KR101741881B1 - Amsan copolymer, method for preparing the copolymer and heat resistance thermoplastic resin composition comprising the same - Google Patents

Abstract

The present invention relates to an AMSAN copolymer, and more particularly to an AMSAN copolymer which is copolymerized with an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer, And a thermoplastic heat-resistant resin composition containing the same.
According to the present invention, there is provided an AMSAN copolymer having improved polymerization stability and polymerization rate, an AMSAN copolymer prepared therefrom, and an effect of providing a thermoplastic heat-resistant resin composition excellent in reactivity, productivity, heat resistance and mechanical properties, have.

Description

TECHNICAL FIELD [0001] The present invention relates to AMSAN copolymers, a process for producing the same, and a thermoplastic heat-resistant resin composition containing the same. BACKGROUND ART AMSAN COPOLYMER, METHOD FOR PREPARING THE COPOLYMER AND HEAT RESISTANCE THERMOPLASTIC RESIN COMPOSITION COMPRISING THE SAME,

More particularly, the present invention relates to a method for producing an AMSAN copolymer having improved polymerization stability and polymerization rate, an AMSAN copolymer prepared from the copolymer, and a method for producing the AMSAN copolymer having excellent reactivity, productivity, heat resistance and mechanical properties And a thermoplastic heat-resistant resin composition.

In general, acrylonitrile-butadiene-styrene copolymer (ABS) resin has excellent processability and excellent appearance characteristics such as styrene processability, acrylonitrile stiffness, chemical resistance, and impact resistance of butadiene rubber. , Housings for home appliances, and toys. In particular, since automobile interior materials are always exposed to a high temperature environment, high thermal properties (heat distortion resistance, HDT) are required.

(AMSAN), which is prepared by emulsion polymerization or solution polymerization and has a high glass transition temperature (Tg), in order to satisfy such high thermal properties in ABS resin, a rubber prepared by emulsion polymerization A method of producing a reinforced graft copolymer (ABS copolymer) by melt-mixing it in a range having a fixed rubber content, and the like have been proposed.

The alpha-methylstyrene-acrylonitrile copolymer is prepared by copolymerizing an alpha-methylstyrene monomer and a vinyl cyanide monomer by emulsion polymerization. Due to the low reactivity of alpha-methylstyrene and the deterioration of polymerization stability , The polymerization rate is greatly lowered and the amount of the coagulated product is increased, resulting in a problem that productivity and heat resistance are lowered.

Therefore, in order to solve the above-mentioned problems, there is a continuing demand for studies on AMSAN copolymers having excellent polymerization stability and excellent polymerization rate.

In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a process for producing an AMSAN copolymer having improved polymerization stability and polymerization rate.

Another object of the present invention is to provide an AMSAN copolymer produced from the above-mentioned production process.

Another object of the present invention is to provide a thermoplastic heat-resistant resin composition having excellent reactivity, productivity, heat resistance and mechanical properties including the AMSAN copolymer.

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

In order to achieve the above object, the present invention provides a copolymerized AMSAN copolymer comprising an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer.

The present invention also provides an emulsion polymerization method comprising an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer.

The present invention also provides a thermoplastic heat-resistant resin composition comprising 60 to 90% by weight of the AMSAN copolymer and 10 to 40% by weight of an acrylonitrile-butadiene-styrene (ABS) resin, and a molded article produced therefrom.

According to the present invention, there is provided an AMSAN copolymer having improved polymerization stability and polymerization rate, an AMSAN copolymer prepared therefrom, and a thermoplastic heat-resistant resin composition excellent in reactivity, productivity, heat resistance and mechanical properties, .

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have continued to study a copolymer having excellent heat resistance and excellent polymerization stability. As a result, it has been found that when copolymerized with an alpha-methylstyrene monomer and an acrylonitrile monomer containing a metal (meth) allyl sulfonate monomer, And an AMSAN copolymer having an improved polymerization rate can be prepared, and a thermoplastic heat-resistant resin composition having excellent reactivity, productivity, heat resistance, and mechanical properties can be prepared. Thus, the present invention has been accomplished on the basis thereof.

The AMSAN copolymer of the present invention, its preparation method and the thermoplastic heat-resistant resin composition containing the same are as follows.

