KR20200037979A - Method for preparing graft copolymer and method for preparing thermoplastic resin composition containing thereof - Google Patents

Abstract

The present description relates to a method for preparing a graft copolymer and a method for preparing a thermoplastic resin composition comprising the same. More particularly, the present invention relates to a method for preparing a graft copolymer, in which a thiol compound having a specific structure is introduced in a step of graft polymerization by adding an aromatic vinyl monomer and a vinyl cyan monomer to conjugated diene rubber latex that has been enlarged by a polymer flocculant; and to a method for preparing a thermoplastic resin composition comprising the same. According to the present description, the graft copolymer prepared by using the polymer flocculant and the specific thiol compound together has a synergistic effect that both impact strength and fluidity are improved.

Description

Method of manufacturing a graft copolymer and a method of manufacturing a thermoplastic resin composition comprising the same {METHOD FOR PREPARING GRAFT COPOLYMER AND METHOD FOR PREPARING THERMOPLASTIC RESIN COMPOSITION CONTAINING THEREOF}

The present invention relates to a method for producing a graft copolymer and a method for producing a thermoplastic resin composition comprising the same, and more specifically, to graft polymerization by introducing an aromatic vinyl monomer and a vinyl cyan monomer into the conjugated diene enlarged with a polymer flocculant. It relates to a method for preparing a graft copolymer having a synergistic effect with improved impact strength and fluidity, in which a specific compound is introduced in a step, and a method for producing a thermoplastic resin composition comprising the same.

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

These ABS-based copolymers are usually prepared by preparing butadiene rubber latex, followed by graft polymerization of styrene and acrylonitrile. At this time, physical properties such as impact resistance, mechanical strength, and glossiness of the graft copolymer are greatly affected by the average particle size, particle size distribution, dispersion state, and coagulation content of the rubber latex.

In particular, the core technology of the high-impact ABS-based copolymer may be referred to as an average particle diameter of a polybutadiene latex (PBL) of the core, and an appropriate particle diameter of the required rubber latex is about 3,000 to 3,500Å. . 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 produced by emulsifying a small-diameter (about 1,000 to 1,500)) PBL by emulsion polymerization, and then increasing it to emulsify. It is also possible to prepare directly through polymerization.

The large-diameter PBL prepared directly through emulsion polymerization has an advantageous advantage in terms of impact resistance due to its narrow particle size distribution and low content of coagulation, but the average particle diameter of rubber latex is closely related to the emulsion polymerization time, and in order to obtain large-diameter PBL There was a problem that the process efficiency was low because a reaction of 30 hours or more was required.

Accordingly, a method of shortening the reaction time by adding an additive such as vinyl cyanide monomer or continuously adding an emulsifier during emulsion polymerization has been proposed, but the effect is insufficient, and when the polymerization reaction temperature is increased to increase the reaction rate, the latex particle size This has caused other problems such as small and increased coagulant content.

On the other hand, the method for producing a small-diameter PBL by shortening can shorten the reaction time by about half, which is advantageous in terms of productivity, but usually uses acid as a coagulant (particle thickening agent). This is difficult, pH adjustment is required, there was a problem that a large amount of coagulum is produced.

Accordingly, a method of enlarging a small-diameter PBL using a polymer flocculant (agglomerated latex) has been proposed, and the polymer flocculant has improved impact strength compared to acetic acid, but the particle size distribution (PSD) is broad, resulting in lower fluidity, resulting in lower processability There is a need for a technology that can solve this.

Korean Registered Patent No. 384375

In order to solve the problems of the prior art as described above, this substrate is a polymer flocculant and the following formula 1

[Formula 1]

(R ₁ to R ₇ are independently a C 1 to C 5 alkyl group) using a compound represented by the stability of the latex while ensuring the productivity is excellent, both impact resistance and fluidity of the graft copolymer production method It aims to provide.

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

In addition, the present substrate is a large-diameter rubber core; And a graft polymerized shell comprising an aromatic vinyl monomer and a vinyl cyan monomer in the core, wherein the large-diameter rubber core contains a polymer flocculant in a conjugated diene rubber, and the graft copolymer is Formula 1

[Formula 1]

A vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprising a compound represented by (R ₁ to R ₇ is an alkyl group having 1 to 5 carbon atoms independently) at 2000 to 5500 ppm. It aims to provide.

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

In order to achieve the above object, the present invention is a step of preparing a conjugated diene rubber latex by adding a polymer flocculant to a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 mm 2; Including the step of adding an aromatic vinyl monomer and vinyl cyan monomer to the enlarged conjugated diene rubber latex and graft polymerization to prepare a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; Polymerization is represented by the following formula 1

[Formula 1]

It provides a method for producing a graft copolymer, characterized in that the compound represented by (R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms).

In addition, the present invention is a step of preparing a conjugated diene rubber latex by adding a polymer flocculant to a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 mm 2; Preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by introducing an aromatic vinyl monomer and a vinyl cyan monomer into the enlarged conjugated diene rubber latex and performing graft polymerization; And the step of introducing the prepared graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer into an extruder, melt-kneading, and extruding them.

[Formula 1]

(R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms) provides a method for producing a thermoplastic resin composition comprising a compound represented by.

