CN114891307B - ASA material and preparation method and application thereof - Google Patents

Abstract

The invention discloses an ASA material, a preparation method and application thereof, wherein the ASA material comprises the following components in parts by weight: 40-75 parts of SAN resin, 20-40 parts of ASA rubber powder, 1-8 parts of abnormal sound prevention auxiliary agent and 0.5-6 parts of weather resistant agent, wherein the abnormal sound prevention auxiliary agent is vinyl copolymer and/or styrene-based copolymer. The ASA material provided by the invention has the remarkable characteristics of abnormal sound prevention and high weather resistance, and can solve the problem of abnormal sound encountered by automobile plastic parts.

Description

ASA material and preparation method and application thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an ASA material and a preparation method and application thereof.

Background

Starting from the first gasoline internal combustion engine automobile invented by kart, benz, 19 th century, global automobile yields reached 9686 tens of thousands in 2017 with the continued development of automobile technology and production levels. In modern society, which is also receiving global attention to the problems of energy conservation and emission reduction, automobile weight reduction is always a topic of continuous attention of the automobile industry. The rapid development of polymer material technology makes it possible to replace steel with plastic. Nowadays, large-sized parts such as automobile bumpers, spoilers, luggage racks and the like are gradually "plastic", which reduces the weight of the automobile body and can greatly reduce the fuel consumption of the automobile. According to the statistical estimation in the industry, the fuel consumption can be reduced by 6-8% and the emission can be reduced by 5-6% when the weight of the automobile is reduced by 10%.

Parts such as automobile grilles, spoilers and mirror housings are commonly prepared from acrylonitrile-acrylate-styrene copolymer (i.e., ASA). The automotive manufacturers have found that ASA plastic parts, when assembled with other parts, produce "crunchy" abnormal sounds due to occasional relative friction. Such abnormal sounds are extremely easily generated when the automobile passes over rough road surfaces or when the automobile experiences a large temperature change outdoors, and these abnormal sounds very affect the consumer experience. The conventional solution to the above problems is to apply felt or lubricating oil to the location of the buckle or rail, which complicates the processing and increases the processing cost.

In addition to abnormal sound, extremely high weather resistance is required for articles used outside the cockpit of an automobile. The styrene polymer is easy to excite free radical under illumination, and once free radical is generated, the photo-aged chain reaction can cause obvious yellowing and even pulverization of the copolymer due to degradation, thus influencing the beautiful appearance and the safety of plastic parts. Although ASA itself has better weather resistance, if the weather resistance of ASA can be improved as much as possible, the aesthetic property and the safety of the related automobile plastic parts can be ensured in the long-term use process.

Therefore, how to solve the "crunchy" abnormal sound conditions encountered by automotive plastic parts from the material itself is a problem that needs to be solved.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides an ASA material and a preparation method and application thereof. The ASA material provided by the invention has the remarkable characteristics of abnormal sound prevention and high weather resistance, and can solve the problem of crunchy abnormal sound encountered by automobile plastic parts.

The method is realized by the following technical scheme:

an ASA material comprises the following components in parts by weight:

the abnormal sound prevention auxiliary agent is vinyl copolymer and/or styrene copolymer.

Preferably, the composition comprises the following components in parts by weight:

further, the SAN resin has an acrylonitrile content of 25 to 40 wt.%. If the acrylonitrile content is too low, the weather resistance of the product is poor; if the acrylonitrile content is too high, the abnormal sound resistance of the product is poor, and the damping performance is affected due to insufficient flexibility of a molecular chain of the product caused by the partial rigidity of an acrylonitrile structure.

Further, the vinyl copolymer is one or more of an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene-maleic anhydride copolymer, an ethylene-styrene-maleic anhydride copolymer, an ethylene-propylene-maleic anhydride copolymer or an ethylene-octene-maleic anhydride copolymer.

Further, the styrene-based copolymer is one or more of acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-styrene-ethylene propylene copolymer, acrylate-styrene-butadiene copolymer, styrene-ethylene-styrene copolymer, styrene-hydrogenated ethylene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer or styrene-hydrogenated ethylene-styrene-maleic anhydride copolymer.

Preferably, the abnormal sound prevention auxiliary agent is an ethylene-octene copolymer.

Further, the SAN resin has a melt index of 5-120g/10min under test conditions of 220℃and 10kg.

Preferably, the particle size of the ASA rubber powder is 100-350nm, and compared with ASA rubber powder with large particle size, ASA rubber powder with small particle size can enable the light transmittance of the material to be higher, light can pass through the ASA material more easily, and the aging of the material is prevented from being accelerated due to the fact that a large amount of heat is generated in the material due to the fact that light is gathered, so that the weather resistance of the material is improved. However, if the particle size of the ASA rubber powder is too small, the abnormal sound prevention characteristic is deteriorated, because the particle size of the rubber is too small, the toughness of the product is poor, and the damping performance of the material is poor. The method for testing the particle size of ASA rubber powder comprises the following steps: ASA rubber powder and SAN are blended according to the proportion of 3:7, extruded and granulated by an extruder, and injection molded into ISO dumbbell type bars under the condition of 220 ℃. The slice is taken from the dumbbell type sample bar by means of low-temperature slicing, and after being dyed by the ruthenic acid solvent, the slice is placed under an electron transmission electron microscope for particle size observation and testing.

