An abs resin composition, a method for preparing the same, and an application thereof

Abstract

The application discloses an ABS resin composition which comprises the following components in parts by weight: 70 parts of ABS resin, 10-20 parts of N-phenyl maleimide polymer, 4-16 parts of nano-alumina and 1-4 parts of POE grafted SAN. The POE crosslinking effect of the POE grafted SAN can be more favorable to the dispersion of the nano-alumina, so that better heat conduction, low CLTE and noise reduction performance are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular materials, in particular to an ABS resin composition, a preparation method and application thereof. BACKGROUND

[0002] ABS (acrylonitrile-butadiene-styrene) is a terpolymer of acrylonitrile, butadiene and styrene. ABS resin has excellent impact strength, good processing performance and chemical stability due to the coordination of the superior properties of the three components, is easy to mold, the product is rich in gloss, and has toughness and flexibility, and excellent comprehensive performance. ABS resin is widely used in automobile industry, electronic and electrical industry, light industry, household appliances, textile and building industry due to its excellent comprehensive performance. In recent years, the automobile industry pays more and more attention to the noise in the car. The noise in the car mainly comes from the extrusion of the joint parts in the car and the friction between the parts. The high noise in the car will directly affect the physical and mental health of the driver and passengers, and even affect the safety of driving.

[0003] In order to improve the noise problem in the car, the common method is to use lubricating grease or paste felt to reduce noise, but this method is complicated, high in cost, and cannot achieve the effect of lasting noise reduction. Chinese patent CN102229736A discloses a light noise reduction modified ABS material. In the invention, hollow particle type inorganic filler is added to the formula. The special structure of the hollow particle makes the material have certain noise reduction function, and the material has very low density, which has high application value for automobile light weight, shock absorption and noise reduction. SUMMARY

[0004] The purpose of the present application 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 application is realized by the following technical scheme:

[0006] An ABS resin composition, by weight, comprises the following components:

[0007] ABS resin 70 parts;

[0008] N-phenyl maleimide polymer 10-20 parts;

[0009] Nano alumina 4-16 parts;

[0010] POE grafted SAN 1-4 parts;

[0011] Among them, the SAN accounts for 60-90wt% of the total weight in the POE grafted SAN.

[0012] Preferably, the SAN in the POE grafted SAN accounts for 70-80wt% of the total weight.

[0013] The POE grafted SAN can be a commercially available product or self-made, and can be grafted by using a grafting polymerization method known in the art, such as: using ethylene-1-octene copolymer (POE) to perform emulsion polymerization with styrene monomer and acrylonitrile monomer, the reaction temperature is 60-140℃, and the pressure in the reaction kettle 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 proportion of SAN and POE. The initiator is BPO (dibenzoyl peroxide), and the solvent is toluene.

[0014] The POE is at least one selected from ethylene-octene copolymer and ethylene-butene copolymer.

[0015] The weight ratio of styrene to acrylonitrile in the SAN ranges from (60-80%): (20-40%).

[0016] The N-phenyl maleimide polymer is at least one selected from styrene-N-phenyl maleimide-maleic anhydride copolymer and 1-phenyl-1H-pyrrole-2,5-diketone polymer.

[0017] The average particle size of the nano-aluminum oxide is 10-100nm, preferably 40-60nm. Laser particle size analysis method: the nano-aluminum oxide particles are irradiated by laser, and the particle size distribution and average particle size are determined by measuring the scattering or diffraction of the particles to the laser.

[0018] The melt index of the ABS resin is 5-25g / 10min, under the condition of 220℃, 10kg, and the test standard is ISO1133-2011.

[0019] In the ABS resin composition of the present application, the ABS resin accounts for not less than 55wt% of the total weight of the composition.

[0020] 0-2 parts of an auxiliary agent can be selected to be added or not according to actual conditions, and the auxiliary agent is at least one selected from antioxidant, lubricant and light stabilizer.

[0021] The preparation method of the ABS resin composition of the present application comprises the following steps: uniformly mixing the components according to the ratio, and extruding and granulating by a double-screw extruder to obtain the ABS resin composition. The temperature range of the screw cylinder is 220-245℃.

[0022] The ABS resin composition of the present application is applied to prepare a vehicle-mounted part.

