AS (acrylonitrile-styrene) resin composite material as well as preparation method and application thereof

Abstract

The invention discloses an AS (acrylonitrile-styrene) resin composite material which comprises the following components in parts by weight: 60-100 parts of AS resin; 10 to 40 parts of glass fiber; and 0.5-5 parts of a compatilizer. By regulating the total weight content and molecular weight distribution of acrylonitrile chain segments in the AS resin, the height orientation defect of glass fibers in the injection molding process can be effectively improved, and then the linear combustion rate of HB is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to an AS resin composite material, a preparation method thereof, and an application thereof. Background Art

[0002] AS resin (acrylonitrile-styrene copolymer) is a thermoplastic polymer material with high strength, excellent transparency, and easy processing. The styrene segment makes the AS resin harder and easier to process, and the acrylonitrile segment endows the AS resin with more excellent chemical resistance and heat resistance. AS resin has excellent combustion performance, and its HB combustion performance can meet the standards of the UL94-HB grade. The linear burning rate of a 3-mm-thick sample is about 30 mm / min.

[0003] Glass fiber reinforcement is an important modification method for AS. The addition of glass fiber can significantly improve the strength and rigidity of the material, reduce its linear thermal expansion coefficient, and endow it with more excellent dimensional stability, making it suitable for parts with higher requirements for strength and dimensional stability, such as air conditioner fan blades, audio housings, and keels of sports floors.

[0004] However, due to the wick effect of glass fiber, the combustion performance of the reinforced modified AS composition will be significantly reduced (the linear burning rate of the reinforced AS material with a thickness of 3 mm is 41-46 mm / min, and the combustion performance can no longer meet the standards of the UL94-HB grade). The so-called wick effect is like a candle that needs a wick to burn. When a candle is lit, due to the presence of the wick, a guiding effect is generated. The melted liquid flows along the wick (highly oriented fibers) towards the direction with a higher temperature. The top of the wick is closest to the flame and has the highest temperature, causing the liquid to vaporize and then burn. The heat generated by the combustion promotes the upward transport of the molten liquid for vaporization combustion, and so on, reducing the flame retardancy of the AS resin. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical defects and provide a fiber-reinforced AS resin composition with a low linear burning rate.

[0006] The present invention is achieved by the following technical solutions: An AS resin composite material, by weight, comprises the following components: 60-100 parts of AS resin; 10-40 parts of glass fiber; 0.5-5 parts of compatibilizer; Among them, the acrylonitrile chain segment in the AS resin accounts for 28-35 wt% of the total weight of the AS resin, the part of the AS resin with a weight average molecular weight range of 100,000-120,000 accounts for 60-90 wt% of the total weight of the AS resin, and the part with a weight average molecular weight range of 500,000-600,000 accounts for 10-40 wt% of the total weight of the AS resin.

[0007] Preferably, the part of the AS resin with a weight average molecular weight range of 100,000-120,000 accounts for 65-85 wt% of the total weight of the AS resin, and the part with a weight average molecular weight range of 500,000-600,000 accounts for 15-35 wt% of the total weight of the AS resin.

[0008] More preferably, the part of the AS resin with a weight average molecular weight range of 100,000-120,000 accounts for 70-80 wt% of the total weight of the AS resin, and the part with a weight average molecular weight range of 500,000-600,000 accounts for 20-30 wt% of the total weight of the AS resin.

[0009] The weight average molecular weight distribution of the AS resin is tested by gel permeation chromatography (GPC), and a TDA 302 type GPC analyzer produced by Viscotek Corporation of the United States is used to determine the relative molecular weight and its distribution of the polymer. Polystyrene is used as the standard sample, tetrahydrofuran is used as the eluent, the flow rate is 1.0 ml / min, and the test temperature is 30 °C.

[0010] The AS resin can be a commercially available product or obtained by self-making. Among them, the self-making method can be: adopting a continuous bulk polymerization production process, continuously adding acrylonitrile and styrene monomers and a molecular weight regulating agent according to a set ratio while continuously discharging the reaction solution from the reactor, and separating unreacted monomers and polymers during the devolatilization process. The polymerization product is transported to the extrusion process for granulation to become a finished product, and the unreacted monomers are recovered in the recovery process and then all returned to the raw material process for recycling. The unreacted monomers and polymers are separated during the devolatilization process. The polymerization product is transported to the extrusion process for granulation to become a finished product, and the unreacted monomers are recovered in the recovery process and then all returned to the raw material process for recycling.

