KR20220023126A - Method for preparing graft copolymer, graft copolymer and thermoplastic resion composition comprising graft copolymer - Google Patents

Abstract

The present invention relates to a preparation method of a graft copolymer which comprises a step of adding, to a reactor, a compound represented by chemical formula 1, a diene-based rubbery polymer, a (meth)acrylate-based monomer, a vinyl aromatic monomer, and a vinyl cyanide-based monomer and polymerizing the same, a graft copolymer, and a thermoplastic resin composition comprising the same.

Description

Method for producing a graft copolymer, a thermoplastic resin composition comprising a graft copolymer and a graft copolymer TECHNICAL FIELD

The present invention relates to a method for preparing a graft copolymer, a graft copolymer and a thermoplastic resin composition comprising the graft copolymer, and a method for preparing a graft copolymer excellent in processability, transparency and mechanical properties, the graft copolymer It relates to a thermoplastic resin composition comprising a copolymer and a graft copolymer.

The transparent thermoplastic resin composition is a (meth) acrylate-based monomer unit, a vinyl aromatic monomer unit, and a graft copolymer comprising a diene-based rubber polymer in which a vinyl cyanide-based monomer unit is grafted, and a (meth) acrylate-based monomer A non-graft copolymer including a unit, a vinyl aromatic monomer unit, and a vinyl cyanide monomer unit is uniformly mixed and then extruded. Here, the transparency of the thermoplastic resin composition may be improved as the refractive indices of the graft copolymer and the non-graft copolymer match, or the refractive indices of the diene-based rubber polymer and the remaining components match.

On the other hand, in order to prepare a thermoplastic resin composition that matches the refractive index of a butadiene rubber polymer, which is a type of diene-based rubbery polymer, methyl having a low refractive index among acrylonitrile monomers, styrene monomers and methyl methacrylate monomers, which are raw materials constituting the matrix region. A high content of methacrylate monomer is used. However, unlike the acrylonitrile monomer that improves chemical resistance, methyl methacrylate not only decreases chemical resistance, but also tends to further decrease chemical resistance as the content increases. In addition, methyl methacrylate is thermally decomposed at a high temperature of 300 ° C. or higher, and may deteriorate the color and thermal stability of the final product.

In order to improve this problem, methods for improving chemical resistance by using a styrene-butadiene rubber polymer instead of a butadiene rubber polymer to increase the refractive index of the product and lower the methyl methacrylate monomer content have been proposed.

In addition, there are US3,787,522A and JP1988-042940B as a technology for producing a transparent thermoplastic resin composition having excellent transparency and mechanical properties so far, and these patents disclose a method for imparting impact resistance to transparent polymethyl methacrylate. there is. However, this method has excellent transparency and processability, but has very weak impact resistance, so there is a limit to product application.

In order to solve this problem, research is being conducted to prepare a thermoplastic resin composition excellent in transparency and mechanical properties by improving the physical properties of the graft copolymer.

US3,787,522A JP1988-042940B

An object to be solved by the present invention is to provide a graft copolymer excellent in processability, transparency and mechanical properties, a method for preparing the same, and a thermoplastic resin composition including the same.

In order to solve the above problems, the present invention is a reactor, a compound represented by the following formula (1), a diene-based rubber polymer, a (meth) acrylate-based monomer, a vinyl aromatic monomer, and a vinyl cyanide-based monomer are introduced and polymerized It provides a method for preparing a graft copolymer comprising the steps of:

<Formula 1>

In Formula 1,

L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,

R ₂ to R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a silica unit, but at least one of R ₂ to R ₄ is a silica unit.

In addition, the present invention, in a reactive group, at least one member selected from the group consisting of a compound represented by Formula 1, a derivative of the compound represented by Formula 1, and a monomer unit represented by Formula 1; And it provides a graft copolymer comprising a diene-based rubbery polymer to which a vinyl aromatic monomer unit and a vinyl cyanide-based monomer unit are grafted.

In addition, the present invention is the above-mentioned graft copolymer; And (meth) provides a thermoplastic resin composition comprising a non-graft copolymer comprising an acrylate-based monomer unit, a vinyl aromatic monomer unit, and a vinyl cyanide-based monomer unit.