AMSAN copolymer

The AMSAN copolymer according to the present invention is characterized in that it is copolymerized with an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer.

The alpha-methylstyrene monomer may be contained in an amount of 50 to 90% by weight, 60 to 85% by weight, or 65 to 80% by weight based on the total weight of the AMSAN copolymer. When the content of the alpha-methylstyrene is less than 50% by weight, the glass transition temperature of the alpha-methylstyrene copolymer is lowered. When the content of the alpha-methylstyrene exceeds 90% by weight, There is a problem that the glass transition temperature is lowered.

The acrylonitrile monomer may be contained in an amount of 5 to 45% by weight, 10 to 35% by weight, or 15 to 30% by weight based on the total weight of the AMSAN copolymer, There is an effect of excellent physical properties.

The acrylonitrile-based monomer may be, for example, acrylonitrile, methacrylonitrile or ethacrylonitrile.

The metal (meth) allyl sulfonate monomer may be contained in an amount of 0.05 to 10% by weight, 0.1 to 5% by weight, 0.1 to 3% by weight, or 0.5 to 2% by weight based on the total weight of the AMSAN copolymer, The polymerization stability is excellent and the polymerization rate is excellent.

The metal of the metal (meth) allylsulfonate monomer may be, for example, an alkali metal.

The AMSAN copolymer may have an average particle diameter of 470 to 800 ANGSTROM, 500 to 700 ANGSTROM or 600 to 700 ANGSTROM, and has an excellent polymerization rate and polymerization stability within this range.

The AMSAN copolymer may be one copolymerized by emulsion polymerization.

Method for producing AMSAN copolymer

The method for producing an AMSAN copolymer according to the present invention includes the step of emulsion polymerization comprising an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer.

In the emulsion polymerization, the components may be added in a batch or in whole or in part.

As the emulsion polymerization, for example, the acrylonitrile monomer may be separately added at the time of polymerization initiation and at the polymerization conversion rate of 30 to 40%. In this case, polymerization stability is excellent.

As another example, the emulsion polymerization may be carried out by charging the acrylonitrile monomer in an amount of 50 to 90% by weight of the total amount of the acrylonitrile monomer at the start of the polymerization and then adding 10 to 50% by weight of the acrylonitrile monomer at a polymerization conversion rate of 30 to 40% And there is an effect of excellent polymerization stability within this range.

The continuous charging can be continuously performed for 2 to 3 hours, for example.

The emulsion polymerization may include, for example, a step of adding 0.05 to 10% by weight of the metal (meth) allyl sulfonate monomer at the start of polymerization, and the polymerization rate is excellent within this range.

As another example, the emulsion polymerization can be carried out by separately feeding the metal (meth) allyl sulfonate monomer at the time of polymerization initiation and at the polymerization conversion rate of 30 to 40%. In this case, the polymerization reactivity is excellent and the effect of controlling the latex viscosity have.

As another example, in the emulsion polymerization, 10 to 50% by weight of the metal (meth) allyl sulfonate monomer is added at the time of starting polymerization, and the remaining 50 to 90% by weight is polymerized at a polymerization conversion rate of 30 to 40% Can be added in a batch or continuously, and the polymerization reactivity within this range is excellent and the latex viscosity is controlled.

The continuous charging can be continuously performed for 2 to 3 hours, for example.

As the emulsion polymerization, for example, the polymerization conversion ratio may be 95% or 97% or more.

As another example, the emulsion polymerization can be polymerized by a process of batch, semi-batch or continuous process.

The emulsion polymerization may further include at least one selected from the group consisting of emulsifiers, electrolytes, molecular weight regulators and initiators.

The emulsifier may be at least one selected from the group consisting of an anionic adsorption type emulsifier, a nonionic emulsifier, a reactive emulsifier, and a polymer reaction type emulsifier. In this case, polymerization stability and latex storage stability are excellent.

The anionic adsorption type emulsifier may be, for example, a fatty acid alkali salt, and specific examples thereof may be an alkali salt of palmitic acid or an alkali salt of oleic acid.

