An abs composition, its preparation and use

Abstract

The application discloses an ABS composition, which comprises the following components in parts by weight: ABS resin 69-71 parts; styrene / nitrogen phenyl maleimide / maleic anhydride copolymer 1-18 parts; carbon molecular sieve 2-6 parts; styrene-acrylonitrile-glycidyl methacrylate copolymer 0.4-3 parts. The application has the advantages that by adding styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene / nitrogen phenyl maleimide / maleic anhydride copolymer with specific contents, the styrene-acrylonitrile-glycidyl methacrylate copolymer is compatible with ABS, the styrene-acrylonitrile-glycidyl methacrylate copolymer has a chain extension effect, the system molecular weight is increased, and the system is staggered into a net structure; the carbon molecular sieve is distributed in the interpenetrating grid, so that the ABS composition with low noise characteristics is obtained, and the ABS composition has the advantage that the ABS composition is not easy to crack under impact at-30 DEG C.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to an ABS composition, its preparation method, and its application. Background Technology

[0002] ABS (acrylonitrile-butadiene-styrene) is a terpolymer of acrylonitrile, butadiene, and styrene. Because ABS resin combines the superior properties of its three components, it possesses excellent impact strength, good processability, and chemical stability. It is easy to mold, producing glossy finished products that are both tough and flexible, exhibiting excellent overall performance. ABS resin is widely used in the automotive, electronics, light industry, textile, and construction industries due to its outstanding comprehensive properties. In recent years, the automotive industry has paid increasing attention to in-vehicle noise and emissions. In-vehicle noise mainly originates from the compression of internal components and friction between them. Excessive in-vehicle noise can directly affect the physical and mental health of drivers and passengers, and even impact driving safety.

[0003] To improve in-vehicle noise, common methods include using grease or applying felt, but these methods are cumbersome, costly, and lack long-lasting noise reduction. Chinese patent CN102229736A discloses a lightweight, noise-reducing modified ABS material. This invention incorporates hollow particle-type inorganic fillers into the formula. The unique structure of these hollow particles gives the material a certain noise-reducing function, and its low density makes it highly valuable for automotive lightweighting and vibration damping. However, noise reduction through the addition of hollow particles is prone to breakage during extrusion by the screw, thus losing its noise-reducing effect and deteriorating the material's physical properties. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical defects and provide an ABS composition with low noise and good resistance to low-temperature impact cracking.

[0005] This invention is achieved through the following technical solution:

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

[0007] 69-71 parts of ABS resin;

[0008] 1-18 parts of styrene / nitrophenyl maleimide / maleic anhydride copolymer;

[0009] 0.4-3 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer;

[0010] 2-6 parts of carbon molecular sieve;

[0011] The weight ratio of styrene / nitrophenyl maleimide / maleic anhydride copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, and carbon molecular sieve is (0.5-3):(0.2-0.5):1.

[0012] The maleic anhydride content of the styrene / nitrophenyl maleimide / maleic anhydride copolymer that can achieve the purpose of this invention ranges from about 7-13 wt%.

[0013] Preferably, the weight ratio of styrene / nitrophenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve is (1.1-2.1):(0.2-0.5):1, more preferably (1.3-1.8):(0.3-0.4):1.

[0014] The glycidyl methacrylate content in the styrene-acrylonitrile-glycidyl methacrylate copolymer that achieves the purpose of this invention is in the range of 1.5-2.5% by weight.

[0015] This invention does not impose any particular restrictions on ABS resin. The purpose of the invention can be achieved when the melt flow rate of ABS resin is between 10-80 g / 10 min. The test conditions are 220℃ and 10 kg, and the test method is ISO1133-1:2011.

[0016] The average particle size of the carbon molecular sieve is 0.1-5 micrometers. Preferably, the average particle size of the carbon molecular sieve is 1.0-2.5 micrometers. The average particle size of the carbon molecular sieve is measured using a laser particle size analyzer.

[0017] Depending on actual needs, you can choose to add 0-2 parts of additives, which can be selected from antioxidants, lubricants, etc.

[0018] Antioxidants can be: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,5-di-tert-butyl-4-hydroxybenzyl dimethylamine; diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; stearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglycerol allyl ether)-1,3,5-triazine; N,N'-hexamethylene di( 3,5-Di-tert-butyl-4-hydroxy-hydrogenated cinnamamide; N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine; octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; triethylene glycol-bis[3-(3,5-dimethyl-4-hydroxyphenyl)propionate]; triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 2,2'-thiodiethyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.

[0019] The lubricant may be at least one of the following: stearate lubricant, fatty acid lubricant, and stearate ester lubricant; wherein the stearate lubricant is selected from at least one of calcium stearate, magnesium stearate, and zinc stearate; wherein the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; and wherein the stearate ester lubricant is selected from at least one of pentaerythritol stearate.