In addition, the present invention provides a thermoplastic resin molded article prepared from the above-described thermoplastic resin composition, having a transparency measured according to ASTM D1003 of 3.6% or less, and having an impact strength of 25 kg·cm/cm or more measured according to ASTM D256 do.

The graft copolymer and the thermoplastic resin composition according to the present invention are excellent in processability, transparency and mechanical properties.

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

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Definition of Terms

The term 'average particle diameter' used in the present invention may mean an arithmetic average particle diameter in a particle size distribution measured by dynamic light scattering, specifically, an average particle diameter of scattering intensity. The average particle diameter can be measured using Nicomp 380 equipment (product name, manufacturer: PSS Nicomp).

As used herein, the term 'index of refraction' refers to the absolute refractive index of a material, which can be recognized as the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in a material, where the radiation has a wavelength of 450 nm. It may be visible light having a wavelength of to 680 nm, and specifically, it may be visible light having a wavelength of 589.3 nm. The refractive index can be measured using a known method, that is, an Abbe Refractometer.

The term 'polymerization conversion rate' used in the present invention can be calculated from the following formula:

Polymerization conversion (%) = {(total weight of monomers added until polymerization is completed)-(total weight of unreacted monomers at the time when polymerization conversion is measured)}/ (total weight of monomers added until polymerization is complete) weight) × 100

The term 'diene-based rubbery polymer' used in the present invention may refer to a synthetic rubber prepared by cross-linking and polymerizing a diene-based monomer.

The diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene is preferable.

The diene-based rubbery polymer may have an average particle diameter of 50 to 500 nm, preferably 100 to 400 nm. When the above conditions are satisfied, a graft copolymer having excellent impact resistance and surface gloss can be prepared.

The term '(meth)acrylate-based monomer' used in the present invention includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate pentyl (meth)acrylate, Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate and decyl (meth) It may mean at least one selected from the group consisting of acrylates. The (meth)acrylate-based monomer is preferably methyl methacrylate.

The term 'vinyl aromatic monomer' used in the present invention includes styrene, α-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, 4-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 4- It may mean at least one selected from the group consisting of bromostyrene and 2-bromostyrene. The vinyl aromatic monomer is preferably styrene.

The term 'vinyl cyanide-based monomer' used in the present invention may mean at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and 2-chloroacrylonitrile. The vinyl cyanide-based monomer is preferably acrylonitrile.

The term '(meth)acrylate-based monomer unit' used in the present invention may be a unit derived from a (meth)acrylate-based monomer.

The term 'vinyl aromatic monomer unit' used in the present invention may be a unit derived from a vinyl aromatic monomer.

The term 'vinyl cyanide-based monomer unit' used in the present invention may be a unit derived from a vinyl cyanide-based monomer.

The term 'alkyl group' used in the present invention may be a linear or cyclic alkyl group. Specific examples of the C ₁ to C ₁₀ alkyl group include a methyl group, cyclopentylmethyl group, cyclohexylmethyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, n-butyl group , isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, n-pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 2-propylpentyl group, n-hexyl group, isohexyl group, 1-methylhexyl group , 4-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, n-heptyl group, tert-heptyl group, 2,2-dimethylheptyl group, n-octyl group, tert-octyl group, n-no Nyl group, tert-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclo and a hexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The term 'alkylene group' used in the present invention refers to a thing having two bonding positions in an alkyl group, that is, a divalent group. Except that these are divalent groups, the above description of the alkyl group may be applied.

The term 'silica unit' used in the present invention may be a unit derived from silica. Here, the silica may be in an oligomeric or polymeric form.

In order to minimize the effect on the transparency of the thermoplastic resin composition, it is preferable to use transparent or opalescent silica.

As the silica, commercially available products may be used, and specifically, ST-O (average particle diameter: 10 to 20 nm) manufactured by Nissan Chemical America Corporation may be used.

1. Method for preparing graft copolymer

The method for producing a graft copolymer according to an embodiment of the present invention comprises a compound represented by the following Chemical Formula 1 in a reactor, a diene-based rubbery polymer, a (meth)acrylate-based monomer, a vinyl aromatic monomer, and a vinyl cyanide-based monomer. Including the step of adding the monomer and polymerization.