The electrolyte may be, for example, potassium chloride (KCl), sodium chloride (NaCl), potassium bicarbonate (KHCO ₃ ), sodium bicarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ) (KHSO _3), sodium bisulfate (NaHSO _3), potassium pyrophosphate _{(K 4 P 2 O 7)} , sodium pyrophosphate _{(Na 4 P 2 O 7)} , tree, potassium phosphate (K ₃ PO _4), trisodium phosphate (Na ₃ PO ₄ ), dipotassium hydrogen phosphate (K ₂ HPO ₄ ) and disodium hydrogen phosphate (Na ₂ HPO ₄ ).

The molecular weight regulator may be, for example, a mercaptan-based molecular weight regulator.

The initiator may be at least one selected from the group consisting of cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutylonitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide and benzoyl peroxide have.

The latex of the AMSAN copolymer produced by the emulsion polymerization may have a viscosity of 10 to 100 cp, 15 to 80 cp or 20 to 60 cp, for example, and has excellent polymerization stability within this range.

For example, the latex of the AMSAN copolymer prepared by the emulsion polymerization may have a solid content of 1.2% or less (based on the solid content), or 0.8% or less (based on the solid content), or 0.5% Excellent balance of physical properties, and excellent heat resistance.

Thermoplastic heat-resistant resin composition

The thermoplastic heat-resistant resin composition according to the present invention is characterized by containing 60 to 90% by weight of the AMSAN copolymer and 10 to 40% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin.

The thermoplastic heat-resistant resin composition has an excellent heat resistance and mechanical properties within the range of the AMSAN copolymer and the ABS resin.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof.

The conjugated diene-based compound may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, pentadiene, pyrylene, derivatives thereof, and the like.

The vinyl aromatic compound may be at least one selected from the group consisting of styrene, alpha-methylstyrene, alpha-ethylstyrene, para-methylstyrene, vinyltoluene, and derivatives thereof.

The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin may be a graft copolymer resin prepared by emulsion polymerization.

The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin may include, for example, 5 to 25% by weight or 5 to 15% by weight of a vinyl cyan compound, 40 to 70% by weight or 50 To 70% by weight of the aromatic vinyl compound, and 20% to 40% by weight or 15% to 35% by weight of the aromatic vinyl compound.

As another example, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin may include an aromatic vinyl compound and a vinyl cyan compound in a ratio of 50:50 to 90:10 or 70:30 to 80:20.

The thermoplastic heat-resistant resin composition may have a glass transition temperature (Tg) of 139 占 폚 or higher, 140 占 폚 or higher, or 140 占 폚 to 200 占 폚, for example.

As another example, the thermoplastic heat-resistant resin composition may have an impact strength of 10.5 kg · cm / cm or more, 13.0 kg · cm / cm or more, or 13.5 to 40.0 kg · cm / cm.

As another example, the thermoplastic heat-resistant resin composition may have a heat distortion temperature (HDT) of 108 ° C or more, 109 ° C or more, or 109 to 115 ° C.

The thermoplastic heat-resistant resin composition may optionally contain additives such as a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, an antimicrobial agent or a lubricant within a range not affecting the physical properties.

The AMSAN copolymer and the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin may be mixed in a conventional mixer, for example.

Examples of the kneading apparatus of the AMSAN copolymer and the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin include a Banbury mixer, a single screw extruder, a twin screw extruder, A buss kneader or the like can be used.

The present invention also provides a molded article produced from the thermoplastic heat-resistant resin composition. The molded article may be, for example, office equipment, electrical and electronic products, or automobile interior and exterior materials.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example 1

160 parts by weight of ion-exchanged water, 75 parts by weight of alpha-methyl styrene as a monomer, 3.0 parts by weight of a potassium salt of palmitic acid as an emulsifier, 14.5 parts by weight of acrylonitrile, 0.5 part by weight of sodium methallylsulfonate 0.1 part by weight of trisodium phosphate (Na ₃ PO ₄ ) as an electrolyte, 0.5 part by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.1 part by weight of tertiary butyl hydroperoxide as an initiator and 0.025 part by weight of dextrose 0.05 parts by weight of sodium pyrophosphate, and 0.00005 parts by weight of ferrous sulfate were put in a batch and then reacted at a reaction temperature of 60 占 폚. 30 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile and 0.5 part by weight of potassium salt of palmitic acid were continuously fed for 2 to 3 hours in an emulsified state at a polymerization conversion rate of 30 to 40% And polymerization was carried out for 5 hours. The reaction was terminated to prepare an AMSAN copolymer latex.