According to the present description, the graft copolymer prepared by graft polymerization of the conjugated diene rubber latex enlarged with a polymer flocculant with an aromatic vinyl monomer and a vinyl cyan monomer in the presence of a compound having a specific structure has a reduced molecular weight distribution and an excellent graft rate. It has a synergistic effect that improves fluidity and impact resistance at the same time.

The present inventors graft polymerized with a small diameter conjugated diene rubber latex with a polymer flocculant and then graft polymerized with an aromatic vinyl monomer and a vinyl cyan monomer have excellent impact strength, but PSD (Particle Size Distribution) broadens the fluidity. As a result of relentless efforts to solve the low problem, when a thiol compound of a specific structure is added in the step of graft polymerization by adding an aromatic vinyl monomer and a vinyl cyan monomer to the conjugated diene rubber latex that has been enlarged with a polymer flocculant, impact strength and fluidity After confirming the effect of improving all of them, the present invention was completed by further focusing on the research.

The method of manufacturing the graft copolymer according to the present disclosure and the method of manufacturing the thermoplastic resin composition are divided into the following and will be described in detail.

Graft  Method for preparing copolymer

The method of manufacturing the graft copolymer of the present disclosure is a step of preparing a conjugated diene rubber latex by adding a polymer flocculant to a conjugated diene rubber latex having an average particle diameter of 500 to 1,500 mm 2 (hereinafter referred to as a 'small diameter rubber latex'). ; Including the step of adding an aromatic vinyl monomer and vinyl cyan monomer to the enlarged conjugated diene rubber latex and graft polymerization to prepare a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; Polymerization is represented by the following formula 1

[Formula 1]

(R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms) is characterized in that the compound is added, and in this case, as well as impact strength, there is an effect that the fluidity is excellent together.

When the small-diameter rubber latex is enlarged with a polymer flocculant, a unique micro-agglomerated rubber structure is formed in the rubber latex, and an effect of improving the impact strength of the graft copolymer including the same is exhibited.

The polymer flocculant may be added in an amount of 0.5 to 5 parts by weight, 1 to 4.5 parts by weight, 2 to 3.5 parts by weight, or 2 to 3 parts by weight with respect to 100 parts by weight of the conjugated diene rubber latex as an example, and this range The stability of the latex is excellent in the inside and there is an effect that the formation of coagulum is reduced.

The polymer flocculant may have, for example, an average particle diameter of 800 to 1500 mm 2, 900 to 1300 mm 2, or 900 to 1100 mm 2, and has excellent latex stability and non-interactive effect within this range.

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

The polymer flocculant may be, for example, a polymer flocculant polymerized with an unsaturated acid compound, specifically, a polymer flocculant polymerized with an unsaturated acid compound and a monomer copolymerizable therewith, and in this case, a hypertrophic effect may be obtained. great.

The unsaturated acid compound may be, for example, one or more selected from the group consisting of (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid and anhydrides thereof, and preferably includes (meth) acrylic acid In this case, more preferably, it contains methacrylic acid, and in this case, it has excellent cohesive effect and reduced coagulant production, thereby contributing to productivity improvement.

The unsaturated acid compound and the copolymerizable monomer may be, for example, one or more selected from the group consisting of (meth) acrylic acid alkyl esters, aromatic vinyl compounds, and vinyl cyan compounds, in which case latex stability is excellent and coagulation formation is reduced. It works.

The (meth) acrylic acid alkyl ester monomer may be, for example, a (meth) acrylic acid alkyl ester having 1 to 10 carbon atoms in an alkyl group, and specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ( It may be at least one selected from the group consisting of n-butyl methacrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate and 2-ethyl hexyl (meth) acrylate, preferably ethyl acrylate, n-acrylate Butyl, or mixtures thereof.

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

The aromatic vinyl monomers are, 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-bro It may be one or more selected from the group consisting of parent styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene and vinyl naphthalene.

The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.

As another example, the polymer flocculant may be, for example, a polymer flocculant having a core-shell structure, and in this case, it has an excellent effect of enlarging a small-diameter rubber latex, but has excellent stability of the enlarged rubber latex and reduced coagulant production. The effect of contributing to the improvement of productivity is great.

The core-shell structured polymer coagulant is, for example, 30 to 55% by weight of the core and 45 to 70% by weight of the shell, 35 to 50% by weight of the core and 50 to 65% by weight of the shell, or 40 to 50% by weight of the core and 50 to 50% of the shell It may be 60% by weight, excellent in the rubber latex stability is increased in this range, and the production of coagulation is reduced, and also when using it in the manufacture of a graft copolymer, there is an effect of excellent mechanical properties such as impact strength.

The core-shell structured polymer flocculant includes, for example, a polymer polymerized with 25 to 55% by weight of (meth) acrylic acid alkyl ester and 0 to 5% by weight of an unsaturated acid compound; And a polymerized shell surrounding the core and comprising 35 to 60% by weight of (meth) acrylic acid alkyl ester and 5 to 15% by weight of an unsaturated acid compound; and may be used to enlarge a small diameter rubber latex within this range. The effect is excellent, but the stability of the enlarged rubber latex is excellent and the production of coagulum is reduced, which greatly contributes to productivity improvement.