<Formula 1>

In Formula 1,

L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,

R ₂ to R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a silica unit, but at least one of R ₂ to R ₄ is a silica unit.

The compound represented by Formula 1 may improve mechanical properties while maintaining the processability and transparency of the graft copolymer at the same level as before.

In Formula 1, L ₁ is a C ₁ to C ₄ alkylene group, R ₁ is a C ₁ to C ₄ alkyl group, R ₂ to R ₄ are each independently hydrogen or a silica unit, but not all hydrogen That is, at least one of R ₂ to R ₄ is preferably a silica unit. When the above-described conditions are satisfied, the graft copolymer may have excellent transparency, and mechanical properties may be improved.

Meanwhile, the compound represented by Formula 1 may be prepared by the method described in Scheme 1 below.

<Scheme 1>

Referring to Scheme 1, the compound represented by Formula 1 is a compound represented by Formula 1-1 (R ₁ is a C ₁ to C ₄ alkyl group, R ₂ to R ₄ are each independently C ₁ to C ₁₀ , which is an alkyl group); After surface-modifying the hydrolyzate with silica, centrifuging to remove the supernatant, and drying the remainder; may be prepared by a manufacturing method comprising. Hydrolysis may occur in an aqueous solvent including water and alcohol, and in order to promote hydrolysis, the pH of the aqueous solvent may be adjusted to 4 to 5.

And, in order to maximize the effect of improving the mechanical properties of the compound represented by Formula 1, it is preferable that the entire surface of the compound is modified with silica.

The compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1-1 to 1-3, and among these, compounds represented by Formula 1-3 are preferred:

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

At least one selected from the group consisting of compounds represented by Formulas 1-1 to 1-3 may be prepared by the method described in Scheme 1-1 below.

<Reaction Scheme 1-1>

On the other hand, 0.1 to 1.5 parts by weight of the compound represented by Formula 1, based on 100 parts by weight of the total of the diene-based rubbery polymer, (meth)acrylate-based monomer, vinyl aromatic monomer, and vinyl cyanide-based monomer, preferably Preferably, it can be added to the reactor in an amount of 0.4 to 1 part by weight. When the above-mentioned conditions are satisfied, a graft copolymer with improved mechanical properties while maintaining transparency at the same level as before can be prepared.

The diene-based rubber polymer is used in an amount of 40 to 60 parts by weight, preferably 45 to 55 parts by weight, based on 100 parts by weight of the total of the (meth)acrylate-based monomer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. can be put into When the above-described conditions are satisfied, a graft copolymer having excellent impact resistance can be prepared.

20 to 45 parts by weight, preferably 25 to 40 parts by weight, based on 100 parts by weight of the (meth)acrylate-based monomer, the total of the (meth)acrylate-based monomer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer It can be added to the reactor by part. When the above conditions are satisfied, a graft copolymer having excellent transparency can be prepared.

The vinyl aromatic monomer, 5 to 20 parts by weight, preferably 7 to 15 parts by weight, based on 100 parts by weight of the total of the (meth) acrylate-based monomer, the vinyl aromatic monomer and the vinyl cyanide-based monomer in the reactor can be put into When the above conditions are satisfied, a graft copolymer having excellent processability can be prepared.

The vinyl cyanide-based monomer is added in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the total of the (meth)acrylate-based monomer, the vinyl aromatic monomer and the vinyl cyanide-based monomer. It can be put into the reactor. When the above conditions are satisfied, a graft copolymer having excellent chemical resistance and excellent color characteristics can be prepared.

In order to improve polymerization stability, the compound represented by Formula 1 is preferably continuously introduced into the reactor.

The starting time of continuous input of the compound represented by Formula 1 may be a time point at which the polymerization conversion rate is 0% to 10%, preferably 0% to 5%. When the above-described conditions are satisfied, the compound represented by Formula 1 may be uniformly dispersed in the polymerization solution, and thus the transparency of the graft copolymer may be realized at the same level as before.