[0011] The compatibilizer is selected from at least one of ABS-g-MAH, AS-g-MAH, methyl methacrylate, styrene-maleic anhydride copolymer, and styrene-acrylonitrile-glycidyl methacrylate copolymer.

[0012] Preferably, the compatibilizer is selected from methyl methacrylate.

[0013] By weight, it further includes 0 - 1 part of lubricant. The lubricant can be at least one of stearate lubricants, fatty acid lubricants, and stearic acid ester lubricants; the stearate lubricants are selected from at least one of calcium stearate, magnesium stearate, and zinc stearate; the fatty acid lubricants are selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; the stearic acid ester lubricants are selected from at least one of pentaerythritol stearate.

[0014] The preparation method of the AS resin composite material of the present invention includes the following steps: according to the ratio, mix each component evenly, and extrude and pelletize through a twin-screw extruder. The temperature range of the screw is 210 - 250 °C, and the rotation speed is 100 - 500 r / min.

[0015] The application of the AS resin composite material of the present invention is used for preparing electrical appliance casings.

[0016] The present invention has the following beneficial effects: In the present invention, the AS resin with a specific molecular weight distribution and a specific acrylonitrile chain segment content has a very strong interaction with glass fiber. At the same time, a compatibilizer is selected to further improve the interaction between the matrix material and glass fiber. The low molecular weight AS resin has excellent processability but low viscosity, and the glass fiber is more likely to be oriented along the flow direction during the injection molding process. In this patent, a part of ultra-high molecular weight AS resin is compounded to further increase the viscosity of the material, thereby reducing the orientation of glass fiber along the injection molding flow direction, making the glass fiber more evenly distributed in the matrix resin, and greatly reducing the influence of the orientation of glass fiber on the HB combustion performance of the material, so that the HB linear combustion rate of the glass fiber reinforced AS material is significantly decreased to meet the standard requirements of UL94 for HB combustion, and greatly improve the safety of using the reinforced AS material. Specific embodiments

[0017] The following will describe the present invention in detail with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0018] The sources of the raw materials used in the present invention are as follows: The above AS resin is self-made.

[0019] Glass fiber: ECS13 - 4.5 - 534A, China National Bluestar (Group) Co., Ltd.; ABS-g-MAH: KT-2H, Shenyang Ketong, China; AS-g-MAH: S601N, UMG, Japan; Methyl methacrylate: PMMA CM-207, Chi Mei, Taiwan, China; Styrene-maleic anhydride copolymer: SMA 700, Hua Wen, Shanghai, China; Styrene-acrylonitrile-glycidyl methacrylate copolymer: SAG-002, Jia Yirong, Jiangsu, China; Preparation method of the AS resin composite in the examples and comparative examples: According to the ratio, mix each component evenly, and extrude and pelletize through a twin-screw extruder. The temperature range of the screw is: the first zone of the screw is 220 - 250 °C, the second zone is 220 - 240 °C, the third zone is 210 - 220 °C, the fourth zone is 210 - 230 °C, the fifth zone is 210 - 230 °C, the die temperature is 220 - 230 °C, and the rotation speed is 100 - 500 r / min. Each test method: (1) HB linear burning rate: UL 94-2018 HB combustion performance test, the thickness of the specimen is 3 mm, and the test equipment is the horizontal and vertical combustion tester HVUL2 of ATLAS, USA. Generally, when the HB linear burning rate is less than 38 mm / min, it is considered that the wick effect is effectively improved. The purpose of the present invention is to limit the HB linear burning rate to below 36 mm / min.

[0020] Table 1: Component contents (parts by weight) and test results of the AS resin composites in the examples and comparative examples Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Type of AS resin C D E C C C Content of AS resin 48 48 48 36 39 42 Type of AS resin K M L K K K Content of AS resin 12 12 12 24 21 18 Glass fiber 10 10 10 10 10 10 AS-g-MAH 3 3 3 3 3 3 Acrylonitrile content, % 28 30 35 28 28 28 HB linear burning rate, (mm / min) 33.9 33.4 33.9 35.2 34.4 33.6 As can be seen from Examples 1 / 4 - 8, when within the preferred molecular weight ratio range of the AS resin, the HB linear burning rate is lower.

