KR102429679B1 - Composition containing styrene copolymer - Google Patents

Abstract

Provided is a composition containing a styrene copolymer that improves the properties of the acrylonitrile-butadiene-styrene copolymer.
[Solutions] An isocyanurate-based compatibilizer and a styrene copolymer composition component represented by Formula I, wherein R ¹ , R ² , R ³ are all a kind of C ₄ to C ₁₈ alkyl group, and the styrene The copolymer composition component is a styrene copolymer-containing composition, characterized in that it comprises an acrylonitrile-butadiene-styrene copolymer and an acrylonitrile-styrene copolymer.
Formula I

Description

Styrene copolymer containing composition {COMPOSITION CONTAINING STYRENE COPOLYMER}

The present invention relates to a composition containing a styrene copolymer, and more particularly, to a composition containing a styrene copolymer comprising an isocyanurate-based compatibilizer.

For example, Patent Document 1 and Patent Document 2 describe an acrylonitrile-butadiene-styrene copolymer (hereinafter also referred to as ABS resin). In addition, the ABS resin with a high content of butadiene has excellent mechanical properties, chemical resistance, and dimensional stability, and thus is used in various fields such as electric products and automobile products. As the performance requirements for products in this area increase, research on improving the properties of ABS resins with high butadiene content is also being conducted.

One of the methods of modifying the ABS resin having a high butadiene content is to add an acrylonitrile-styrene copolymer to the acrylonitrile-butadiene-styrene copolymer having a high butadiene content. However, since the content of butadiene in the acrylonitrile-butadiene-styrene copolymer is high, compatibility between the acrylonitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer is poor, and the properties of the ABS resin are effectively improved It is difficult to improve.

Japanese Patent Laid-Open No. 2013-253205 Japanese Patent Laid-Open No. 2016-216573

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composition containing a styrene copolymer that improves the properties of the acrylonitrile-butadiene-styrene copolymer.

In order to achieve the above object, the present invention is an isocyanurate-based compatibilizer and a styrene copolymer represented by Formula I, wherein R ¹ , R ² , and R ³ are all C ₄ to C ₁₈ alkyl groups. It provides a composition containing a styrene copolymer, characterized in that it includes a composition component, and the styrene copolymer composition component includes an acrylonitrile-butadiene-styrene copolymer and an acrylonitrile-styrene copolymer.

Formula I

Since the styrene copolymer-containing composition of the present invention contains the isocyanurate-based compatibilizer represented by Formula I, compatibility between the acrylonitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer is increased, Since the ronitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer can be mixed more uniformly, the impact strength of the molded article is higher than that of the prior art.

The composition containing the styrene copolymer of the present invention includes an isocyanurate-based compatibilizer and a styrenic copolymer composition in which R ¹ , R ² , and R ³ are all a kind of C ₄ to C ₁₈ alkyl group represented by Formula I do.

Formula I

The styrene copolymer composition component includes an acrylonitrile-butadiene-styrene copolymer and an acrylonitrile-styrene copolymer.

The alkyl group includes a chain alkyl group and a cycloalkyl group.

In some embodiments, R ¹ , R ² , R ³ in Formula I are the same alkyl group.

In some embodiments, R ¹ , R ² , and R ³ in Formula I are all a type of C ₇ -C ₁₇ alkyl group.

In some embodiments, R ¹ , R ² , and R ³ in Formula I are all a type of C ₇ alkyl group.

In some embodiments, R ¹ , R ² , and R ³ in Formula I are all a type of C ₁₁ alkyl group.

In some embodiments, in Formula I, R ¹ , R ² , and R ³ are all a type of C ₁₇ alkyl group.

Examples of the C ₇ to C ₁₇ alkyl group include 1-ethylpentyl (1-ethylpentyl), undecyl group, and heptadecyl group (heptadecyl).

In some embodiments, based on 100 parts by weight of the styrene copolymer composition component, the weight part of the isocyanurate-based compatibilizer is in the range of 0.1 parts by weight to 2.5 parts by weight.