The continuous input of the compound represented by Chemical Formula 1 may be terminated at a time point from a polymerization conversion rate of 60% to a polymerization completion time point, preferably from 70 to 90%. When the above conditions are satisfied, polymerization can be stably performed.

Meanwhile, in order to improve polymerization stability, it is preferable to continuously introduce a (meth)acrylonitrile-based monomer, a vinyl aromatic monomer and a vinyl cyanide-based monomer to the reactor together with the compound represented by Formula 1 above.

The polymerization is preferably emulsion polymerization capable of producing a graft copolymer having excellent surface gloss and mechanical properties.

The emulsion polymerization may be carried out in the presence of at least one selected from the group consisting of an emulsifier, an initiator, an activator, a molecular weight regulator, and an aqueous solvent.

The emulsifiers include sodium dicyclohexyl sulfosuccinate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate, potassium rosinate and sodium rosin. It may be at least one selected from the group consisting of nates.

The emulsifier is present in an amount of 0.15 to 2.0 parts by weight, preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, (meth)acrylate-based monomer, vinyl cyanide-based monomer and vinyl aromatic monomer. can When the above-mentioned range is satisfied, it is possible to prepare a graft copolymer having a desired average particle diameter while improving polymerization stability.

The initiator is sodium persulfate, potassium persulfate, ammonium persulfate, hydroperoxide, t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide Oxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azo It may be at least one selected from the group consisting of bis-isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis cyclohexanecarbonitrile, and azobis-isobutyric acid (butyric acid) methyl, of which hydroperoxide is preferable

The initiator is used in an amount of 0.001 to 1.0 parts by weight, preferably 0.01 to 0.8 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, (meth)acrylate-based monomer, vinyl cyanide-based monomer and vinyl aromatic monomer. may exist. When the above-mentioned range is satisfied, the residual amount of the initiator in the graft copolymer can be minimized while improving the polymerization stability of the graft polymerization.

In order to promote the initiation reaction together with the initiator, an activator may be further added. The activator may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, disodium ethylenediamine tetraacetate, iron (II) sulfate, dextrose, tetrasodium pyrophosphate, sodium pyrophosphate anhydros and sodium sulfate. Among them, at least one selected from the group consisting of disodium ethylenediamine tetraacetate, iron (II) sulfate, and sodium formaldehyde sulfoxylate is preferable.

The activator is used in an amount of 0.001 to 0.5 parts by weight, preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, (meth)acrylate-based monomer, vinyl cyanide-based monomer and vinyl aromatic monomer. may exist. If the above-mentioned range is satisfied, the residual amount of the activator in the graft copolymer may be minimized while improving polymerization stability.

The molecular weight modifier may be at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan and α-methyl styrene dimer, of which t-dodecyl mercaptan and α-methyl styrene dimer are desirable.

The molecular weight modifier is 0.1 to 1.0 parts by weight, preferably 0.2 to 0.8 parts by weight, based on 100 parts by weight of the total of the diene-based rubbery polymer, (meth)acrylate-based monomer, vinyl cyanide-based monomer, and vinyl aromatic monomer. can exist as wealth. When the above-described range is satisfied, a graft copolymer having a desired weight average molecular weight can be prepared.

The aqueous solvent may be ion-exchanged water or pure water.

2. Graft copolymer

The graft copolymer according to an embodiment of the present invention includes at least one selected from the group consisting of a compound represented by the following formula (1), a derivative of the compound represented by the following formula (1), and a monomer unit represented by the following formula (1); and a diene-based rubbery polymer grafted with a vinyl aromatic monomer unit and a vinyl cyanide-based monomer unit:

<Formula 1>

In Formula 1,

L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,

R ₂ to R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a silica unit, but at least one of R ₂ to R ₄ is a silica unit.

Although the derivative of the compound represented by Formula 1 is not chemically bonded to the chain of the graft copolymer, it may mean that it is changed without maintaining its original state in a polymerization environment.

The monomer unit represented by Formula 1 may refer to a remaining portion of the compound represented by Formula 1 in the chain of the graft copolymer, that is, a unit derived from the monomer represented by Formula 1 above. Specifically, the monomer represented by Formula 1 is grafted to the diene-based rubbery polymer, or selected from the group consisting of the (meth)acrylate-based monomer unit, a vinyl aromatic monomer unit, and a vinyl cyanide-based monomer unit. It may refer to a residue chemically bound to a species or more.

