ABS (Acrylonitrile Butadiene Styrene) resin composition as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) resin composition which comprises the following components in parts by weight: 70 parts of ABS resin; 10 to 20 parts of an N-phenyl maleimide polymer; 4 to 16 parts of nanometer aluminum oxide; and 1 to 4 parts of POE grafted SAN. According to the invention, the POE crosslinking effect in the POE grafted SAN is selected, so that the dispersion of the nano aluminum oxide can be facilitated, and better heat conduction, low CLTE and noise reduction performance can be achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to an ABS resin composition and a preparation method and application thereof. Background Art

[0002] ABS (acrylonitrile-butadiene-styrene) is a terpolymer of acrylonitrile-butadiene-styrene. Since ABS resin coordinates the superior properties of the three components, it has excellent impact strength, good processing performance and chemical stability, is easy to mold, and the products are glossy, tough and flexible, with excellent comprehensive performance. ABS resin is widely used in the automotive industry, electronic and electrical industry, light industrial appliances, textiles and construction industries due to its excellent comprehensive performance. In recent years, the automotive industry has paid more and more attention to the noise inside the car. The noise inside the car mainly comes from the extrusion of the joint parts inside the car and the friction between the parts. The high noise inside the car will directly affect the physical and mental health of the driver and passengers, and even affect the driving safety.

[0003] In order to improve the noise problem in the car, the common method is to use grease or felt to reduce the noise, but this method has complicated procedures, high costs, and cannot achieve a lasting anti-noise effect. Chinese patent CN102229736A discloses a lightweight noise reduction modified ABS material. In the invention, hollow particle-type inorganic fillers are added to the formula. The special structure of the hollow particles makes the material have a certain noise reduction function. At the same time, the material density is very low, which has high application value for automobile lightweight and shock absorption and noise reduction. Summary of the invention

[0004] The object of the present invention is to provide an ABS resin composition with good thermal conductivity, low CLTE and noise reduction performance, and a preparation method and application thereof.

[0005] The present invention is achieved through the following technical solutions: An ABS resin composition, comprising the following components in parts by weight: ABS resin 70 parts; 10-20 parts of N-phenylmaleimide polymer; 4-16 parts of nano-alumina; POE grafted SAN 1-4 parts; Among them, in POE grafted SAN, SAN accounts for 60-90wt% of the total weight.

[0006] Preferably, in the POE-grafted SAN, SAN accounts for 70-80 wt% of the total weight.

[0007] POE grafted SAN can be a commercial product or homemade, and can be grafted copolymerized using a grafting polymerization method known in the art, such as: using ethylene-1-octene copolymer (POE) and styrene monomer acrylonitrile monomer for emulsion polymerization, the reaction temperature is 60-140°C, and the pressure in the reactor is 0.1-1.2MPa. The POE grafted SAN copolymer (POE-g-SAN) is synthesized. The weight content of SAN in the POE grafted SAN is adjusted by controlling the ratio of SAN to POE. The initiator is BPO (dibenzoyl peroxide) and the solvent is toluene.

[0008] The POE is selected from at least one of ethylene-octene copolymer and ethylene-butene copolymer.

[0009] In SAN, the weight ratio of styrene to acrylonitrile ranges from (60-80%) to (20-40%).

[0010] The N-phenylmaleimide polymer is selected from at least one of styrene-N-phenylmaleimide-maleic anhydride copolymer and 1-phenyl-1H-pyrrole-2,5-dione polymer.

[0011] The average particle size of the nano-alumina is 10-100 nanometers, preferably 40-60 nanometers. Laser particle size analysis: The nano-alumina particles are irradiated with laser, and the particle size distribution and average particle size are determined by measuring the scattering or diffraction of the particles to the laser.

[0012] The melt index of the ABS resin is 5-25 g / 10 min, the conditions are 220° C., 10 kg, and the test standard is ISO1133-2011.

[0013] In the ABS resin composition of the present invention, the ABS resin accounts for no less than 55 wt % of the total weight of the composition.

[0014] It is possible to choose whether to add 0-2 parts of auxiliary agent according to actual conditions, and the auxiliary agent is selected from at least one of an antioxidant, a lubricant, and a light stabilizer.

[0015] The preparation method of the ABS resin composition of the present invention comprises the following steps: mixing the components uniformly according to the proportion, extruding and granulating through a twin-screw extruder to obtain the ABS resin composition. The temperature range of the screw barrel is 220-245°C.

[0016] The ABS resin composition of the present invention is used for preparing vehicle-mounted parts.