[0020] The preparation method of the ABS composition of the present invention includes the following steps: mixing the components evenly according to the formula, extruding and granulating them through a twin-screw extruder, wherein the screw temperature range is 220-245°C, to obtain the ABS composition.

[0021] The application of the ABS composition of the present invention, wherein the noise hazard value of the ABS composition of the present application is ≤5, is used to manufacture automotive parts.

[0022] The present invention has the following beneficial effects:

[0023] This invention, by adding a styrene / nitrophenyl maleimide / maleic anhydride copolymer to carbon molecular sieves in a specific ratio, enables the styrene / nitrophenyl maleimide / maleic anhydride copolymer and carbon molecular sieves to form a stable interpenetrating network structure in the resin composition system. The carbon molecular sieves are more evenly distributed in the resin matrix, significantly improving the noise hazard value of the ABS composition and enhancing its impact crack resistance at low temperatures, making it suitable for automotive interior parts. Detailed Implementation

[0024] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0025] The raw materials used in this invention are sourced from the following sources:

[0026] ABS-1: Melt flow rate of 20g / 10min, test conditions 220℃ / 10kg, Shanghai Gaoqiao Petrochemical Company, grade ABS 8434;

[0027] ABS-2: Melt flow rate of 35g / 10min, test conditions of 220℃ / 10kg, Kumho Petrochemical, South Korea, grade ABS750 NSW;

[0028] ABS-3: Melt flow rate of 55 g / 10 min, test conditions 220℃ / 10 kg, LG Chem, grade ABSHP181.

[0029] Styrene / nitrophenyl maleimide / maleic anhydride copolymer A (hereinafter referred to as NA in the examples and comparative tables): Denki Kagaku, Japan, brand name MS-NIP, maleic anhydride content 10±2wt%;

[0030] Styrene / nitrophenyl maleimide / maleic anhydride copolymer B (hereinafter referred to as NB in ​​the examples and comparative tables): Jiaxing Huawen, grade HW-330, maleic anhydride content 10±2wt%;

[0031] Styrene / nitrophenyl maleimide / maleic anhydride copolymer C (hereinafter referred to as NC in the examples and comparative tables): Xingbeida, ST-AN3221, maleic anhydride content is 10±2wt%;

[0032] The carbon molecular sieve was purchased from Huzhou Xin'ao, and the raw material with the corresponding average particle size was obtained through grinding and screening.

[0033] Carbon molecular sieve A: average particle size is 0.1 micrometers;

[0034] Carbon molecular sieve B: average particle size is 1.1 micrometers;

[0035] Carbon molecular sieve C: average particle size is 2.4 micrometers;

[0036] Carbon molecular sieve D: average particle size is 4.8 micrometers.

[0037] Styrene-acrylonitrile-glycidyl methacrylate copolymer A (hereinafter referred to as CA in the examples and comparative examples table): Jiaxing Huawen RAS-302, with a glycidyl methacrylate content of approximately 1.9%;

[0038] Styrene-acrylonitrile-glycidyl methacrylate copolymer B (hereinafter referred to as CB in the examples and comparative examples table): Jia Yi Rong SAG-002, with a glycidyl methacrylate content of approximately 2%;

[0039] Styrene-acrylonitrile-glycidyl methacrylate copolymer C (hereinafter referred to as CC in the examples and comparative examples table): Starbeda ST-AN3224, with a glycidyl methacrylate content of approximately 2.2%;

[0040] Lubricant: PETS-AP, ester-based lubricant (PETS);

[0041] Preparation method of ABS composition in examples and comparative examples: Mix the components evenly, extrude and granulate them through a twin-screw extruder, set the screw temperature to 220 / 230 / 240 / 245 / 240℃ and the rotation speed to 300 rpm to obtain the ABS composition.

[0042] Test methods:

[0043] (1) Noise hazard value evaluation: The German Association of the Automotive Industry (VDA) 230-206 sticky-slip test standard (RPN value) is adopted. The noise hazard value is divided into 10 segments, with 1-3 being low risk, 4-5 being gray area, and 6-10 being high risk.

[0044] (2) Low temperature drop ball test: After the part is stored at -30℃ for 6 hours, it is taken out and immediately dropped by a 500g ball at a height of 600mm to test the low temperature drop ball performance of the part.

[0045] Table 1: Weight parts of each component and test results of the ABS compositions in Examples 1-8

[0046] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 ABS-1 70 70 70 70 70 70 ABS-2 70 ABS-3 70 NA 1 10 18 2 4.4 5.2 7.2 8.4 CA 0.4 1.2 3 0.8 0.8 1.2 1.6 2 Carbon molecular sieve A 2 4 6 4 4 4 4 4 lubricant 0.2 Noise Hazard Values 5 4 4 4 3 1 2 3 Low-temperature drop ball cracking No cracking No cracking No cracking No cracking No cracking No cracking No cracking No cracking

[0047] As can be seen from Examples 4-9, the weight ratio of styrene / nitrophenyl maleimide / maleic anhydride copolymer: polystyrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve significantly affects the noise hazard value and low-temperature drop ball cracking resistance of the ABS composition, and the noise hazard value is lower at the preferred and more preferred weight ratios.