When the graft copolymer includes at least one selected from the group consisting of a compound represented by Formula 1, a derivative of the compound represented by Formula 1, and a monomer unit represented by Formula 1, processability and transparency are improved While maintaining the same level as the graft copolymer of , the mechanical properties can be improved.

Accordingly, the description of the compound represented by Chemical Formula 1 is ‘1. As described above in 'Method for producing a graft copolymer'.

The graft copolymer may have a refractive index of 1.51 to 1.52, preferably 1.512 to 1.518. When the above-described conditions are satisfied, the difference in refractive index with the non-grafted copolymer to be described later is minimized, thereby providing a thermoplastic resin composition having excellent transparency.

3. Thermoplastic resin composition

The thermoplastic resin composition according to another embodiment of the present invention includes the graft copolymer according to an embodiment of the present invention and a (meth)acrylate-based monomer unit, a styrene-based monomer unit and an acrylonitrile-based monomer unit. non-grafted copolymers.

The thermoplastic resin composition may include the graft copolymer and the non-graft copolymer in a weight ratio of 10:90 to 40:60, preferably 20:80 to 30:70. When the above-mentioned range is satisfied, a thermoplastic resin composition having excellent processability and impact resistance can be manufactured.

The non-graft copolymer may be prepared by copolymerizing a (meth)acrylate-based monomer, a vinyl aromatic monomer, and a vinyl cyanide-based monomer.

The (meth) acrylate-based monomer is 60 to 80 parts by weight, preferably 65 to 75 parts by weight, based on 100 parts by weight of the total of the (meth) acrylate-based monomer, the styrene-based monomer and the acrylonitrile-based monomer. can be used When the above conditions are satisfied, a non-grafted copolymer having excellent transparency can be prepared.

The vinyl aromatic monomer may be used in an amount of 15 to 35 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of the total of the (meth)acrylate-based monomer, the styrene-based monomer and the acrylonitrile-based monomer. there is. When the above-mentioned conditions are satisfied, a non-graft copolymer having excellent processability can be prepared.

The vinyl cyanide-based monomer is used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the total of the (meth)acrylate-based monomer, the styrene-based monomer and the acrylonitrile-based monomer. can When the above conditions are satisfied, a non-graft copolymer having excellent chemical resistance can be prepared.

The difference in refractive index between the graft copolymer and the non-graft copolymer may be 0 to 0.01, preferably 0 to 0.005, and more preferably 0. When the above conditions are satisfied, it is possible to provide a thermoplastic resin composition having excellent transparency.

The non-graft copolymer may have a refractive index of 1.51 to 1.52, preferably 1.512 to 1.518. When the above-described conditions are satisfied, the difference in refractive index with the above-described graft copolymer is minimized, thereby providing a thermoplastic resin composition having excellent transparency.

The non-graft copolymer may be a methyl methacrylate/styrene/acrylonitrile copolymer.

Meanwhile, the thermoplastic resin composition may include a compound represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2,

L ₂ is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₅ to R ₈ are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.

In Formula 2, L ₂ may be a C ₁ to C ₄ alkylene group, and R ₅ to R ₈ may each independently be a C ₁ to C ₄ alkyl group. When the above-described conditions are satisfied, the thermoplastic resin composition can improve mechanical properties such as impact resistance and tensile resistance while maintaining excellent transparency.

The compound represented by Formula 2 may be a raw material of the compound represented by Formula 1, ie, a starting material.

The compound represented by Formula 2 may be at least one selected from the group consisting of compounds represented by Formulas 2-1 to 2-4, and a compound represented by 2-3 below is preferable.

<Formula 2-1>

<Formula 2-2>

<Formula 2-3>

<Formula 2-4>

The compound represented by Chemical Formula 2 can implement transparency of the thermoplastic resin composition at the same level as before, and improve mechanical properties.