The prepared emulsion polymerized copolymer latex was agglomerated by the addition of 3 parts by weight of calcium chloride, followed by dehydration after coagulation and drying to obtain an AMSAN copolymer resin powder. 75 parts by weight of an acrylonitrile-butadiene-styrene (ABS) resin powder (product name: DP 271; styrene: acrylonitrile = 75:25, butadiene content: 60%) was mixed with 75 parts by weight of the obtained AMSAN copolymer resin powder, 25 parts by weight were mixed in a conventional mixer and melted and kneaded at 240 DEG C using a twin-screw extruder to prepare a resin composition in the form of a pellet. The resin composition in the form of pellets was extruded by an extruder to prepare a specimen .

Example 2

0.25 parts by weight of sodium methallylsulfonate was added at the start of the reaction in Example 1, 9.5 parts by weight of acrylonitrile was added at a polymerization conversion rate of 30 to 40%, 0.75 parts by weight of sodium methallylsulfonate was added Was prepared in the same manner as in Example 1 above.

Comparative Example 1

Of acrylonitrile in the reaction initiation time from the first embodiment and at the same time 15 parts by weight of trisodium phosphate (Na ₃ PO ₄₎ and 0.2 parts by weight, and the initiator tertiary butyl hydroperoxide added instead of potassium persulfate and 0.3 parts by weight Except that sodium methallylsulfonate was not added and 20 parts by weight of ion exchange water and 1.0 part by weight of palmitoic acid potassium salt were added at a polymerization conversion rate of 10 to 40% .

[Test Example]

The physical properties of the thermoplastic heat-resistant resin composition specimens obtained in Examples 1 and 2 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

How to measure

Latex Viscosity (cp): Measured at 25 rpm using a Brookfield viscometer at 40 rpm.

* Average particle size (Å): Measured using a dynamic laser light skating method using 370 HPL manufactured by Nicomp, USA.

Polymerization Conversion (%): 2 g of each copolymer latex was dried in a hot air drier at 150 ° C for 15 minutes, and the weight was measured to determine the total solid content (TSC).

[Equation 1]

Polymerization Conversion = total solid content (TSC) x (parts by weight of added monomers and additives) / 100 - (parts by weight of added additives other than monomers)

* Coagulated product (%): Each copolymer latex produced was filtered through a 100 mesh network filter, and the total solid content determined theoretically for the filtered coagulum was recorded as% according to the following formula (2).

&Quot; (2) "

Solidification water content = (weight of coagulum produced in reactor / weight of total monomer administered) x 100

* Glass transition temperature (Tg, ° C): Measured using Q20 DSC from TA instruments.

* Impact strength (Notched Izod, kg · cm / cm): Measured according to standard measurement ASTM D256, with the thickness of the specimen being 1/4 ".

Heat distortion temperature (HDT, ° C): Measured according to standard measurement ASTM D648 using specimens.

division Example 1 Example 2 Comparative Example 1 Copolymer
Properties Latex viscosity (cp) 32 21 180 Average particle diameter (A) 620 660 460 Polymerization Conversion (%) 97.1 97.0 94.5 Coagulation product (%) 0.12 0.08 1.25 Heat-resistant resin composition
Properties Glass transition temperature (캜) 140.8 140.0 138.2 Impact strength
(kg · cm / cm) 14.0 13.6 10.2 Heat deformation temperature (캜) 110.0 109.6 107.1

As shown in the above Table 1, in Examples 1 and 2 in which sodium methallylsulfonate, which is metal (meth) allyl sulfonate, was copolymerized with monomers together with alpha-methylstyrene and acrylonitrile in accordance with the present invention, It was confirmed that the latex had a viscosity of 100 cp or less, an average particle size of 470 Å or more, and a solidification product of 1.2% or less, excellent polymerization stability, and a polymerization conversion rate of 95% or more.

In addition, according to the present invention, the thermoplastic heat-resistant resin composition including the AMSAN copolymer containing sodium methallylsulfonate as the monomer (meth) allylsulfonate as a monomer had a glass transition temperature of 139 DEG C or higher, an impact strength of 10.5 kg · cm / cm or more and a heat distortion temperature of 108 ° C or more, it was confirmed that the heat resistance and the mechanical properties were excellent.