[0023] The present application has the following beneficial effects:

[0024] The application adds POE grafted SAN as a compatibilizer of ABS resin and N-phenyl maleimide polymer, and meanwhile, the crosslinking of POE in POE grafted SAN is beneficial to the dispersion of nano-alumina, so that the N-phenyl maleimide polymer and nano-alumina are uniformly dispersed, the damping coefficient of the system is also improved, and the absorption capacity of the material itself to external noise is improved under the joint action of the two, so that better heat conduction, CLTE reduction and noise reduction effects are achieved. DETAILED DESCRIPTION

[0025] The application will be described in detail below in combination with specific examples. The following examples will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that, for those skilled in the art, without departing from the concept of the application, a number of modifications and improvements can be made. These all belong to the protection scope of the application.

[0026] The raw materials used in the application are as follows:

[0027] ABS resin: Shanghai Gaobridge Petrochemical Company, brand ABS 8434;

[0028] N-phenyl maleimide polymer: Japan Electric Chemistry, brand MS-NI;

[0029] Nano-alumina is purchased from Hangzhou Jiupeng New Material Co., Ltd., and raw materials with different average particle sizes are obtained by screening:

[0030] Nano-alumina A: average particle size 12.1 nanometers;

[0031] Nano-alumina B: average particle size 41.0 nanometers;

[0032] Nano-alumina C: average particle size 57.9 nanometers;

[0033] Nano-alumina D: average particle size 99.3 nanometers;

[0034] Nano-alumina E: average particle size 6.3 nanometers;

[0035] Nano-alumina F: average particle size 144.2 nanometers.

[0036] POE grafted SAN-1: SAN (st / AN weight ratio 3:2) accounts for 60wt% of the total weight, self-made;

[0037] POE grafted SAN-2: SAN (st / AN weight ratio 3:2) accounts for 70wt% of the total weight, self-made;

[0038] POE grafted SAN-3: SAN (st / AN weight ratio 3:2) 80wt% of total weight, self-made;

[0039] POE grafted SAN-4: SAN (st / AN weight ratio 3:2) 90wt% of total weight, self-made;

[0040] POE grafted SAN-5: SAN (st / AN weight ratio 3:1) 90wt% of total weight, self-made

[0041] POE grafted SAN-6: SAN (st / AN weight ratio 3:2) 50wt% of total weight, self-made;

[0042] POE grafted SAN-7: SAN (st / AN weight ratio 3:2) 95wt% of total weight, self-made.

[0043] The self-made method is: emulsion polymerization of ethylene-1-octene copolymer (POE) with styrene monomer and acrylonitrile monomer, the reaction temperature is 60-140℃, the pressure in the reaction kettle is 0.1-1.2MPa; POE grafted SAN copolymer (POE-g-SAN) is synthesized. 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, USA Dow.

[0044] Maleic anhydride grafted POE: N406, Ningbo Nengzhi Light.

[0045] Antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1, produced by Ciba Company;

[0046] Lubricant: pentaerythritol stearate, produced by LOZA Company, with the brand GLYCOLUBE-P.

[0047] Preparation method of ABS resin composition of examples and comparative examples: after mixing the components, they are added into the main cylinder of a double screw extruder (screw diameter 35mm, length-diameter ratio L / D=48). The control temperature of each section of the main cylinder (from the feeding port to the exit of the die head) is 220℃, 230℃, 240℃, 245℃, 240℃, the rotation speed of the double screw is 300r / min, and the extruded strip is cooled in a water tank and then pelletized to obtain the ABS resin composition.

[0048] Test methods:

[0049] (1) Thermal conductivity: tested according to ISO 8301:1991 standard.

[0050] (2) CLTE: tested according to ISO 11359-2:2011 standard.

[0051] (3) Noise risk value evaluation: tested according to VDA standard, noise risk value is divided into 10 segments, 1-3 is low risk, 4-5 is grey area, 6-10 is high risk.

[0052] Table 1: ABS resin composition of each component content (parts by weight) and test results of examples 1-7

[0053] 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 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 Lubricant 0.2 0.2 0.2 0.2 0.2 0.2 Thermal conductivity / (W / mK) 25 21 17 27 28 24 24 CLTE / (pm / (m*°C)) 61 48 69 58 57 62 61 Noise hazard value 3 3 3 2 2 3 3

[0054] From examples 1 / 4 / 5 / 6 / 7, it can be seen that the preferred SAN grafting rate is higher, the thermal conductivity is higher, the CLTE value is smaller, and the noise risk value is lower.