The compound represented by Formula 2 may be included in an amount of 0.05 to 1 part by weight, preferably 0.1 to 0.25 parts by weight, based on 100 parts by weight of the total of the graft copolymer and the non-graft copolymer. When the above-mentioned conditions are satisfied, the transparency of the thermoplastic resin composition can be realized at the same level as the existing ones, and mechanical properties can be improved.

On the other hand, the thermoplastic resin composition according to another embodiment of the present invention is an anti-drip agent, a flame retardant, an antibacterial agent, an antistatic agent, a stabilizer, a release agent, a heat stabilizer, an ultraviolet stabilizer, an inorganic additive, a lubricant, an antioxidant, a light stabilizer, a pigment, a dye and one or more additives selected from the group consisting of inorganic fillers.

The thermoplastic resin composition according to an embodiment of the present invention preferably includes at least one selected from the group consisting of lubricants, antioxidants and UV stabilizers.

4. Thermoplastic resin molded products

A thermoplastic resin molded article according to another embodiment of the present invention is made of the above-described thermoplastic resin composition, the transparency measured according to ASTM D1003 is 3.6% or less, and the impact strength measured according to ASTM D256 is 25 kg· It may be more than cm/cm, and it can be seen that both transparency and impact resistance are secured within this range.

The thermoplastic resin molded article preferably has a transparency measured according to ASTM D1003 of 3.5% or less, an impact strength measured according to ASTM D256 of 26 kg·cm/cm or more, and a transparency measured according to ASTM D1003 of 3.0% Hereinafter, it is more preferable that the impact strength measured according to ASTM D256 is 28 kg·cm/cm or more.

Here, the transparency may be measured with a specimen having a thickness of 3 mm at room temperature, and the impact strength may be measured with a specimen having a thickness of 1/4 In.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Preparation Example 1: Preparation of a compound represented by Formula 1

A mixed solution was prepared by mixing ethanol and distilled water in a volume ratio of 80:20. 300 ml of the mixed solution was added to the flask, acetic acid was added, the pH was adjusted to 4, and the mixture was stirred at a speed of 250 rpm with a magnetic stirrer for 10 minutes. 13 g of 3-(trimethoxysilylpropyl)methacrylate was added to the flask and hydrolyzed for 1 hour. After the hydrolysis was completed, 6 g of silica (ST-O from Nissan Chemical America Corporation, average particle diameter: 10 to 20 nm) was added to the flask, and the surface was stirred with a magnetic stirrer at a speed of 300 rpm for 2 hours. modified. After the surface modification was completed, the solution in the flask was centrifuged at 4,000 rpm for 30 minutes using a centrifuge, and the supernatant was discarded. The remainder was dried at 60° C. for 30 minutes in a dry oven, and then dried overnight at room temperature to obtain a powder containing at least one selected from the group consisting of compounds represented by Chemical Formulas 1-1 to 1-3.

Preparation Example 2: Preparation of non-grafted copolymer pellets

A mixed solution containing 69 parts by weight of methyl methacrylate, 24 parts by weight of styrene, 7 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.15 parts by weight of t-dodecyl mercaptan was prepared.

The mixed solution was continuously introduced into the nitrogen-substituted reactor at a constant rate so that the residence time was 3 hours, and the temperature of the reactor was maintained at 148 °C. The polymerization solution discharged from the reactor was heated in a preheating tank, and unreacted monomers were volatilized in the volatilization tank. Then, it was extruded at 210° C. using a polymer transfer pump extruder to obtain non-grafted copolymer pellets (refractive index: 1.516).

Example 1

<Preparation of graft copolymer powder>

100 parts by weight of ion-exchanged water, 32 parts by weight of methyl methacrylate, 11 parts by weight of styrene, 7 parts by weight of acrylonitrile, 1 part by weight of the powder of Preparation Example 1, 0.04 parts by weight of cumene hydroperoxide, sodium dodecylbenzenesulfonate A mixed solution containing 1 part by weight, 0.3 parts by weight of t-dodecyl mercaptan, 0.048 parts by weight of sodium formaldehyde sulfoxylate, 0.012 parts by weight of disodium ethylenediaminetetraacetate, and 0.001 parts by weight of iron(II) sulfate was prepared. .