The core-shell structured polymer coagulant is another example (meth) acrylic acid alkyl ester 30 to 50% by weight and a polymerized core containing an unsaturated acid compound 0 to 5% by weight; And a polymerized shell surrounding the core and comprising 40 to 55% by weight of (meth) acrylic acid alkyl ester and 5 to 10% by weight of an unsaturated acid compound; and may be used to enlarge a small diameter rubber latex within this range. The effect is excellent, but the stability of the enlarged rubber latex is excellent and the production of coagulum is reduced, which greatly contributes to productivity improvement.

The unsaturated acid compound used in the core of the polymer flocculant may be, for example, 0.1 to 5% by weight or 0.1 to 4% by weight.

The polymer coagulant can be polymerized by including, for example, 0.05 to 1 part by weight of initiator or 0.1 to 0.5 part by weight, and has an effect of improving polymerization efficiency within this range.

The initiator may be, for example, one or more selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, and butyl hydroperoxide, and in this case, there is an effect of improving polymerization efficiency.

The polymer flocculant may be polymerized by adding, for example, 0.1 to 2 parts by weight of an emulsifier, 0.5 to 1.5 parts by weight, or 0.5 to 1 part by weight.

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

The C12-C18 alkyl sulfosuccinate metal salt 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 sulfate ester of 12 to 20 carbons or a derivative thereof, the metal salt of alkyl sulfonic acid of 12 to 20 carbons or a derivative thereof is, for example, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium It may be one or more selected from the group consisting of oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate.

In the step of preparing the enlarged conjugated diene rubber latex, for example, the conjugated diene rubber latex having an average particle size of 500 to 1,500 Å is heated to a temperature of 45 to 55 ° C or 47 to 52 ° C, and then the polymer flocculant is added for 20 to 40 minutes. Alternatively, it may be stirred for 25 to 35 minutes, and within this range, the small diameter rubber latex is uniformly enlarged and the latex stability is excellent.

The small-diameter rubber latex may have, for example, an average particle diameter of 500 to 1,500 Å, 700 to 1,200 Å or 900 to 1,100 ,, and within this range, a large-diameter latex can be enlarged within a short period of time, thereby providing excellent productivity.

The small-diameter rubber latex is, for example, 85 to 95 parts by weight of 100 parts by weight of the conjugated diene monomer, 1 to 4 parts by weight of the emulsifier, 0.1 to 0.6 parts by weight of the polymerization initiator, 0.1 to 1 parts by weight of the electrolyte, and 0.1 to 0.5 parts by weight of the molecular weight regulator Polymerizing at 50 to 60 ° C. by adding 70 to 130 parts by weight of parts and ion-exchanged water; A polymerization conversion rate of 30 to 40%, adding 0.05 to 1.2 parts by weight of the initiator, and heating to 65 to 75 ° C. to polymerize; Polymerization by introducing 5 to 15 parts by weight of the conjugated diene monomer at a polymerization conversion rate of 60 to 70%; And the polymerization conversion rate of 93 to 98% to terminate the polymerization; can be prepared, including, in this case it has the effect of stably producing a small diameter rubber latex within a short time.

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 pyrylene. It may be one or more selected from the group consisting of.

The emulsifier used in the preparation of the small-diameter rubber latex may be 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, a rubber latex having excellent stability of a polymerization reaction and having a desired particle diameter can be produced.

The electrolyte used in manufacturing the small diameter 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 latex is excellent.

The molecular weight modifier used in manufacturing the small-diameter rubber latex may be at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and carbon tetrachloride, for example, t -Dodecyl mercaptan.

Initiators used in the production of the small-diameter rubber latex include cumene hydroperoxide, diisopropyl benzenehydro peroxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, benzoyl peroxide, etc. Fat-soluble persulfate; Peroxy monomers; And redox-based polymerization initiator in combination with an oxidizing agent-reducing agent; may be one or more selected from the group consisting of, in this case, the emulsion polymerization can be efficiently performed.

The enlarged conjugated diene rubber latex may be, for example, an average particle diameter of 2,500 to 4,000 mm 2, 500 to 3,500 mm 2, 500 to 3,300 mm 2, or 2,900 to 3,300 mm 2, and grafts including the prepared latex within this range In the case of preparing a copolymer, the impact strength of the produced copolymer is excellent.

In the step of preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by graft polymerization by adding an aromatic vinyl monomer and a vinyl cyan monomer to the enlarged conjugated diene rubber latex, the graft polymerization is One

[Formula 1]

(The R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms) is added, the molecular weight distribution of the graft copolymer prepared in this case is lowered and the graft efficiency is excellent, resulting in fluidity and resistance. It has an excellent effect on both impact properties.

The R ₁ to R ₇ may be, for example, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms, and in this range, the molecular weight distribution is low and the graft efficiency is excellent, so that both fluidity and impact strength are excellent. There is.

The compound represented by Chemical Formula 1 may be 2,2,4,6,6-pentamethylheptane-4-thiol as a specific example. In this case, the molecular weight distribution is low and the graft efficiency is excellent, so that fluidity and impact strength are excellent. All have excellent effects.