In order for the molded article of the styrene copolymer-containing composition to have better impact resistance, the weight part of the isocyanurate-based compatibilizer is in the range of 1 part by weight to 2.5 parts by weight based on 100 parts by weight of the styrene copolymer composition component. it is preferable

As the acrylonitrile-butadiene-styrene copolymer, for example, an acrylonitrile-butadiene-styrene copolymer powder having a high butadiene rubber content purchased from GARND PACIFIC PETROCHEMICAL CORPORATION in Taiwan can be mentioned.

In some embodiments, in 100 parts by weight of the styrene copolymer composition, parts by weight of the acrylonitrile-butadiene-styrene copolymer are in the range of 15 parts by weight to 40 parts by weight.

As the acrylonitrile-styrene copolymer, for example, an acrylonitrile-styrene copolymer purchased from Taiwan GARND PACIFIC PETROCHEMICAL CORPORATION can be mentioned.

In some embodiments, in 100 parts by weight of the styrene copolymer composition, parts by weight of the acrylonitrile-styrene copolymer are in the range of 60 parts by weight to 85 parts by weight.

In some embodiments, the styrenic copolymer containing composition further comprises an additive composition component having at least one additive.

Examples of the additive include lubricants, antioxidants, and combinations thereof.

As the lubricant, for example, N,N'-ethylenebisoctadecanamide (N,N-ethylene-bis-stearamide, abbreviation EBS) can be mentioned.

As antioxidants, for example, pentaerythritol tetrakis(3,5-di-tert-butyl) -4-hydroxyhydrocinnamate), CAS number:6683-19-8), or phosphorous acid tris(2,4-di-tert-butylphenyl)phosphite, CAS number:31570 -04-4) and the like.

The styrene copolymer-containing composition of the present invention is used for the manufacture of molded articles requiring impact resistance, for example, for the manufacture of refrigerator doors and helmet shells.

Hereinafter, an embodiment of the present invention will be described. It is to be understood that these examples are illustrative and illustrative, and should not be construed as limiting the present invention.

Preparation Example 1. Isocyanurate-based compatibilizer

A stirrer and a Dean-Stark Trap were installed in the three-necked flask. 26.2 g of tris(2-hydroxyethyl) isocyanurate (1,3,5-tris(2-hydroxyethyl) cyanuric acid, CAS number: 839-90-7), 88.2 g of stearic acid, 660 g of toluene and 1.4 g of p-toluenesulfonic acid was added to a three-necked flask, heated to a reflux temperature of 110° C. to 120° C., and reacted at the reflux temperature for 6 hours, when no water was produced The reaction was terminated.

Then, the temperature was gradually lowered to -4°C, a white solid was precipitated, and the white solid was collected by filtration.

Then, the white solid was washed with cold heptane, and the white solid was left in a vacuum oven set at 35° C. for 2 hours, and 97.8 g of the white isocyanurate system represented by the formula I-1 A compatibilizer was obtained.

Formula I-1

Preparation Example 2. Isocyanurate-based compatibilizer

A stirring device and a Dean-Stark device were installed in the three-necked flask. 26.2 g of isocyanuric acid tris(2-hydroxyethyl), 66.1 g of lauric acid, 640 g of toluene and 1.4 g of p-toluenesulfonic acid were added to a three-necked flask, and the reflux temperature was 110° C. to 120° C. It was heated to ℃, reacted at the reflux temperature for 6 hours, and the reaction was terminated when no water was generated.

Then, the temperature was gradually lowered to -4°C, a white solid was precipitated, and the white solid was collected by filtration.

Then, the white solid was washed with cold heptane, and the white solid was left in a vacuum oven set at 35° C. for 2 hours, and 74 g of a white isocyanurate system represented by Formula I-2. A compatibilizer was obtained.

Formula I-2

Preparation Example 3. Isocyanurate-based compatibilizer

A stirring device and a Dean-Stark device were installed in the three-necked flask. 26.2 g of tris(2-hydroxyethyl) isocyanurate, 46.1 g of 2-ethylhexanoic acid, 500 g of toluene and 1 g of p-toluenesulfonic acid were added to a three-necked flask, and the reflux temperature was 110°C. It was heated to ~ 120 °C, reacted at the reflux temperature for 6 hours, and the reaction was terminated when no water was produced.