50 parts by weight (based on solid content) of polybutadiene latex (average particle diameter: 300 nm, refractive index: 1.516, gel content: 70%) was put into a nitrogen-substituted reactor, and then the reactor was heated to 75 ° C., and polymerization conversion rate Polymerization was carried out while continuously introducing the mixed solution at a constant rate for 5 hours from the time of 0% until the polymerization conversion reached 90%.

Immediately after the continuous input of the mixed solution was finished, the internal temperature of the reactor was raised to 80° C. for 1 hour, and after aging, polymerization was terminated to obtain a graft copolymer latex (polymerization conversion rate: 93%).

The graft copolymer latex was aggregated with an aqueous calcium chloride solution, aged, washed, dehydrated and dried to obtain a graft copolymer powder (refractive index: 1.516).

<Production of thermoplastic resin composition>

40 parts by weight of the graft copolymer powder and 60 parts by weight of the non-graft copolymer pellets of Preparation Example 2 were uniformly mixed to prepare a thermoplastic resin composition.

Examples 2 to 5

<Preparation of graft copolymer powder>

A graft copolymer powder was prepared in the same manner as in Example 1, except that in Example 1, the powder of Preparation Example 1 was added in the amount shown in Table 1 below.

<Production of thermoplastic resin composition>

40 parts by weight of the graft copolymer powder, 60 parts by weight of the non-graft copolymer pellets of Preparation Example 2, and 3-(trimethoxysilylpropyl)methacrylate (TMSM) in the content shown in Table 1 below are uniformly mixed, A thermoplastic resin composition was prepared.

Comparative Example 1

A graft copolymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that the powder of Preparation Example 1 was not added in the preparation of the graft copolymer powder of Example 1.

Comparative Example 2

<Preparation of graft copolymer powder>

A graft copolymer powder was prepared in the same manner as in Example 1, except that 1 part by weight of 3-(trimethoxysilylpropyl)methacrylate was added without adding the powder of Preparation Example 1 in Example 1 did

<Production of thermoplastic resin composition>

40 parts by weight of the graft copolymer powder and 60 parts by weight of the non-graft copolymer pellets of Preparation Example 2 were uniformly mixed to prepare a thermoplastic resin composition.

Experimental Example 1

The physical properties of the graft copolymers of Examples and Comparative Examples were evaluated by the method described below, and the results are described in Tables 1 to 3 below.

(1) Final polymerization conversion (%): It was calculated by the following formula.

Polymerization conversion (%) = {(total weight of monomers added until polymerization is completed)-(total weight of unreacted monomers when polymerization conversion is measured)}/ (total weight of monomers added until polymerization is complete) weight) × 100

(2) Refractive index: It was measured with an Abbe refractometer using visible light of 589.3 nm.

Experimental Example 2

The thermoplastic resin compositions of Examples and Comparative Examples were put into a twin-screw extrusion kneader set at 230° C., and pellets were prepared. The pellets were evaluated for physical properties by the method described below, and the results are shown in Tables 1 to 3 below.

(1) Melt Flow Index (g/10 min): According to ASTM D1238, it was measured at 220 °C and 10 kg.

Experimental Example 3

A specimen was prepared by injecting the pellets prepared in Experimental Example 2, and the physical properties of the specimen were evaluated by the method described below, and the results are shown in Tables 1 to 3 below.

(1) Transparency (haze, %): The haze value of the sheet (thickness: 3 mm) was measured at room temperature according to ASTM D1003.

(2) Notched Izod impact strength (kg·cm/cm): The notched Izod impact strength of the sheet (thickness: 1/4 In) was measured according to ASTM D256.