The compound represented by Chemical Formula 1 is, for example, 0.25 to 0.55 parts by weight, 0.3 to 0.5 parts by weight, or 0.3 to 0.45 parts by weight based on 100 parts by weight of the total of the conjugated diene rubber latex, the aromatic vinyl monomer, and the vinyl cyan monomer. It is possible to reduce the molecular weight distribution of the graft copolymer within this range, thereby improving fluidity.

For example, 100 parts by weight of the combined conjugated diene rubber latex, aromatic vinyl monomer, and vinyl cyan monomer is 50 to 70 parts by weight of the enlarged conjugated diene rubber latex, 20 to 40 parts by weight of aromatic vinyl monomer, and 1 to 20 parts of vinyl cyan monomer. Parts by weight; Or it may be to include the 55-65 parts by weight of the conjugated diene rubber latex, 25 to 35 parts by weight of an aromatic vinyl monomer and 5 to 15 parts by weight of a vinyl cyanide monomer; excellent impact strength and physical property balance within this range It works.

The compound represented by Chemical Formula 1 may be added to the enlarged conjugated diene rubber latex by mixing with the aromatic vinyl monomer and vinyl cyan monomer, for example, and in this case, the graft polymerization reaction is uniformly performed.

The compound represented by Chemical Formula 1 serves as a molecular weight modifier as an example, and a separate molecular weight modifier may not be added during the graft polymerization reaction.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, and chlorostyrene, and the vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture date thereof. You can.

The graft copolymer may have, for example, a molecular weight distribution (MWD) of 2.0 to 2.6, 2.1 to 2.5, 2.2 to 2.5, or 2.2 to 2.4, and improve fluidity within this range, thereby improving the processability. There is.

In the present description, the molecular weight distribution can be calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

In the present description, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are each using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C. through gel chromatography (GPC) filled with porous silica as a column filling material. It can be obtained by measuring the relative value of a standard polystyrene (PS) sample.

The graft copolymer may have, for example, a graft rate of 30 to 42%, 33 to 40%, or 35 to 40%, for example, and has an excellent impact strength within this range.

Graft rate in this substrate is obtained by coagulating, washing and drying the graft polymer latex to obtain a powder form, 2 g of this powder is added to 300 ml of acetone and stirred for 24 hours, and then the solution is separated using an ultracentrifuge and separated acetone solution. Drop into methanol to obtain an ungrafted portion. It was dried to measure the weight and then calculated according to Equation 1 below.

[Equation 1]

Graft rate (%) = weight of grafted monomer (g) / rubber weight (g) x 100

When the graft polymerization is an example, 0.01 to 1 part by weight of the initiator may be added, and the stability of the polymerization reaction is excellent and the polymerization efficiency is improved within the above range.

Examples of the initiators include fat-soluble persulfate such as cumene hydroperoxide, diisopropyl benzenehydro peroxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, and benzoyl peroxide; Peroxy monomers; And redox-based polymerization initiator in combination of an oxidizing agent-reducing agent; may be one or more selected from the group consisting of, in this case, the polymerization can be efficiently performed.

In the polymerization of the graft copolymer, for example, an oxidation-reduction catalyst may be further included. The oxidation-reduction catalyst is not particularly limited as long as it is a type used in the manufacture of graft copolymers, and can be selected and used as needed.

The step of preparing the graft copolymer may include, for example, aggregating, aging, dehydrating and drying the latex prepared after the graft polymerization, and the graft copolymer prepared by including the step is in powder form. It can be provided as. The agglomeration, aging, dehydration and drying steps are not particularly limited when the method is generally used in the art.

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

Other reaction conditions, such as reaction time, reaction temperature, pressure, reactant input time, etc. in the method for preparing a graft copolymer in addition to the above-described substrates are not particularly limited if they are within the range commonly used in the technical field to which the present invention pertains. It can be carried out by appropriately selecting according to.

Manufacturing method of thermoplastic resin composition

인 공액디엔 고무 라텍스에 고분자 응집제를 투입하여 비대화된 공액디엔 고무 라텍스를 제조하는 단계; 상기 비대화된 공액디엔 고무 라텍스에 방향족 비닐 단량체 및 비닐시안 단량체를 투입하고 그라프트 중합시켜 비닐시안 화합물-공액디엔 화합물-방향족 비닐 화합물 그라프트 공중합체를 제조하는 단계; 및 제조된 그라프트 공중합체 및 방향족 비닐 화합물-비닐시안 화합물 공중합체를 압출기에 투입하고 융융혼련한 후 압출하는 단계;를 포함하되, 상기 그라프트 중합은 하기 화학식 1The manufacturing method of the thermoplastic resin composition of the base material is 500 to 1,500 average particle diameter.

Preparing a hyperconjugated conjugated diene rubber latex by adding a polymer flocculant to the phosphorus conjugated diene rubber latex; Preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by introducing an aromatic vinyl monomer and a vinyl cyan monomer into the enlarged conjugated diene rubber latex and performing graft polymerization; And a step of introducing the prepared graft copolymer and aromatic vinyl compound-vinyl cyan compound copolymer into an extruder, melt-kneading, and extruding them.

[Formula 1]

It is characterized in that it comprises a compound represented by (R ₁ to R ₇ is an alkyl group having 1 to 5 carbon atoms independently), there is an effect of improving both the impact strength and fluidity of the thermoplastic resin composition prepared in this case. .

