KR20140131007A - Terpolymer Having Improved Heat Resistance and Thermoplastic Resin Composition Including Same - Google Patents

Abstract

Maleic acid anhydride-aromatic group vinyl-unsaturated nitrile terpolymer, according to the present invention, comprises (A) 60-80 wt% of an aromatic vinyl-based monomer; (B) 15-30 wt% of an unsaturated nitrile-based monomer; and (C) 3-15 wt% of maleic acid anhydride, is a terpolymer whose content ratio of nitrile based-monomer is 0.23-0.5 for the aromatic group vinyl-based monomer and has a single glass transition temperature and excellent heat resistance.

Description

(Terpolymer Having Improved Heat Resistance and Thermoplastic Resin Composition Including Same)

The present invention relates to a terpolymer having excellent heat resistance. More specifically, the present invention relates to a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer having excellent heat resistance with a single glass transition temperature.

Generally, a styrene-acrylonitrile copolymer resin (hereinafter referred to as "SAN resin") is prepared by copolymerizing styrene, which is an aromatic vinyl monomer, and acrylonitrile, which is an unsaturated nitrile monomer. Such a SAN resin is excellent in transparency and processability and is commercially produced in large quantities.

However, the SAN resin is not excellent in heat resistance and can be used as an aromatic vinyl monomer having an excellent heat resistance, such as an α-methylstyrene-acrylonitrile copolymer resin (hereinafter referred to as "AMS-SAN") using α-methylstyrene Resin ') was used instead of the SAN resin for applications requiring heat resistance. However, since the supply and demand of? -Methylstyrene is unstable, the price fluctuation of AMS-SAN resin made of? -Methylstyrene becomes large and the use of? -Methylstyrene is limited. To overcome this problem, an N-phenylmaleimide-styrene-acrylonitrile copolymer resin (hereinafter referred to as "PMI-SAN resin") using N-phenylmaleimide (PMI) having an imide structure excellent in heat resistance AMS-SAN resin. However, since N-phenylmaleimide is expensive, PMI-SAN made of N-phenylmaleimide is expensive.

Recently, in order to solve such problems, a maleic anhydride-styrene-acrylonitrile copolymer resin (hereinafter referred to as "MAH-SAN") having excellent heat resistance by using maleic anhydride (MAH) Resin '). The maleic anhydride is difficult to produce using suspension polymerization or emulsion polymerization using water because of the presence of unstable anhydride groups and side reactions with water, and can be produced by solution polymerization or bulk polymerization. The MAH-SAN resin thus produced has a low content of maleic anhydride due to the reactivity between the monomers, and MAH-SAN resin has been commercialized. However, since the MAH-SAN resin using maleic anhydride is a terpolymer of maleic anhydride, styrene and acrylonitrile, the physical properties are uneven, and when the composition containing the maleic anhydride is compounded with other additives, There is a problem that the physical properties are deteriorated.

Accordingly, the present inventors have developed a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer having uniform physical properties by controlling the content ratio of the aromatic vinyl monomer and the unsaturated nitrile monomer.

An object of the present invention is to provide a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer excellent in heat resistance.

Another object of the present invention is to provide a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer having a single glass transition temperature.

Another object of the present invention is to provide a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer excellent in flowability.

These and other objects of the invention are all achievable by the invention which is described below.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer according to the present invention comprises (A) 60 to 80% by weight of an aromatic vinyl monomer, (B) 15 to 30% by weight of an unsaturated nitrile monomer, and (C) 3 to 15% by weight, the content ratio of the unsaturated nitrile-based monomer to the aromatic vinyl-based monomer is 0.23 to 0.5, and has a single glass transition temperature and excellent heat resistance.

The aromatic vinyl-based monomer of the present invention may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, ≪ / RTI >

The unsaturated nitrile monomer of the present invention is acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention is a monomer copolymerizable with an aromatic vinyl-based monomer, and includes an alkyl acrylate-based monomer, a methacrylate alkyl ester-based monomer, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, Maleimide-based monomers, and mixtures thereof.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention may further include an initiator, a molecular weight modifier, a heat stabilizer, an antioxidant, an inorganic additive, and a mixture thereof as an additive.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a glass transition temperature of from 110 to 130 DEG C measured at a heating rate of 10 DEG C / minute using a differential scanning calorimeter and has a single glass transition temperature.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a Becket softening point of 111 to 135 ° C measured under a load of 5 kg according to ISO 306.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a yellowness index (YI) of from 15 to 25 as measured by a spectrophotometer according to ASTM E313.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a flow index (MI) of 15 to 40 g / 10 min as measured according to ASTM D 1238 at 220 ° C / 10 kg.

The thermoplastic resin composition according to the present invention comprises the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer.

Hereinafter, the present invention will be described in detail.

The ternary copolymer according to the present invention has the effect of the present invention, which has a single glass transition temperature and provides a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer excellent in heat resistance and fluidity.