(3) Tensile strength (kgf/cm 2 ): Measured according to ASTM D638.

division Example 1 Example 2 Example 3 Example 4 Example 5 graft copolymer powder Powder of Preparation Example 1 (parts by weight) One 0.75 0.6 0.5 0.4 final polymerization conversion 93 92 94 93 94 refractive index 1.516 1.517 1.516 1.516 1.516 Thermoplastic resin composition
(parts by weight) graft copolymer powder 40 40 40 40 40 Non-graft copolymer pellets of Preparation Example 2 60 60 60 60 60 TMSM 0 0.1 0.15 0.2 0.25 pellet flow index 16.8 17.8 17.2 17.5 18.0 Psalter transparency 3.6 3.5 3.5 3.0 2.8 impact strength 25.2 26.2 27.0 28.0 28.5 tensile strength 588 588 600 615 630

division Comparative Example 1 Comparative Example 2 graft copolymer powder Powder of Preparation Example 1 (parts by weight) 0 0 TMSM (parts by weight) 0 One final polymerization conversion 93 94 refractive index 1.516 1.517 Thermoplastic resin composition
(parts by weight) graft copolymer powder 40 40 Non-graft copolymer pellets of Preparation Example 2 60 60 TMSM 0 0 pellet flow index 18.0 17.2 Psalter transparency 2.2 3.7 impact strength 20.2 21.8 tensile strength 520 550

Referring to Tables 1 and 2, Examples 1 to 5, in which 0.4 to 1 parts by weight of the powder of Preparation Example 1 were added in the preparation of the graft copolymer powder, realized high flow index, impact strength and tensile strength. did

However, Comparative Example 1 in which the powder of Preparation Example 1 was not added during the preparation of the graft copolymer powder had excellent transparency compared to Examples 1 to 5, but the impact strength and tensile strength were significantly reduced.

In addition, in Comparative Example 2, in which 3-(trimethoxysilylpropyl)methacrylate was added during the preparation of the graft copolymer powder, the impact strength and tensile strength were significantly lowered compared to Examples 1 to 5.

Claims (10)

Preparation of a graft copolymer comprising adding a compound represented by the following Chemical Formula 1, a diene-based rubbery polymer, a (meth)acrylate-based monomer, a vinyl aromatic monomer, and a vinyl cyanide-based monomer to a reactor and polymerizing method:
<Formula 1>

In Formula 1,
L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group,
R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,
R ₂ to R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a silica unit, but at least one of R ₂ to R ₄ is a silica unit.
The method according to claim 1,
The method for producing a graft copolymer, wherein the compound represented by Formula 1 is added in an amount of 0.4 to 1 part by weight based on 100 parts by weight of the total of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer.
The method according to claim 1,
A method for producing a graft copolymer in which the compound represented by Formula 1 is continuously added.
4. The method according to claim 3,
The starting point of continuous input of the compound represented by Formula 1 is a time point at which the polymerization conversion rate is 0% to 10%,
The method for producing a graft copolymer is the time when the continuous input of the compound represented by the formula (1) is terminated from the time when the polymerization conversion rate is 60%.
at least one selected from the group consisting of a compound represented by the following formula (1), a derivative of the compound represented by the following formula (1), and a monomer unit represented by the following formula (1); and
A graft copolymer comprising a diene-based rubbery polymer grafted with a vinyl aromatic monomer unit and a vinyl cyanide-based monomer unit:
<Formula 1>

In Formula 1,
L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group,
R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,
R ₂ to R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a silica unit, but at least one of R ₂ to R ₄ is a silica unit.
The graft copolymer according to claim 5; and
A thermoplastic resin composition comprising a (meth) acrylate-based monomer unit, a vinyl aromatic monomer unit, and a non-grafted copolymer including a vinyl cyanide-based monomer unit.
7. The method of claim 6,
A thermoplastic resin composition comprising a compound represented by the following formula (2):
<Formula 2>

In Formula 2,
L ₂ is a direct bond or a C ₁ to C ₁₀ alkylene group,
R ₅ to R ₈ are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.
8. The method of claim 7,
A thermoplastic resin composition comprising the compound represented by Formula 2 in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the total of the graft copolymer and the non-graft copolymer.
8. The method of claim 7,
The compound represented by Formula 2 is a thermoplastic resin composition that is at least one selected from the group consisting of compounds represented by Formulas 2-1 to 2-4:
<Formula 2-1>

<Formula 2-2>

<Formula 2-3>

<Formula 2-4>

It is prepared from the thermoplastic resin composition according to claim 6,
Transparency measured according to ASTM D1003 is 3.6% or less,
A thermoplastic resin molded article having an impact strength of 25 kg·cm/cm or more measured in accordance with ASTM D256.