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

The aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 100,000 to 200,000 g / mol, 110,000 to 170,000 g / mol, or 130,000 to 150,000 g / mol, and excellent impact strength within this range. It works.

In this description, the weight average molecular weight is a relative value to a standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica with a column filling material. It can be obtained by measuring.

The aromatic vinyl compound-vinyl cyan compound copolymer is, for example, an aromatic vinyl compound 60 to 95% by weight, 65 to 90% by weight, or 70 to 85% by weight; And 5 to 40% by weight of vinyl cyan compound, 10 to 35% by weight, or 15 to 30% by weight; may include a polymerized copolymer.

The melt-kneading may be performed at 200 to 280 ° C, or 220 to 260 ° C, for example.

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

When melt-kneading, one or more additives selected from the group consisting of a colorant, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a lubricant, a plasticizer, an antistatic agent, and a processing aid may be selectively added as necessary.

In the manufacturing method of the thermoplastic resin composition, the content overlapping with the step of preparing the graft copolymer described above is omitted.

The thermoplastic resin composition has, for example, an Izod impact strength (thickness 1/4 ") measured in accordance with ASTM D256 of 26 kgf · cm / cm or more, or 26 to 30 kgf · cm / cm, and an impact strength within the above range. It is excellent and can be applied to various products.

The thermoplastic resin composition may have, for example, a flow index (220 ° C., 10 kg) measured according to ASTM D1238 of 18 g / 10 min or more, 18-25 g / 10 min, or 18.8-20 g / 10 min. Excellent fluidity within the range, there is an effect of easy processing.

The present invention may include, for example, a method for manufacturing an injection molded article comprising a method for manufacturing a thermoplastic resin composition according to the present disclosure.

The manufacturing method of the injection molded article may include, for example, injection molding the thermoplastic resin composition according to the present disclosure using an injection machine.

The injection molded article may be, for example, an electrical component, an electronic component, an office equipment, or an automobile component.

The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure includes a large-diameter rubber core; And a graft polymerized shell comprising an aromatic vinyl monomer and a vinyl cyan monomer in the core, wherein the large-diameter rubber core contains a polymer flocculant in a conjugated diene rubber, and the graft copolymer is Formula 1

 [Formula 1]

(R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms), characterized in that it comprises a compound of 2000 to 5500 ppm, in this case, the impact strength and fluidity is excellent effect.

The graft copolymer may include, for example, 2500 to 5000 ppm, 3000 to 4800 ppm, or 3200 to 4500 ppm of the compound represented by Chemical Formula 1, and has excellent effects in both impact strength and fluidity within this range. have.

The content of the compound represented by Chemical Formula 1 in the graft copolymer can be obtained from the following formula after measuring the content of S element using ion chromatography (IC-AQP).

[Equation 2]

Content of Formula 1 (ppm) = [(S element content of final graft copolymer-S element content of small diameter rubber latex)] X (molecular weight of formula 1) / (mole mass of S element)

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

 [Example]

<Preparation Example 1: Preparation of polymer flocculant>

To the reactor, 208 parts by weight of distilled water, 0.75 parts by weight of an emulsifier (dioctyl sulfosuccinate sodium, DOSS) were added and stirred while heating to 80 ° C., 0.2 parts by weight of an initiator (potassium persulfate, KPS) and butyl acrylate (BA ) 50 parts by weight was added and reacted for 90 minutes. Subsequently, 41 parts by weight of butyl acrylate and 9 parts by weight of methacrylic acid (MAA) were added to react, and finally, a polymer coagulant having a core-shell structure having an average particle diameter of 1,000 MPa (weight ratio of core to shell: 50:50, core: 50 parts by weight of BA, shell 41 parts by weight of BA and 9 parts by weight of MAA) were obtained.

<Production Example 2: Preparation of small-diameter rubber latex>

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 as an electrolyte ( K2CO3) 0.1 parts by weight, 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) as molecular weight regulator, 0.15 parts by weight of tertiary butyl hydroperoxide as initiator, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrophosphate and ferrous sulfate 0.0025 parts by weight was put in a batch and polymerization reaction was started at 55 ° C. After 0.3% by weight of potassium persulfate was added to the polymerization conversion rate of 30 to 40%, the temperature was raised to 72 ° C to perform polymerization reaction, and then 10% by weight of 1,3-butadiene was added from 60 to 70% of polymerization conversion rate, followed by polymerization conversion rate of 95 The reaction was terminated at%. At this time, the average particle size of the small-diameter rubber latex was 1,000 mm 2.

<Preparation Example 3: Preparation of large-diameter rubber latex by enlarging with a polymer flocculant>

The reactor was stirred while heating 100 parts by weight of the small-diameter rubber latex (average particle size 1,000 Å) prepared in Preparation Example 2 (based on solid content) at 50 ° C., and then the core-shell structured polymer flocculant prepared in Preparation Example 1 was 2.2. After adding the parts by weight, the mixture was agitated for 30 minutes, and then the enlarged rubber latex had an average particle diameter of 2930 mm 2 and a PSD of 0.65.