[0048] Table 2: Weight parts of each component and test results of ABS compositions in Examples 9-16

[0049] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 ABS-1 70 70 70 70 70 70 70 70 NA 12 4.4 4.4 4.4 4.4 4.4 NB 4.4 NC 4.4 CA 2 0.8 0.8 0.8 0.8 0.8 CB 0.8 CC 0.8 Carbon molecular sieve A 4 4 4 4 4 Carbon molecular sieve B 4 Carbon molecular sieve C 4 Carbon molecular sieve D 4 Noise Hazard Values 4 3 3 3 3 1 2 3 Low-temperature drop ball cracking No cracking No cracking No cracking No cracking No cracking No cracking No cracking No cracking

[0050] As can be seen from Examples 5 / 14-16, the preferred carbon molecular sieve has a lower noise hazard value when the average particle size is lower. This is at least because, within the system of the present invention, smaller carbon molecular sieve particle sizes are at risk of agglomeration due to viscosity, while larger particle sizes are more prone to shearing and uneven dispersion during dispersion.

[0051] Table 3: Weight parts of each component and test results of the comparative ABS compositions

[0052] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 ABS-1 70 70 70 70 70 70 70 NA 0 1 0 16 2 12 7.2 CA 0 0 1 2.8 0.8 4 0 Carbon molecular sieve A 4 4 4 4 1 8 4 Noise Hazard Values 8 7 7 6 7 6 5 Low-temperature drop ball cracking cracking No cracking cracking No cracking No cracking No cracking cracking

[0053] As shown in Comparative Examples 1-7, the weight ratio of styrene / nitrophenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve needs to be within the range of this invention to simultaneously obtain low noise hazard values ​​and good resistance to low-temperature falling ball cracking. Specifically, as shown in Comparative Examples 1 / 2 / 3 / 7, if the system does not contain styrene / nitrophenyl maleimide / maleic anhydride copolymer and / or styrene-acrylonitrile-glycidyl methacrylate copolymer, a through-network structure cannot be formed, resulting in uneven distribution of carbon molecular sieve. As shown in Comparative Examples 4 / 5, if the weight ratio of styrene / nitrophenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve is not within the range of this invention, it may be due to the instability of the formed through-network structure leading to uneven distribution of carbon molecular sieve. However, as shown in Comparative Example 6, when the carbon molecular sieve content is too high, even if the above three distribution ratios are within the range of this invention, the distribution state of the carbon molecular sieve is easily disrupted, causing an increase in noise hazard values.

Claims

1. An ABS composition, characterized in that, By weight parts, including the following components: ABS resin 69-71 parts; Styrene / nitrogen phenyl maleimide / maleic anhydride copolymer 1-18 parts; Styrene-acrylonitrile-glycidyl methacrylate copolymer 0.4-3 parts; Carbon molecular sieve 2-6 parts; The weight ratio of styrene / nitrogen phenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve is (0.5-3):(0.2-0.5):

1.

2. The ABS composition according to claim 1, characterized in that, The weight ratio of styrene / nitrogen phenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve is (1.1-2.1):(0.2-0.5):

1.

3. The ABS composition according to claim 2, characterized in that, The weight ratio of styrene / nitrogen phenyl maleimide / maleic anhydride copolymer: styrene-acrylonitrile-glycidyl methacrylate copolymer: carbon molecular sieve is (1.3-1.8):(0.3-0.4):

1.

4. The ABS composition according to claim 1, characterized in that, The weight content of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer is 1.5-2.5%.

5. The ABS composition according to claim 1, characterized in that, The melt flow rate of the ABS resin is 10-80 g / 10 min, test conditions 220℃, 10 kg.

6. The ABS composition according to claim 1, characterized in that, The average particle size of the carbon molecular sieve is 0.1-5 microns.

7. The ABS composition according to claim 6, characterized in that, The average particle size of the carbon molecular sieve is 1.0-2.5 microns.

8. The ABS composition according to claim 1, characterized in that, By weight parts, also including 0-2 parts of auxiliary, auxiliary selected from at least one of antioxidant, lubricant.

9. A process for the preparation of the ABS composition according to any one of claims 1 to 8, characterized in that, Including the following steps: according to the ratio, mix each component uniformly, extrude and granulate through double screw extruder, screw temperature range is 220-245℃, get ABS composition.

10. Use of the ABS composition according to any one of claims 1 to 8, characterized in that For preparing vehicle parts. For preparing vehicle parts.