Further, the weather-proof agent is benzotriazole light stabilizer and/or triazine ultraviolet light absorber.

Further, the benzotriazole-based light stabilizers include, but are not limited to, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, and 2-hydroxy-4-n-octoxybenzophenone. The triazine ultraviolet light absorbers include, but are not limited to, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 2- (2-hydroxy-4-malonate diacetoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine and 2- (2-hydroxy-4-malonate diacetoxyphenyl) -4, 6-bis (4-methyl) phenyl-1, 3, 5-triazine.

Preferably, the weathering agent is a combination of a benzotriazole-based light stabilizer and a triazine-based ultraviolet light absorber.

Further, 0.5-2 parts of auxiliary agent is included.

Further, the auxiliary agent is one or more of an antioxidant, a lubricant or toner.

Further, the antioxidants include, but are not limited to, one or more of tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane, or distearylthiopropionate.

Further, the lubricant includes, but is not limited to, one or more of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bisstearamide, silicone lubricant, and pentaerythritol stearate.

Further, the toner may be selected from pigment and/or dye additives.

The invention also provides a preparation method of the ASA material, which comprises the following steps:

s1, weighing the components according to the proportion, and premixing to obtain a premix;

s2: and (3) feeding the premix in the step (S1) into an extruder for blending, extruding and granulating to obtain the ASA material.

Further, the extruder is a double-screw extruder, the extrusion temperature is 200-240 ℃, and the screw rotating speed is 300-1000r/min.

The invention also provides application of the ASA material in vehicle parts.

Compared with the prior art, the invention has the beneficial effects that:

the damping of the material is optimized by using the abnormal sound prevention auxiliary agent. ASA material is hard and easy to generate harshness and abnormal sound due to stick-slip during friction. The soft chain segment of the abnormal sound prevention auxiliary agent has better flexibility than the acrylic ester chain segment of ASA, so that the damping property is better, the damping property of the ASA material can be enhanced, the vibration frequency of the material during friction can be reduced, and the abnormal sound can be reduced. In addition, by adding a specific weather-proof agent, the weather-proof agent can shield and absorb ultraviolet light on one hand and capture free radicals excited by photons in the material on the other hand, so that the weather-proof performance of the material is further enhanced.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

< preparation of examples and comparative examples >

The raw materials used in the examples and comparative examples of the present invention were all commercially available.

SAN resin A: the acrylonitrile content was 35wt%, and the melt flow rate was measured at 220℃under 10kg under conditions of 30g/10min for the melt flow rate obtained from Jinhu petrochemicals, trade mark 350;

SAN resin B: the acrylonitrile content is 20wt%, and the melt flow rate is measured at 220 ℃ and 10kg under the conditions of 30g/10min, which are obtained from Jinhu petrochemical industry, brand 310;

SAN resin C: the acrylonitrile content was 42wt%, and was obtained from a bench, under the trade designation NX3400, at a melt flow rate of 10g/10min, under the test conditions of 220℃and 10kg;

ASA powder 1: purchased from Jinhu petrochemical industry with the brand XC500 and the grain size of 300nm;

ASA powder 2: purchased from Mitsubishi Li yang, brand SX006, particle size 80nm;

ASA powder 3: purchased from UMG, trade mark A600N, particle size 400nm;

abnormal sound prevention auxiliary agent 1: ethylene-octene copolymer available from dow chemical under the designation 8842;

an anti-abnormal sound additive 2, an acrylonitrile-butadiene-styrene copolymer, which is purchased from Jinhu petrochemical industry with the trade mark HR181;

weather-resistant agent A:2- (2-hydroxy-5-methylphenyl) benzotriazole, available from basf;

weather-resistant agent B:2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, available from Li Anlong;

weather-resistant agent C: the combination ratio of the weather-proof agent A to the weather-proof agent B is 1:1;

an antioxidant: commercial, parallel experiments used the same commercial product;

and (3) a lubricant: commercially available, the same commercial product was used for the parallel test.

The ASA materials of the examples and comparative examples were prepared as follows:

s1, weighing the components according to the proportion, and premixing to obtain a premix;

s2: and (3) putting the premix obtained in the step (S1) into a double-screw extruder for blending, extruding and granulating, wherein the extrusion temperature is 200-240 ℃, and the screw rotating speed is 300-1000r/min.

In the present specification, "parts" means "parts by weight" unless specifically stated otherwise.

< test Standard >

The performance test criteria for each of the examples and comparative examples of the present invention are as follows:

abnormal sound prevention performance: the test was performed according to standard VDA 230-206-2005, test conditions: 40N, speed 4mm/s. According to this standard, RPNs total 1-10. Rpn=1-3, and is judged to be abnormal sound prevention; rpn=4-6, and is determined to be medium noise; rpn=7-10, and is determined to be high noise.