<Preparation Example 4: Preparation of large-diameter rubber latex by making it large by polymer flocculant>

The reactor was stirred while heating 100 parts by weight of the small-diameter rubber latex (average particle size 1,000Å) prepared in Preparation Example 2 (based on solid content) at 50 ° C., and the core-shell structured polymer flocculant prepared in Preparation Example 1 was 1.1. After adding the weight part, the mixture was agitated and stirred for 30 minutes, and the enlarged rubber latex had an average particle diameter of 2,540 mm 2 and a PSD of 0.68.

<Preparation Example 5: Preparation of large-diameter rubber latex by enlarging with a polymer flocculant>

The reactor was stirred while heating 100 parts by weight of the small-diameter rubber latex (average particle size 1,000 Å) prepared in Preparation Example 2 (based on solid content) at 50 ° C., and the core-shell structured polymer flocculant prepared in Preparation Example 1 was 3.3. After adding the parts by weight, the mixture was agitated for 30 minutes, and then the enlarged rubber latex had an average particle size of 3,110 mm 3 and a PSD of 0.60.

<Preparation Example 6: Preparation of large-diameter rubber latex by making it large by polymer flocculant>

The reactor was stirred while heating 100 parts by weight of the small-diameter rubber latex (average particle size 1,000 Å) prepared in Preparation Example 2 (based on solid content) at 50 ° C., and the core-shell structured polymer flocculant prepared in Preparation Example 1 was 4.4. After adding the weight part, the mixture was agitated and stirred for 30 minutes, and the enlarged rubber latex had an average particle diameter of 3,300 mm 3 and a PSD of 0.56.

<Production Example 7: Preparation of large-diameter rubber latex by blotting with acetic acid>

The reactor was stirred while heating 100 parts by weight of the small-diameter rubber latex (average particle size 1,000 제조) prepared in Preparation Example 2 at 40 ° C., and then 0.1 parts by weight of stabilized emulsifier and 2.83 parts by weight of acetic acid were added, followed by stirring for 10 minutes. In this case, the rubberized latex, which was enlarged, had an average particle size of 3080 Å and a PSD of 0.37.

<Preparation of graft copolymer and thermoplastic resin composition>

Example  One

28.8 parts by weight of styrene, 11.2 parts by weight of acrylonitrile, and 2,2,4,6,6-pentamethylheptane-4-thiol (PMH) to 60 parts by weight of the unsaturated rubber latex prepared from Preparation Example 3 (based on solid content) 0.34 parts by weight of the mixture was continuously added for 3 hours and subjected to graft polymerization to obtain an ABS graft copolymer latex. The obtained ABS graft copolymer latex as an antioxidant was added 1.2 parts by weight of an emulsion (average particle size 0.9㎛) mixed with Wingstay-L (Raton Korea) and IR107 (Raton Korea) at a weight ratio of 0.8: 0.2 84 After heating up to ℃ ℃ was added to magnesium sulfate (MgSO ₄ ) 3.0 parts by weight to aggregate. Thereafter, the temperature was raised to 94 ° C over 10 minutes, followed by dehydration in a dehydrator, followed by drying in an oven to obtain powder.

Subsequently, the ABS graft copolymer powder 25% by weight and acrylonitrile-styrene copolymer 75% by weight were added to a mixer to be mixed, then pelletized using a twin-screw extruder, and then a specimen for physical property measurement using an injection machine Was produced. The acrylonitrile-styrene copolymer is a copolymer having a weight average molecular weight of 140,000 g / mol, and 24% by weight of acrylonitrile and 76% by weight of styrene.

Example  2

In Example 1, 2,2,4,6,6-pentamethylheptane-4-thiol was used in the same manner as in Example 1, except that 0.42 parts by weight was used.

Example  3

In Example 1, 2,2,4,6,6-pentamethylheptane-4-thiol was used in the same manner as in Example 1, except that 0.50 parts by weight was used.

Example  4

It was carried out in the same manner as in Example 1, except that the enlarged rubber latex prepared from Preparation Example 4 was used instead of the enlarged rubber latex prepared from Preparation Example 3 in Example 1.

Example  5

It was carried out in the same manner as in Example 1, except that the enlarged rubber latex prepared from Preparation Example 5 was used instead of the enlarged rubber latex prepared from Preparation Example 3 in Example 1.

Example  6

It was carried out in the same manner as in Example 1 except that in Example 1, instead of the enlarged rubber latex prepared in Preparation Example 3, the enlarged rubber latex prepared in Preparation Example 6 was used.

Comparative example  One

As in Example 1, except that 0.34 parts by weight of t-dodecyl mercaptan (TDDM) was used as a molecular weight modifier in Example 1 instead of 2,2,4,6,6-pentamethylheptane-4-thiol. It was carried out.

Comparative example  2

It was carried out in the same manner as in Example 1, except that 0.50 parts by weight of t-dodecyl mercaptan was used instead of 2,2,4,6,6-pentamethylheptane-4-thiol in Example 1.

Comparative example  3

It was carried out in the same manner as in Example 1, except that 0.34 parts by weight of t-dodecyl mercaptan was used in the enlarged rubber latex prepared from Preparation Example 7 instead of the enlarged rubber latex prepared from Preparation Example 3 in Example 1. .