On the other hand, in Comparative Example 1 in which metal (meth) allyl sulfonate was not added as a monomer, the reactivity was low due to a very high latex viscosity, small average particle size and solidified product of 1.25%, and polymerization stability was deteriorated. It was confirmed that the polymerization rate was greatly reduced and the reactivity and productivity were lowered.

In addition, in Comparative Example 1, which is a thermoplastic resin composition containing an AMSAN copolymer containing no metal (meth) allyl sulfonate, sodium methallylsulfonate as a monomer, both the glass transition temperature, impact strength and heat distortion temperature were low, It was confirmed that the mechanical properties were deteriorated.

In conclusion, the process for producing an AMSAN copolymer of the present invention is characterized in that, when copolymerizing an α-methylstyrene monomer and an acrylonitrile monomer, copolymerization of a metal (meth) allyl sulfonate together with a monomer results in excellent polymerization stability and polymerization rate AMSAN copolymer having improved polymerization stability and polymerization rate due to the above-mentioned invention, AMSAN copolymer prepared therefrom, and a thermoplastic heat-resistant resin composition having excellent reactivity, productivity, heat resistance and mechanical properties Can be implemented.

Claims (19)

60 to 90% by weight of an AMSAN copolymer copolymerized with an alpha-methylstyrene monomer, an acrylonitrile monomer and a metal (meth) allyl sulfonate monomer and having an average particle diameter of 600 to 800 ANGSTROM and a vinyl cyanide-conjugated diene- And 10 to 40% by weight of a compound-aromatic vinyl compound copolymer resin, and has a glass transition temperature of 140 ° C or higher. The method according to claim 1,
Wherein the alpha-methylstyrene monomer is contained in an amount of 50 to 90% by weight based on the total weight of the AMSAN copolymer. The method according to claim 1,
Wherein the acrylonitrile-based monomer is contained in an amount of 5 to 45% by weight based on the total weight of the AMSAN copolymer. The method according to claim 1,
Wherein the acrylonitrile-based monomer is acrylonitrile, methacrylonitrile, or ethacrylonitrile. The method according to claim 1,
Wherein the metal (meth) allylsulfonate monomer is contained in an amount of 0.05 to 10% by weight based on the total weight of the AMSAN copolymer. The method according to claim 1,
Wherein the metal of the metal (meth) allyl sulfonate monomer is an alkali metal. delete Alpha-methylstyrene monomer, an acrylonitrile monomer, and a metal (meth) allyl sulfonate monomer; AMSAN copolymer latex prepared by emulsion polymerization is agglomerated and then dehydrated and dried to obtain an AMSAN copolymer powder; And 60 to 90% by weight of the AMSAN copolymer and 10 to 40% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer to prepare a resin composition,
Wherein the AMSAN copolymer has an average particle diameter of 600 to 800 ANGSTROM, and the resin composition has a glass transition temperature of 140 DEG C or more. 9. The method of claim 8,
Wherein the metal (meth) allyl sulfonate monomer is contained in an amount of 0.05 to 10% by weight based on the total weight of the AMSAN copolymer. 9. The method of claim 8,
Wherein the metal (meth) allyl sulfonate monomer is added in a portion of the total amount of the metal (meth) allyl sulfonate monomer at the start of the polymerization, and then the remaining amount is continuously or batchwise introduced at a polymerization conversion rate of 30 to 40% Way. 9. The method of claim 8,
Wherein the emulsion polymerization has a polymerization conversion rate of 95% or more. 9. The method of claim 8,
Wherein the emulsion polymerization is carried out by further comprising at least one member selected from the group consisting of an emulsifier, an electrolyte, a molecular weight regulator and an initiator. 9. The method of claim 8,
Wherein the latex of the AMSAN copolymer produced by the emulsion polymerization has a viscosity of 10 to 100 cp. 9. The method of claim 8,
Wherein the latex of the AMSAN copolymer produced by the emulsion polymerization has a coagulated product of 1.2% or less (based on the solid content). delete delete The method according to claim 1,
Wherein the thermoplastic heat-resistant resin composition has an impact strength of 10.5 kg · cm / cm or more. The method according to claim 1,
Wherein the thermoplastic heat-resistant resin composition has a heat distortion temperature (HDT) of 108 ° C or higher. A molded article produced from the thermoplastic heat-resistant resin composition of claim 1.