[0055] Table 2: ABS resin composition of each component content (parts by weight) and test results of examples 8-10

[0056] 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 Antioxidant 0.2 0.2 0.2 Lubricant 0.2 0.2 0.2 Thermal conductivity / (W / mK) 30 29 17 CLTE / (pm / (m*°C)) 58 57 62 Noise hazard value 1 1 3

[0057] From examples 1 / 8-10, it can be seen that the preferred average particle size range of nano zinc oxide is higher, the thermal conductivity is higher, the dimensional stability is better, and the noise risk value is lower.

[0058] From the above examples, it can be seen that the thermal conductivity of the ABS resin composition of the present application can reach more than 17 W / mK, the CLTE is less than 69 μm / (m*℃), and the noise risk value is less than or equal to 3.

[0059] Table 3: ABS resin composition of each component content (parts by weight) and test results of comparative examples 1-3

[0060] 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 Antioxidant 0.2 0.2 0.2 Lubricant 0.2 0.2 0.2 Thermal conductivity / (W / mK) 11 16 18 CLTE / (pm / (m*°C)) 75 70 71 Noise hazard value 6 5 5

[0061] From comparative examples 1-3, it can be seen that if POE grafted SAN is not contained or the content is too low or too high, an effective thermal conduction and noise reduction network cannot be formed in the resin matrix.

[0062] Table 4: ABS resin composition of each component content (parts by weight) and test results of comparative examples 4-8

[0063] 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 Antioxidant 0.2 0.2 0.2 0.2 0.2 Lubricant 0.2 0.2 0.2 0.2 0.2 Thermal conductivity / (W / mK) 15 16 11 12 14 CLTE / (pm / (m*°C)) 68 67 71 72 71 Noise hazard value Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 ABS resin N-phenylmaleimide polymer Nano alumina A Nano alumina E Nano alumina F POE grafted SAN-1 POE grafted SAN-5 POE grafted SAN-6 Maleic anhydride grafted POE Antioxidant Lubricant Thermal conductivity / (W / mK) CLTE / (pm / (m*°C)) Noise hazard value 6 6 5 5 4

[0064] From comparative examples 4 / 5, it can be seen that when the content of SAN in POE grafted SAN is not within the range of the present application, an effective thermal conduction and noise reduction network cannot be formed.

[0065] From comparative examples 6 / 7, it can be seen that when the average particle size of nano aluminum oxide is not within the range of the present application, it is difficult to disperse and difficult to form a network structure for thermal conduction and noise reduction, thereby reducing the effect of thermal conduction and noise reduction.

[0066] As can be seen from Comparative Example 8, the commonly used compatibilizer maleic anhydride grafted POE cannot achieve the technical effects of the present application.

Claims

1. An ABS resin composition, characterized by comprising: Parts by weight, comprising the following components: ABS resin 70 parts; N-phenyl maleimide polymer 10-20 parts; Nano-alumina 4-16 parts; POE grafted SAN 1-4 parts; Among them, the SAN in POE grafted SAN accounts for 60-90wt% of the total weight; The average particle size of the nano-alumina is 10-100 nanometers.

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

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

4. The ABS resin composition according to claim 1, characterized by The N-phenyl maleimide polymer is selected from at least one of styrene-N-phenyl maleimide-maleic anhydride copolymer, 1-phenyl-1H-pyrrole-2,5-diketone polymer.

5. The ABS resin composition according to Claim 1, characterized by The average particle size of the nano-alumina is 40-60 nanometers.

6. The ABS resin composition according to claim 1, characterized by The melt index of the ABS resin is 5-25g / 10min, under the condition of 220℃, 10kg, and the test standard is ISO1133-2011.

7. The ABS resin composition according to claim 1, characterized by Parts by weight, further comprising 0-2 parts of auxiliary, the auxiliary is selected from at least one of antioxidant, lubricant, light stabilizer.

8. A process for producing the ABS resin composition as claimed in any one of claims 1 to 7, characterized by, Comprising the following steps: according to the ratio, mix each component uniformly, extrude and granulate through double screw extruder, to obtain ABS resin composition.

9. Use of the ABS resin composition according to any one of claims 1 to 7, characterized in that, For preparing vehicle parts.