Comparative example  4

In Example 1, 0.42 parts by weight of 2,2,4,6,6-pentamethylheptane-4-thiol was used for the non-sized rubber latex prepared in Example 7 instead of the large-sized rubber latex prepared in Preparation Example 3. Then, it was carried out in the same manner as in Example 1.

Reference example  One

In Example 1, 2,2,4,6,6-pentamethylheptane-4-thiol was used in the same manner as in Example 1, except that 0.10 part by weight was used.

Reference example  2

In Example 1, 2,2,4,6,6-pentamethylheptane-4-thiol was used in the same manner as in Example 1, except that 0.65 parts by weight was used.

[Test Example]

The properties of the specimens prepared in Examples 1 to 6, Comparative Examples 1 to 4 and Reference Examples 1 to 2 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

How to measure

) 측정: 입도분석기(particle size analyzer: NICOMP 380)로 측정하였다.* Average particle size (

) Measurement: Measured with a particle size analyzer (NICOMP 380).

* PSD (Particle Size Distribution): measured by particle size analyzer (particle size analyzer: NICOMP 380).

* Number average molecular weight (Mn; g / mol): relative to a standard PS (Standard polystyrene) sample using THF as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica with a column filling material The value was measured.

* Weight average molecular weight (Mw; g / mol): Relative to standard PS (Standard polystyrene) sample using THF as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica with column filling material The value was measured.

* Molecular Weight Distribution (MWD): Calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

* Graft rate (GR;%): Graft polymer latex is coagulated, washed and dried to obtain a powder form, 2 g of this powder is added to 300 ml of acetone and stirred for 24 hours, and then the solution is separated and separated using an ultracentrifuge. The diluted acetone solution is dropped into methanol to obtain an ungrafted portion. It was dried to measure the weight, and then calculated according to the following formula.

[Equation 1]

Graft rate (%) = weight of grafted monomer (g) / rubber weight (g) x 100

* Izod impact strength (kgf · cm / cm): Specimen thickness 1/4 ″ was measured according to ASTM D256.

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

* PMH content in graft resin (ppm): The content of S element was measured using Ion Chromatography (ICAQP) method, and then obtained through the following equation.

[Equation 2]

PHM content (ppm) = [(S element content of final graft copolymer-S element content of small diameter rubber latex)] X (molecular weight of PHM) / (molar mass of S element)

In Equation 2, the molecular weight of PHM was 202.40 g / mol, and the molar mass of S element was 32.07 g / mol.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Large caliber
Rubber
Latex Kinds Preparation Example 3 Preparation Example 3 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Polymer
Flocculant
(Parts by weight) 2.2 2.2 2.2 1.1 3.3 4.4 Average particle diameter
(Å) 2930 2930 2930 2540 3110 3300 PSD 0.65 0.65 0.65 0.68 0.60 0.56 ABS
Graft
Copolymer PMH
(Parts by weight) 0.34 0.42 0.50 0.42 0.42 0.42 Mn (× 10 ⁵ ) 3.60 3.42 3.08 3.38 3.44 3.40 Mw (× 10 ⁵ ) 8.01 8.10 7.25 8.00 7.88 8.09 MWD 2.25 2.37 2.41 2.36 2.29 2.38 PSD 0.64 0.65 0.65 0.69 0.61 0.56 GR (%) 39.7 36.1 33.6 35.7 36.0 36.5 PMH content
(ppm) 3220 4010 4760 3980 4010 3930 Thermoplastic
Suzy
Composition Impact strength 27.4 29.0 26.0 28.8 29.2 29.0 MI 19.1 19.4 19.3 20.0 18.9 18.8

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Reference Example 1 Reference Example 2 Large caliber
Rubber
Latex Kinds Preparation Example 3 Preparation Example 3 Preparation Example 7 Preparation Example 7 Preparation Example 3 Preparation Example 3 Polymer
Flocculant
(Parts by weight) 2.2 2.2 - - 2.2 2.2 Acetic acid
(Parts by weight) - - 1.7 1.7 - - Average particle diameter
(Å) 2930 2930 3080 3080 2950 2950 PSD 0.65 0.65 0.37 0.37 0.64 0.64 ABS
Graft
Copolymer PMH
(Parts by weight) - - - 0.42 0.1 0.65 TDDM
(Parts by weight) 0.34 0.50 0.34 - - - Mn (× 10 ⁴ ) 3.84 3.60 3.60 3.52 4.98 2.78 Mw (× 10 ⁴ ) 10.9 10.3 10.5 8.08 12.60 7.22 MWD 2.84 2.91 2.90 2.31 2.54 2.60 PSD 0.63 0.64 0.38 0.40 0.66 0.69 GR (%) 46.8 45.4 31.4 33.2 55.2 30.7 PMH content
(ppm) - - - 3500 430 5400 Thermoplastic
Suzy
Composition Impact strength 25.3 19.5 20.9 20.5 24.5 23.5 MI 17.1 19.0 20.8 22.1 14.9 23.3

As shown in Table 1 and Table 2, Examples 1 to 6 containing the polymer flocculant and 2,2,4,6,6-pentamethylheptane-4-thiol according to the present invention are prepared graft copolymers The MWD is low, the graft ratio is within 30 to 42%, and the thermoplastic resin composition containing the same had excellent synergistic effects both in impact strength and fluidity.