The present invention relates to a terpolymer having excellent heat resistance, and relates to a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer having excellent heat resistance and having a single glass transition temperature.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer according to the present invention comprises (A) 60 to 80% by weight of an aromatic vinyl monomer, (B) 15 to 30% by weight of an unsaturated nitrile monomer, and (C) 3 to 15% by weight, the content ratio of the unsaturated nitrile-based monomer to the aromatic vinyl-based monomer is 0.23 to 0.5, and has a single glass transition temperature and excellent heat resistance.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention is obtained by dissolving a solid maleic anhydride (C) in an unsaturated nitrile-based monomer (B) having polarity and introducing it together with an aromatic vinyl-based monomer (A) can do. At this time, the maleic anhydride (C) and the aromatic vinyl monomer (A) react first, and the aromatic vinyl monomer (A) Since the monomer (A) reacts with the unsaturated nitrile monomer (B), it can be polymerized through a continuous reaction.

This reaction sequence allows the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention to have a single glass transition temperature in order to obtain the maleic anhydride-aromatic vinyl-based polymer, which is the product of the first reaction, The polarities of the aromatic vinyl-unsaturated nitrile-based polymers should be similar. Therefore, in order to obtain the desired glass transition temperature, the content of the maleic anhydride (C) is controlled so that the content ratio of the unsaturated nitrile monomer (B) to the aromatic vinyl monomer (A) .

When the content range of the maleic anhydride (C) having a high glass transition temperature is less than 3% by weight based on 100% by weight of the aromatic vinyl monomer (A), the unsaturated nitrile monomer and (C) the maleic anhydride, the maleic anhydride- -Unsaturated nitrile terpolymer is deteriorated, and when it exceeds 15% by weight, thermal stability during processing is lowered.

When the content ratio of the unsaturated nitrile monomer (B) to the aromatic vinyl monomer (A) is less than 0.23 or more than 0.5, the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer in a non-homogeneous state having a glass transition temperature of 2 or more So that the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer can not be mixed well and can not have uniform physical properties.

The maleic anhydride (C) is preferably polymerized by solution polymerization or bulk polymerization because the hydrolysis reaction occurs under the polymerization conditions in which water is present and the reactivity is lowered. Particularly, bulk polymerization is more preferable in terms of continuous reaction. However, a solvent such as toluene, ethylbenzene or the like may be used in order to lower the viscosity at the time of bulk polymerization.

Examples of the aromatic vinyl monomer (A) of the present invention include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromo Styrene, and mixtures thereof, but are not limited thereto. Styrene may be preferably used.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention is a monomer copolymerizable with the aromatic vinyl monomer (A), which is an acrylic acid alkyl ester monomer, a methacrylic alkyl ester monomer, an unsaturated carboxylic acid, Acid anhydrides, maleimide-based monomers, and mixtures thereof.

As the alkyl acrylate monomer, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, cyclohexyl acrylate, n-hexyl acrylate and mixtures thereof may be used, and alkyl methacrylate As the ester-based monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, and mixtures thereof can be used .

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and mixtures thereof. As the unsaturated carboxylic acid anhydride, maleic anhydride, fumaric anhydride and a mixture thereof may be used. As the maleimide- Maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide, N-phenylmaleimide and N-tolylmaleimide . These unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimide-based monomers, and mixtures thereof can impart heat resistance and processability to the terpolymer.

As the unsaturated nitrile monomer (B) of the present invention, acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof can be used, and acrylonitrile is preferable.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention may further contain an initiator, a molecular weight modifier, a heat stabilizer, an antioxidant, an inorganic additive and a mixture thereof as the additive (D) But it is not necessarily limited thereto.

In the present invention, the additive (D) may be used in an amount of 10 parts by weight or less based on 100 parts by weight of the aromatic vinyl monomer (A), the unsaturated nitrile monomer and (C) the maleic anhydride.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a glass transition temperature of from 110 to 130 ° C measured at a heating rate of 10 ° C / min using TA instruments DSC Q20, a differential scanning calorimeter, Transition temperature.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a vicat softening point of 111 to 135 ° C measured under a load of 5 kg according to ISO 306.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a yellow index (YI) of 15 to 25 as measured by a spectrophotometer, CM-3600d manufactured by Konica Minolta, according to ASTM E313.

The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of the present invention has a melt-flow index (MI) of 15 to 40 g / 10 min as measured according to ASTM D1238 at 220 ° C / 10 kg.

The thermoplastic resin composition according to the present invention comprises the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer. The thermoplastic resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to produce pellets or chips.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of each component used in the following examples and comparative examples are as follows.

(A) an aromatic vinyl monomer

Styrene of MITSUBISHI CORPORATION was used.

(B) an unsaturated nitrile monomer

Acrylonirile of INEOS was used.

(C) maleic anhydride

Maleic anhydride from Yongsan Chemical Co. was used.