Then, toluene and the remaining unreacted raw materials were removed in a vacuum environment under reduced pressure to obtain 55.6 g of an isocyanurate-based compatibilizer represented by Formula I-3 in the form of a colorless gel.

Formula I-3

Example 1. Styrene copolymer-containing composition and molded article thereof

25 parts by weight of acrylonitrile-butadiene-styrene copolymer (purchased from GARND PACIFIC PETROCHEMICAL CORPORATION, Taiwan, product name: 60P), 75 parts by weight of acrylonitrile-styrene copolymer (purchased from GARND PACIFIC PETROCHEMICAL CORPORATION, Taiwan, product name: D20) ), 0.1 parts by weight of the isocyanurate-based compatibilizer of Formula I-1 of Preparation Example 1 and the additive composition were uniformly mixed at 25°C.

The additive composition comprises 2 parts by weight of N,N'-ethylenebisoctadecanamide, 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ] (product name: 1010, abbreviated as 1010 in Table 1 below), and 0.1 parts by weight of tris(2,4-di-tert-butylphenyl) phosphorous acid (product name: 168, abbreviated as 168 in Table 1 below). .

Extrusion was performed using a twin screw extruder (Taiwan SINO-ALLOY MACHINERY INC., model number: PSM20A testing machine) to form an extrudate. The temperature of the extrusion treatment is 190°C to 230°C, the screw rotation speed is 200 rotations/minute, and the input speed is 6 rotations/minute.

Then, the extrudate was subjected to cooling treatment, air drying treatment, granulation treatment and drying treatment to obtain a composition containing a styrene copolymer.

Injection treatment was performed on the styrene copolymer-containing composition at 210° C. using a vertical injection mo(u)lding machine, and left for 24 hours, and the dimensions were 64 mm × 12.7 mm × 10.2 mm. got a molded product.

Examples 2 to 8

The styrene copolymer-containing compositions of Examples 2 to 8 and molded articles thereof were prepared in a manner similar to that of Example 1, except that the amount of each component shown in Table 1 was different from Example 1.

Comparative Example 1

25 parts by weight of acrylonitrile-butadiene-styrene copolymer (GARND PACIFIC PETROCHEMICAL CORPORATION in Taiwan, product name: 60P), 75 parts by weight of acrylonitrile-styrene copolymer (GARND PACIFIC PETROCHEMICAL CORPORATION in Taiwan, product name: D20) and additive composition The ingredients were mixed uniformly at 25°C.

The additive composition contains 2 parts by weight of N,N'-ethylenebisoctadecanamide, 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Product name: 1010), and 0.1 parts by weight of tris(2,4-di-tert-butylphenyl) phosphorous acid (Product name: 168).

Extrusion was performed using a twin-screw extruder (Taiwan SINO-ALLOY MACHINERY INC., model number: testing machine PSM20A) to form an extrudate. The temperature of the extrusion treatment is 190°C to 230°C, the screw rotation speed is 200 rotations/minute, and the input speed is 6 rotations/minute.

Then, the extrudate was subjected to cooling treatment, air drying treatment, granulation treatment and drying treatment to obtain a styrene copolymer-containing composition.

The styrene copolymer-containing composition was subjected to injection treatment at 210°C using a vertical injection molding machine, and left for 24 hours to obtain a molded article having dimensions of 64 mm × 12.7 mm × 10.2 mm.

Comparative Examples 2-3

The styrene copolymer-containing compositions of Comparative Examples 2 to 3 and molded articles thereof were prepared in a manner similar to that of Comparative Example 1, except that the amount of each component shown in Table 1 was different from that of Comparative Example 1.

evaluation item

Impact strength: Three measurement samples were prepared for each Example and Comparative Example. According to ASTM D256 (2004 version) Izod impact test, impact strength measuring device [Pendulum Impact Tester (Taiwan GOTECH, model number: GT-7045-HML) and V-notch sampling machine (V-Notch Sampling) Machine, Taiwan GOTECH, model number: including GT-7016-A3)] under the condition of 23 ° C. got

Each measurement sample was obtained by forming a notch in the molded article of each Example and a comparative example.