[0017] The present invention has the following beneficial effects: The present invention adds POE grafted SAN as a compatibilizer for ABS resin and N-phenylmaleimide polymer. At the same time, the cross-linking effect of POE in the POE grafted SAN is beneficial to the dispersion of nano-alumina, so that the N-phenylmaleimide polymer and the nano-alumina are evenly dispersed, and the damping coefficient of the system is also improved. Under the combined effect of the two, the absorption capacity of the material itself to external noise is improved, thereby achieving better heat conduction, reducing CLTE and noise reduction effects. DETAILED DESCRIPTION

[0018] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0019] The sources of raw materials used in the present invention are as follows: ABS resin: Shanghai Gaoqiao Petrochemical Company, brand ABS 8434; N-phenylmaleimide polymer: Nippon Electric Chemical, brand MS-NI; Nano-alumina was purchased from Hangzhou Jiupeng New Materials Co., Ltd., and raw materials with different average particle sizes were obtained by screening: Nano-alumina A: average particle size is 12.1 nanometers; Nano-alumina B: average particle size is 41.0 nanometers; Nano-alumina C: average particle size is 57.9 nanometers; Nano-alumina D: average particle size is 99.3 nanometers; Nano-alumina E: average particle size is 6.3 nanometers; Nano-alumina F: The average particle size is 144.2 nanometers.

[0020] POE grafted SAN-1: SAN (st / AN weight ratio 3:2) accounted for 60wt% of the total weight and was homemade; POE grafted SAN-2: SAN (st / AN weight ratio 3:2) accounted for 70wt% of the total weight and was homemade; POE grafted SAN-3: SAN (st / AN weight ratio 3:2) accounted for 80wt% of the total weight and was homemade; POE grafted SAN-4: SAN (st / AN weight ratio 3:2) accounted for 90wt% of the total weight and was homemade; POE grafted SAN-5: SAN (st / AN weight ratio 3:1) accounts for 90wt% of the total weight, homemade POE grafted SAN-6: SAN (st / AN weight ratio 3:2) accounted for 50wt% of the total weight and was homemade; POE grafted SAN-7: SAN (st / AN weight ratio 3:2) accounted for 95wt% of the total weight and was homemade.

[0021] The homemade method is: use ethylene-1-octene copolymer (POE) to emulsion polymerize with styrene monomer and acrylonitrile monomer, the reaction temperature is 60-140℃, and the pressure in the reactor is 0.1-1.2MPa; synthesize POE grafted SAN copolymer (POE-g-SAN). The weight content of SAN in POE grafted SAN is adjusted by controlling the ratio of SAN to POE. The initiator is BPO (dibenzoyl peroxide) and the solvent is toluene. POE: POE8450, Dow, USA.

[0022] Maleic anhydride grafted POE: N406, Ningbo Nengzhiguang.

[0023] Antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1, produced and provided by Ciba Company; Lubricant: Pentaerythritol stearate, produced and provided by LOZA Company, with the brand name GLYCOLUBE-P.

[0024] The preparation method of the ABS resin composition of the embodiment and the comparative example is as follows: the components are mixed and added into the main barrel of a twin-screw extruder (screw diameter is 35 mm, aspect ratio L / D=48). The temperature of each section of the main barrel (from the feed port to the die outlet) is controlled at 220°C, 230°C, 240°C, 245°C, and 240°C respectively, the twin-screw speed is 300 rpm, and the extruded material strips are cooled in a water tank and pelletized to obtain the ABS resin composition.

[0025] Various test methods: (1) Thermal conductivity: Tested in accordance with ISO 8301:1991 standard.

[0026] (2) CLTE: Tested in accordance with ISO 11359-2:2011 standard.

[0027] (3) Noise hazard value assessment: The test is conducted in accordance with the standards of the German Association of the Automotive Industry. The noise hazard value is divided into 10 levels, 1-3 is low risk, 4-5 is a gray area, and 6-10 is high risk.

[0028] Table 1: Content of each component (parts by weight) and test results of ABS resin compositions of Examples 1-7 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 ABS resin 70 70 70 70 70 70 70 N-Phenylmaleimide polymer 15 10 20 15 15 15 15 Nano Alumina A 10 15 5 10 10 10 10 POE grafted SAN-1 2 4 1 POE grafted SAN-2 2 POE grafted SAN-3 2 POE grafted SAN-4 2 POE grafted SAN-5 2 Antioxidants 0.2 0.2 0.2 0.2 0.2 0.2 Lubricants 0.2 0.2 0.2 0.2 0.2 0.2 Thermal conductivity / (W / mK) 25 21 17 27 28 24 24 CLTE / (μm / (m*℃)) 61 48 69 58 57 62 61 Noise Danger Level 3 3 3 2 2 3 3 It can be seen from Examples 1 / 4 / 5 / 6 / 7 that the preferred SAN grafting ratio has a higher thermal conductivity, a smaller CLTE value, and a lower noise hazard value.