On the other hand, Comparative Examples 1 and 2 containing the polymer flocculant and t-dodecyl mercaptan have a high MWD of the graft copolymer, the graft ratio exceeds 42%, and the thermoplastic resin composition containing the same has both impact strength and fluidity. Fell.

In addition, in Comparative Examples 3 and 4 including acetic acid, the PSD has a narrow fluidity, but the rubber latex aggregated with acetic acid does not have a unique micro-agglomerated rubber structure unlike rubber latex in which a polymer flocculant is added. Impact strength was lowered.

In addition, Reference Example 1, which contains 0.1 parts by weight of 2,2,4,6,6-pentamethylheptane-4-thiol in the polymer flocculant, has a very high weight average molecular weight and graft rate compared to Examples 1 to 6, and has low fluidity. As a reference, Example 2 containing 2,2,4,6,6-pentamethylheptane-4-thiol as a polymer flocculant in 0.65 parts by weight has a very low weight average molecular weight and lowered impact strength compared to Examples 1 to 6.

Claims (15)

Preparing an enlarged conjugated diene rubber latex by adding a polymer flocculant to the conjugated diene rubber latex having an average particle diameter of 500 to 1,500 mm 2; And
Including the step of preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by graft polymerization by adding an aromatic vinyl monomer and a vinyl cyan monomer to the enlarged conjugated diene rubber latex.
The graft polymerization is the following formula 1
[Formula 1]

(R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms) characterized in that the compound is added
Method for producing graft copolymer.
According to claim 1,
The polymer flocculant is characterized in that 0.5 to 5 parts by weight based on 100 parts by weight of the conjugated diene rubber latex (based on solids)
Method for producing graft copolymer.
According to claim 1,
The polymer flocculant is characterized in that the average particle diameter is 800 to 1500 Å
Method for producing graft copolymer.
According to claim 1,
The polymer flocculant is a polymer flocculant polymerized with an unsaturated acid compound.
Method for producing graft copolymer.
According to claim 1,
The polymer flocculant is a polymer flocculant having a core-shell structure.
Method for producing graft copolymer.
The method of claim 5,
The core-shell structured polymer flocculant comprises 30 to 55 wt% core and 45 to 70 wt% shell
Method for producing graft copolymer.
The method of claim 5,
The polymer flocculant comprises a polymer core comprising 25 to 55% by weight of (meth) acrylic acid alkyl ester and 0 to 5% by weight of an unsaturated acid compound; And a shell wrapped around the core and comprising 35 to 60% by weight of (meth) acrylic acid alkyl ester and 5 to 15% by weight of unsaturated acid compound;
Method for producing graft copolymer.
According to claim 1,
The step of preparing the enlarged conjugated diene rubber latex is characterized in that the conjugated diene rubber latex having an average particle size of 500 to 1,500 mm 2 is heated to a temperature of 45 to 55 ° C., and then the polymer flocculant is added thereto and stirred for 20 to 40 minutes.
Method for producing graft copolymer.
According to claim 1,
The enlarged conjugated diene rubber latex is characterized in that the average particle diameter of 2500 to 4000 Å
Method for producing graft copolymer.
According to claim 1,
The compound represented by Chemical Formula 1 is characterized in that it is 0.25 to 0.55 parts by weight based on 100 parts by weight of the total of the hyperconjugated conjugated diene rubber latex, aromatic vinyl monomer, and vinyl cyan monomer.
Method for producing graft copolymer.
According to claim 1,
The compound represented by Chemical Formula 1 is mixed with the aromatic vinyl monomer and the vinyl cyan monomer, and characterized in that it is added to the enlarged conjugated diene rubber latex.
Method for producing graft copolymer.
According to claim 1,
The graft copolymer is characterized in that the molecular weight distribution (Molecular Weight Distribution) is 2.0 to 2.6
Method for producing graft copolymer.
According to claim 1,
The graft copolymer is characterized in that the graft ratio is 30 to 42%
Method for producing graft copolymer.
Average particle size 500 to 1,500

Preparing a hyperconjugated conjugated diene rubber latex by adding a polymer flocculant to the phosphorus conjugated diene rubber latex;
Preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by introducing an aromatic vinyl monomer and a vinyl cyan monomer into the enlarged conjugated diene rubber latex and performing graft polymerization; And
Including the prepared vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and aromatic vinyl compound-vinyl cyan compound copolymer into an extruder, melt-kneaded and extruded;
The graft polymerization is the following formula 1
[Formula 1]

(R ₁ to R ₇ are independently an alkyl group having 1 to 5 carbon atoms), characterized in that it comprises a compound represented by
Method for manufacturing a thermoplastic resin composition.
Large diameter rubber core; And a graft polymerized shell containing an aromatic vinyl monomer and a vinyl cyan monomer in the core.
The large-diameter rubber core contains a polymer flocculant in the conjugated diene rubber,
The graft copolymer is represented by Chemical Formula 1
[Formula 1]

A vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprising a compound represented by (R ₁ to R ₇ is an alkyl group having 1 to 5 carbon atoms independently) at 2000 to 5500 ppm.