(D) Additive

Perbutyl-D (di-t-butyl peroxide) from Dongseong High Chem Co., Ltd. was used as an initiator and Teridine Dodecyl Mercaptan from ISU Exechem Co. was used as a molecular weight regulator. SONGNOX-1076 (OCTADECYL 3 (3.5-DI.T.BUTYL-4-HYDROXY PHENYL) PROPIONATE) was used.

Example  1 to 2 and Comparative Example  1 to 4

Each component of the content ratio shown in Table 1 below was stirred together with the additive (D) and 20 parts by weight of toluene for 5 hours or more, and then the two reactors were fed into the first reactor of the reactor connected in series at a rate of 1 kg / , And the polymerization was continuously carried out at a temperature of 110 to 120 DEG C in each reactor to prepare maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer.

In Table 1, the mixing ratios of (A), (B) and (C) are expressed in terms of% by weight based on 100% by weight of the total of (A), (B) and (C).

Example Comparative Example One 2 One 2 3 4 (A) 74.0 69.3 73.0 75.0 73.0 72.0 (B) 18.0 16.7 27.0 17.0 17.0 16.0 (C) 8.0 14.0 - 8.0 10.0 12.0 (B) / (A) 0.243 0.241 0.370 0.227 0.233 0.222

The physical properties of the prepared maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer were measured as follows, and the results are shown in Table 2.

(1) Glass transition temperature (Tg, 占 폚): Measured at a heating rate of 10 占 폚 / min using a differential scanning calorimeter DSC Q20 from TA Instruments.

(2) Heat resistance (VST, ° C): Vicat softening point was measured under a load of 5 kg according to ISO 306.

(3) Flowability (MI, g / 10 min): The flow index was measured at 220 캜 / 10 kg in accordance with ASTM D1238.

(4) Number average molecular weight and weight average molecular weight (g / mol): A number average molecular weight (Mn) and a weight average molecular weight (Mw) were measured in a THF solvent at 40 캜 using gel permeation chromatography Alient Technologies 1200 series Respectively.

(5) Yellowness (YI): Yellowness was measured using a spectrophotometer, Konica Minolta CM-3600d according to ASTM E313.

Example Comparative Example One 2 One 2 3 4 Glass transition temperature
(° C) 111.3 123.4 110.0 110.7
122.5 110.4
119.9 111.7
125.8 Beckett softening point
(° C) 114.2 121.2 105.7 114.7 117.2 118.5 Flow index
(g / 10 min) 16.2 28.9 24.6 25.5 29.5 15.2 Number average molecular weight
(g / mol) 65.5 49.9 68.9 64.8 54.6 66.2 Weight average molecular weight
(g / mol) 166.6 107.2 175.0 158.9 134.3 160.2 Molecular weight distribution 2.54 2.15 2.54 2.45 2.46 2.42 Yellowness 16.1 17.8 5.9 18.4 21.4 20.1

In Table 2, Comparative Examples 2 to 4 in which the content ratio of the unsaturated nitrile-based monomer (B) to the aromatic vinyl-based monomer (A) is less than 0.23 show that a homogeneous maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer is prepared It has two glass transition temperatures, and the yellowness is reduced. In addition, it can be seen that Comparative Example 1, which is a general SAN resin, has a single glass transition temperature but has a lowered heat resistance.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

(A) 60 to 80% by weight of an aromatic vinyl monomer;
(B) 15 to 30% by weight of an unsaturated nitrile-based monomer; And
(C) 3 to 15% by weight of maleic anhydride;
Wherein the content ratio of said unsaturated nitrile monomer to said aromatic vinyl monomer is from 0.23 to 0.5 and has a single glass transition temperature.
The aromatic vinyl monomer as claimed in claim 1, wherein the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, Maleic anhydride-maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, and mixtures thereof.
The unsaturated nitrile monomer as claimed in claim 1, wherein the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof. The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer coalescence.
[Claim 2] The method according to claim 1, wherein the maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer is a monomer copolymerizable with the aromatic vinyl monomer, wherein the monomer is an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, an unsaturated carboxylic acid, Maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride and maleic anhydride monomer.
The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of claim 1, further comprising an additive selected from the group consisting of an initiator, a molecular weight modifier, a heat stabilizer, an antioxidant, an inorganic additive, .
The method according to claim 1, wherein the glass transition temperature measured at a heating rate of 10 DEG C / minute using a differential scanning calorimeter is from 110 to 130 DEG C and the glass transition temperature is a single glass transition temperature. -Aromatic vinyl-unsaturated nitrile terpolymer.
The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of claim 1, characterized in that the softening point of the viscose is from 111 to 135 占 폚 as measured under a load of 5 kg according to ISO 306.
The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of claim 1, characterized in that the degree of yellowness, as measured by a spectrophotometer according to ASTM E313, is from 15 to 25.
The maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer of claim 1, characterized in that the flow index measured at 220 ° C / 10 kg according to ASTM D 1238 is 15 to 40 g / 10 min.
10. A thermoplastic resin composition comprising a maleic anhydride-aromatic vinyl-unsaturated nitrile terpolymer according to any one of claims 1 to 9.