"--": not added Example comparative example One 2 3 4 5 6 7 8 One 2 3 Isocyanurate-based compatibilizer represented by the formula (I) production example One One One One One 2 2 3 -- -- -- usage
(parts by weight) 0.1 One One One 2.5 0.1 2.5 One -- -- -- additive
composition
(parts by weight) N,N'-Ethylenebisoctadecanamide 2 2 2 2 2 2 2 2 2 2 2 1010 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 168 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acrylonitrile-butadiene-styrene copolymer usage
(parts by weight) 25 25 15 40 25 25 25 25 25 15 40 Acrylonitrile-Styrene Copolymer usage
(parts by weight) 75 75 85 60 75 75 75 75 75 85 60 Average value of impact strength
(kgf-cm/cm) 35.3 38.6 24.6 44.3 40.5 35.5 39.7 36.8 34.1 22.5 41.8

Through the data in Table 1, when comparing Examples and Comparative Examples in which the amount of the acrylonitrile-butadiene-styrene copolymer and the amount of the acrylonitrile-styrene copolymer are the same, the impact resistance of Examples 1, 2, 5 to 8 It can be seen that the strength is higher than the impact strength of Comparative Example 1, the impact strength of Example 3 is higher than the impact strength of Comparative Example 2, and the impact strength of Example 4 is higher than the impact strength of Comparative Example 3.

That is, the impact strength of the molded article by the composition containing the styrene copolymer including the isocyanurate-based compatibilizer represented by Formula I is the styrene copolymer-containing composition that does not include the isocyanurate-based compatibilizer represented by Formula I. It can be seen that the impact strength of the molded product by

Therefore, by including the isocyanurate-based compatibilizer represented by the formula (I), the compatibility between the acrylonitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer is definitely increased, so acrylonitrile-butadiene-styrene Since the copolymer and the acrylonitrile-styrene copolymer can be mixed more uniformly, the impact strength of the molded article is higher than that of the prior art.

In the above, embodiments and variations of the present invention have been described, but the present invention is not limited thereto, and includes all formulas and equivalent configurations as various configurations included within the spirit and scope of the broadest interpretation.

The styrene copolymer-containing composition of the present invention is particularly suitable for the production of molded articles requiring impact resistance.

Claims (10)

It is represented by the formula (I), wherein R ¹ , R ² , R ³ are all C ₄ ~ It contains an isocyanurate-based compatibilizer and a styrene copolymer composition component, which is a type of C ₁₈ alkyl group, and the styrene copolymer composition component includes an acrylonitrile-butadiene-styrene copolymer and an acrylonitrile-styrene copolymer. A styrene copolymer-containing composition, characterized in that.
Formula I

The method of claim 1,
R ¹ , R ² , R ³ are the same alkyl group, characterized in that the composition containing a styrene copolymer. The method of claim 1,
R ¹ , R ² , and R ³ are all a C ₇ to C ₁₇ alkyl group, characterized in that the composition containing a styrene copolymer. 4. The method of claim 3,
R ¹ , R ² , and R ³ are all a C ₇ alkyl group, characterized in that the styrene copolymer-containing composition. 4. The method of claim 3,
R ¹ , R ² , and R ³ are all a kind of a C ₁₁ alkyl group, a composition containing a styrene copolymer. 4. The method of claim 3,
R ¹ , R ² , and R ³ are all a kind of a C ₁₇ alkyl group, a composition containing a styrene copolymer. The method of claim 1,
Based on 100 parts by weight of the styrene copolymer composition component, the weight part of the isocyanurate-based compatibilizer is in the range of 0.1 parts by weight to 2.5 parts by weight, the composition containing a styrene copolymer. The method of claim 1,
In 100 parts by weight of the styrene copolymer composition component, the weight part of the acrylonitrile-butadiene-styrene copolymer is in the range of 15 parts by weight to 40 parts by weight. The method of claim 1,
A composition containing a styrene copolymer, characterized in that it further comprises an additive composition having at least one additive. 10. The method of claim 9,
wherein the additive is selected from the group consisting of lubricants, antioxidants, and combinations thereof.