polymerized core, 31 to 53 parts by weight of a (meth)acrylic acid alkyl ester monomer, 7 to 11 parts by weight of an unsaturated acid monomer, and the remaining balance of the thermal decomposition initiator by graft polymerization to prepare a shell; characterized by
Method for producing large diameter rubber latex.
7. The method of claim 6,
The (meth)acrylic acid alkyl ester monomer is methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid tert-butyl and (meth) acrylic acid 2-ethylhexyl, characterized in that at least one selected from the group consisting of
Method for producing large diameter rubber latex.
7. The method of claim 6,
The unsaturated acid monomer is (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, characterized in that at least one selected from the group consisting of anhydrides thereof
Method for producing large diameter rubber latex.
7. The method of claim 6,
In the step of preparing the shell, the remaining amount of the thermal decomposition initiator is added in the form of a stock solution prepared so that the concentration of the thermal decomposition initiator is 1 to 5% by weight with water.
Method for producing large diameter rubber latex.
The method of claim 1,
The method for producing the large-diameter rubber latex is characterized in that it comprises the step of adding a polymer coagulant to the conjugated diene rubber latex and stirring for 10 to 40 minutes at 45 to 75 ° C.
Method for producing large diameter rubber latex.
Preparing an enlarged conjugated diene rubber latex by adding 100 parts by weight of a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 Å and 1 to 3 parts by weight of a polymer coagulant having a core-shell structure; and
The step of graft polymerization by adding 20 to 40% by weight of an aromatic vinyl monomer and 5 to 15% by weight of a vinyl cyan monomer to 50 to 75% by weight of the enlarged conjugated diene rubber latex (based on solid content);
The polymer coagulant has a weight average molecular weight of 130,000 to 200,000 g/mol and a weight ratio of the core to the shell of 40 to 60: 40 to 60
Method for producing an ABS-based graft copolymer.
100 parts by weight of the conjugated diene rubber and 1 to 3 parts by weight of a polymer flocculant having a core-shell structure, and a large-diameter rubber latex having an average particle diameter of 2,800 to 4,000 Å, wherein the polymer flocculant has a weight average molecular weight of 130,000 to 200,000 g/mol The weight ratio of the core to the shell is 40 to 60: 40 to 60
Large diameter rubber latex.