Weather resistance: the test was performed according to standard SAE J2527-2004 for 1600 hours. After the test, the gray scale of the appearance of the template was evaluated according to GB250-2008, and the gray scale was 1-5 in total. Wherein, the gray level is more than or equal to 4, and the judgment is qualified; the gray level < 4 level decision fails. The smaller the number, the worse the weatherability.

TABLE 1 examples 1-8 formulations (parts by weight)

Table 2. Formulation examples 9-17 (parts by weight)

TABLE 3 results of example Performance test

TABLE 3 comparative example formulation

Component (A)	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
						SAN resin A (part)	58.5	58.5	57	82	30
ASA rubber powder 1 (part)	37	35	37	10	62
						Abnormal sound prevention aid 1 (part)	-	5	-	5	5
Abnormal sound prevention auxiliary agent 2 (parts)	-	-	-	0	0
						Weather-proof agent	-	-	C	C	C
Weather-proof agent (part)	-	-	2	2	2
						Lubricant (parts)	0.5	0.5	0.5	0.5	0.5
Antioxidant (part)	0.5	0.5	0.5	0.5	0.5

TABLE 4 comparative example Performance test results

When the number of the weather-resistant agent is small, for example, 0.5 part, the addition amount of the abnormal sound prevention auxiliary agent is excessive, and the weather resistance is reduced; when the added part of the weather-proof agent is enough, for example, more than 2 parts, the part of the anti-abnormal sound auxiliary agent is less than 6 parts, and the weather-proof loss is very small.

Comparative example 1 compared with example 1, comparative example 1 was free of addition of anti-abnormal sound auxiliary agent and weather resistance agent, and its RPN value was significantly increased and gray scale was < 4, indicating that the anti-abnormal sound performance and weather resistance of comparative example 1 were poor, and could not meet the requirements.

Comparative example 2 was not added with a weather resistant agent compared with example 3, and although comparative example 2 had a better RPN value, the weather resistance was significantly insufficient.

Comparative example 3 compared to example 4, comparative example 3 has a much higher RPN value than example 4 due to the absence of the anti-abnormal sound additive, indicating that the anti-abnormal sound performance of comparative example 3 is not good.

Comparative examples 4 and 5 have poor anti-abnormal sound properties and weather resistance compared with examples 1 to 17, since the amounts of SAN resin and ASA rubber powder used were both out of the range of the present embodiment.

As can be seen from comparison of example 5 with example 4 and comparison of example 6 with example 5, the ASA material was better in anti-abnormal sound performance and weather resistance in the preferable range as the amounts of the anti-abnormal sound aid and the weather resistance were further increased. Compared with the examples 8 and 9 and the example 1, the compound use effect of the benzotriazole and the triazine weather-resistant agent is better.

Examples 14 and 15 have an acrylonitrile content of less than 25wt% in the SAN resin of example 14, resulting in deterioration of the weatherability of example 14, as compared with example 1; the SAN resin of example 15 has an acrylonitrile content of greater than 40 wt.% resulting in reduced anti-rattle performance of example 15.

Examples 16 and 17 were inferior to example 1 in terms of the particle diameter of example 16 below 100nm, and the abnormal sound preventing performance of example 16 was deteriorated; the particle diameter of example 17 is larger than 350nm, and the weather resistance of example 17 is deteriorated.

Example 18

A sample was prepared from the ASA material of example 1, and its anti-abnormal sound performance and weather resistance were tested, with the following results: the RPN is 2, and the gray level after the weather resistance experiment is 4.1, so that the ASA material provided by the invention can be considered to be suitable for vehicle parts with high requirements on abnormal sound resistance and weather resistance.

The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (8)

1. An ASA material is characterized by comprising the following components in parts by weight:

the abnormal sound prevention auxiliary agent is one or more of ethylene-octene copolymer and acrylonitrile-butadiene-styrene copolymer.

2. ASA material according to claim 1, characterized in that it comprises the following components in parts by weight:

3. ASA material according to claim 1, characterized in that the acrylonitrile content of the SAN resin is 25-40wt%.

4. ASA material according to claim 1 or 2, wherein the SAN resin has a melt index of 5-120g/10min under test conditions of 220 ℃ and 10kg.

5. ASA material according to claim 1 or 2, characterized in that the ASA powder has an average particle size of 100-350nm.

6. ASA material according to claim 1 or 2, characterized in that the weathering agent is a benzotriazole-based light stabilizer and/or a triazine-based uv absorber.

7. A method of preparing an ASA material according to any one of claims 1-6 comprising the steps of:

s1: weighing the components according to the proportion, and premixing to obtain a premix;

s2: and (3) feeding the premix in the step (S1) into an extruder for blending, extruding and granulating to obtain the ASA material.

8. Use of an ASA material according to any of claims 1-6 in a vehicle part.