[0021] Continued Table 1: Example 7 Example 8 Example 9 Example 10 Type of AS resin C C C E Content of AS resin 51 54 64 80 Type of AS resin K K L K Content of AS resin 9 6 16 20 Glass fiber 10 10 20 40 AS-g-MAH 3 3 1 3 Acrylonitrile content, % 28 28 29.4 33.6 HB linear burning rate, (mm / min) 35.1 35.9 34.0 33.3 Continued Table 1: Example 11 Example 12 Example 13 Example 14 AS resin C 48 48 48 48 AS resin K 12 12 12 12 Glass fiber 10 10 10 10 CM-207 3 ABS-g-MAH 3 SAG-002 3 PMMA SMA 700 3 Acrylonitrile content, % 28 28 28 28 HB linear burning rate, (mm / min) 33.2 34.2 34.1 33.8 As can be seen from Examples 1 / 11 - 14, when the compatibilizer is preferably methyl methacrylate, the HB phenomenon burning rate is lower.

[0022] Continued Table 1: Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Type of AS resin C C C A B Content of AS resin 30 57 60 48 48 Type of AS resin K K K K K Content of AS resin 30 3 60 12 12 Glass fiber 10 10 10 10 10 10 AS-g-MAH 3 3 3 3 3 3 Acrylonitrile content, % 28 28 28 28 29.6 24 HB linear burning rate, (mm / min) 37.2 44.5 45.7 38.5 37.2 37.9 As can be seen from Comparative Examples 1 - 4, if the ratio of the two AS resins is not within the scope of the present invention, the HB linear burning rate is too fast.

[0023] As can be seen from Comparative Examples 5 / 9, when the weight average molecular weight of the AS resin is too low, the HB linear burning rate will also increase.

[0024] As can be seen from Comparative Examples 6 / 7 / 10 / 11, when the total acrylonitrile content of the AS resin is not within the scope of the present invention, even if the molecular weight distribution is within the scope of the present application, the HB linear burning rate is relatively fast.

[0025] Continued Table 1: Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Type of AS resin F G C C E C Content of AS resin 48 48 48 48 48 48 Type of AS resin M K H I J N Content of AS resin 12 12 12 12 12 12 Glass fiber 10 10 10 10 10 10 AS-g-MAH 3 3 3 3 3 3 Acrylonitrile content, % 36.4 28 28 27 35.6 28.4 HB linear burning rate, (mm / min) 38.0 36.6 36.8 36.5 36.8 37.6 It can be seen from Comparative Example 8 / 12 that if the weight-average molecular weight of the AS resin is too high, the linear combustion rate of HB is also relatively fast.

Claims

1. An AS resin composite material, characterized in that, By weight parts, it comprises the following components: 60 - 100 parts of AS resin; 10 - 40 parts of glass fiber; 0.5 - 5 parts of compatibilizer; Wherein, the acrylonitrile segment in the AS resin accounts for 28 - 35 wt% of the total weight, the part with a weight-average molecular weight range of 100,000 - 120,000 in the AS resin accounts for 60 - 90 wt% of the total weight of the AS resin, and the part with a weight-average molecular weight range of 500,000 - 600,000 in the AS resin accounts for 10 - 40 wt% of the total weight of the AS resin.

2. The AS resin composite material according to claim 1, wherein The part with a weight-average molecular weight range of 100,000 - 120,000 in the AS resin accounts for 65 - 85 wt% of the total weight of the AS resin, and the part with a weight-average molecular weight range of 500,000 - 600,000 in the AS resin accounts for 15 - 35 wt% of the total weight of the AS resin.

3. The AS resin composite material according to claim 1, characterized in that, The part with a weight-average molecular weight range of 100,000 - 120,000 in the AS resin accounts for 70 - 80 wt% of the total weight of the AS resin, and the part with a weight-average molecular weight range of 500,000 - 600,000 in the AS resin accounts for 20 - 30 wt% of the total weight of the AS resin.

4. The AS resin composite material according to claim 1, characterized in that, The compatibilizer is selected from at least one of ABS-g-MAH, AS-g-MAH, methyl methacrylate, styrene-maleic anhydride copolymer, and styrene-acrylonitrile-glycidyl methacrylate copolymer.

5. The AS resin composite material according to claim 4, wherein The compatibilizer is selected from methyl methacrylate.

6. The AS resin composite material according to claim 1, wherein, By weight parts, it further comprises 0 - 1 part of lubricant.

7. The preparation method of the AS resin composite material according to any one of claims 1-6, characterized in that, It comprises the following steps: according to the ratio, mix each component evenly, and extrude and pelletize through a twin-screw extruder. The temperature range of the screw is 210 - 250 °C, and the rotation speed is 100 - 500 r / min.

8. Use of the AS resin composite material according to any one of claims 1-6, characterized in that, It is used for preparing an electrical appliance housing.