[0029] Table 2: Content of each component (parts by weight) and test results of ABS resin compositions of Examples 8-10 Example 8 Example 9 Example 10 ABS resin 70 70 70 N-Phenylmaleimide polymer 15 15 15 Nano Alumina B 10 Nano Alumina C 10 Nano Alumina D 10 POE grafted SAN-1 2 2 2 Antioxidants 0.2 0.2 0.2 Lubricants 0.2 0.2 0.2 Thermal conductivity / (W / mK) 30 29 17 CLTE / (μm / (m*℃)) 58 57 62 Noise Danger Level 1 1 3 It can be seen from Examples 1 / 8-10 that the preferred average particle size range of nano zinc oxide has higher thermal conductivity, better dimensional stability and lower noise hazard value.

[0030] It can be seen from the above embodiments that the thermal conductivity of the ABS resin composition of the present invention can reach above 17 W / mK, the CLTE is less than 69 μm / (m*°C), and the noise hazard value is less than or equal to 3.

[0031] Table 3: Comparative Examples 1-3 ABS resin composition component content (parts by weight) and test results Comparative Example 1 Comparative Example 2 Comparative Example 3 ABS resin 70 70 70 N-Phenylmaleimide polymer 15 15 15 Nano Alumina A 10 10 10 POE grafted SAN-1 0 0.5 6 Antioxidants 0.2 0.2 0.2 Lubricants 0.2 0.2 0.2 Thermal conductivity / (W / mK) 11 16 18 CLTE / (μm / (m*℃)) 75 70 71 Noise Danger Level 6 5 5 It can be seen from Comparative Examples 1-3 that if POE-grafted SAN is not contained or the content is too low or too high, an effective heat conduction and noise reduction network cannot be formed in the resin matrix.

[0032] Table 4: Comparative Examples 4-8 ABS resin composition component content (parts by weight) and test results Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 ABS resin 70 70 70 70 70 N-Phenylmaleimide polymer 15 15 15 15 15 Nano Alumina A 10 10 10 Nano Alumina E 10 Nano Alumina F 10 POE grafted SAN-1 2 2 POE grafted SAN-5 2 POE grafted SAN-6 2 Maleic Anhydride Grafted POE 2 Antioxidants 0.2 0.2 0.2 0.2 0.2 Lubricants 0.2 0.2 0.2 0.2 0.2 Thermal conductivity / (W / mK) 15 16 11 12 14 CLTE / (μm / (m*℃)) 68 67 71 72 71 Noise Danger Level 6 6 5 5 4 It can be seen from comparative examples 4 / 5 that when the content of SAN in the POE-grafted SAN is not within the range of the present invention, it is impossible to effectively form a heat-conducting and noise-reducing network.

[0033] It can be seen from Comparative Examples 6 / 7 that when the average particle size of nano-alumina is not within the range of the present invention, it is difficult to disperse and form a network structure for heat conduction and noise reduction, thereby reducing the effects of heat conduction and noise reduction.

[0034] It can be seen from Comparative Example 8 that the commonly used compatibilizer maleic anhydride grafted POE in the art cannot achieve the technical effect of the present invention.

Claims

1. An ABS resin composition, characterized in that: By weight, it includes the following components: ABS resin 70 parts; 10-20 parts of N-phenylmaleimide polymer; 4-16 parts of nano-alumina; POE grafted SAN 1-4 parts; Among them, in POE grafted SAN, SAN accounts for 60-90wt% of the total weight.

2. The ABS resin composition according to claim 1, characterized in that In POE-grafted SAN, SAN accounts for 70-80wt% of the total weight.

3. The ABS resin composition according to claim 1, characterized in that: The POE is selected from at least one of ethylene-octene copolymer and ethylene-butene copolymer.

4. The ABS resin composition according to claim 1, characterized in that: The N-phenylmaleimide polymer is selected from at least one of styrene-N-phenylmaleimide-maleic anhydride copolymer and 1-phenyl-1H-pyrrole-2,5-dione polymer.

5. The ABS resin composition according to claim 1, characterized in that: The average particle size of the nano-alumina is 10-100 nanometers.

6. The ABS resin composition according to claim 5, characterized in that: The average particle size of the nano-alumina is 40-60 nanometers.

7. The ABS resin composition according to claim 1, characterized in that: The melt index of the ABS resin is 5-25 g / 10 min, the conditions are 220° C., 10 kg, and the test standard is ISO1133-2011.

8. The ABS resin composition according to claim 1, characterized in that: By weight, the invention further comprises 0-2 parts of auxiliary agents, wherein the auxiliary agents are selected from at least one of antioxidants, lubricants and light stabilizers.

9. The method for preparing the ABS resin composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to the proportion, extruding and granulating through a twin-screw extruder to obtain an ABS resin composition.

10. Use of the ABS resin composition according to any one of claims 1 to 8, characterized in that: Used to prepare vehicle-mounted parts.