CN112759852A - Acrylonitrile-styrene copolymer material and preparation method thereof - Google Patents
Acrylonitrile-styrene copolymer material and preparation method thereof Download PDFInfo
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- CN112759852A CN112759852A CN202011596514.XA CN202011596514A CN112759852A CN 112759852 A CN112759852 A CN 112759852A CN 202011596514 A CN202011596514 A CN 202011596514A CN 112759852 A CN112759852 A CN 112759852A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an acrylonitrile-styrene copolymer material for promoting ultrasonic attenuation and a preparation method thereof, belonging to the technical field of high polymer materials. The acrylonitrile-styrene copolymer material for promoting ultrasonic attenuation comprises the following components in parts by weight: 40-90 parts of acrylonitrile-styrene resin and 10-50 parts of ultrasonic wave attenuating agent; the ultrasonic wave attenuator comprises at least one of acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-styrene-ethylene propylene rubber copolymer, acrylate-styrene-butadiene copolymer and styrene-ethylene-butylene-styrene copolymer. The acrylonitrile-styrene copolymer material prepared by the formula can eliminate the loss of false alarm radar wave signals in the transmission process, and can be used for preparing automobile parts such as automobile grids, bumpers, automobile logos and the like provided with ultrasonic radar wave detectors.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an acrylonitrile-styrene copolymer material and a preparation method thereof.
Background
"intelligentization" is one of the important topics developed by the automotive industry. With the development of automobile electronic technology, automobile intelligent technology has been gradually applied, automobile operation is simpler and simpler, and driving safety is higher and higher. For example, parking assist systems, automatic parking systems, and even automatic driving systems have come into human life and play an important role in driving automobiles from now on into the future.
In the process of automobile parking, the ultrasonic radar is the most common and mature radar detection system, and compared with other radar waves, the ultrasonic radar has the characteristics of higher detection accuracy, higher speed and timely data transmission capability and the like. The transmitting and receiving device of the general car backing radar is embedded in the bumper, the grating and the car logo of the car. Generally, the reverse sensor only detects objects right in front of the detector, but in rainy season, rainwater flows into gaps between the detector and automobile parts, and a small part of radar wave signals are emitted towards the periphery of the side edge of the detector. When the small part of radar signals are conducted in automobile parts, the small part of radar signals can reflect tiny reflection signals back to the radar receiver when encountering metal or electronic parts, so that the radar wave receiver receives the signals too early, false alarm is generated, and drivers feel confused in the driving process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an acrylonitrile-styrene copolymer material capable of promoting the rapid attenuation of ultrasonic waves in parts and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an acrylonitrile-styrene copolymer material comprises the following components in parts by weight: 40-90 parts of acrylonitrile-styrene resin and 10-50 parts of ultrasonic wave attenuating agent; the ultrasonic wave attenuator comprises at least one of acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-styrene-ethylene propylene rubber copolymer, acrylate-styrene-butadiene copolymer and styrene-ethylene-butylene-styrene copolymer.
The applicant of the invention verifies through experiments that the acrylonitrile-styrene copolymer material prepared by the proportion has good performance of promoting ultrasonic attenuation, and can avoid interference to drivers due to reflection of radar signals in automobile parts.
Preferably, the acrylonitrile-styrene copolymer material comprises the following components in parts by weight: 65-75 parts of acrylonitrile-styrene resin and 25-35 parts of ultrasonic wave attenuating agent. Under the component proportion, the composition has excellent ultrasonic attenuation performance, and also has good fluidity, excellent rigidity-toughness balance and good heat resistance.
Preferably, the loss tangent tan delta of the ultrasonic wave attenuating agent is 0.01-0.1, and two peaks of tan delta within-100-150 ℃ respectively appear within-70-30 ℃ and 100-135 ℃.
Preferably, the two peaks of the loss tangent tan delta of the ultrasonic wave attenuating agent within-100 to 150 ℃ respectively occur within-50 to-30 ℃ and 100 to 120 ℃.
Preferably, the acrylonitrile-styrene resin has a melt flow rate of 10 to 60g/10min at 220 ℃ under 10 kg.
Preferably, the acrylonitrile-styrene copolymer material also comprises 0-20 parts of heat-resistant agent and 0.5-2 parts of auxiliary agent; the auxiliary agent comprises at least one of an antioxidant, a lubricant and toner.
Preferably, the heat-resistant agent comprises at least one of an N-phenylimide-maleic anhydride-styrene polymer, a styrene-maleic anhydride polymer, and an N, phenylimide-maleic anhydride-acrylate-styrene polymer.
Preferably, the antioxidant comprises at least one of organic phosphate antioxidants, phenolic antioxidants, thioester antioxidants, aromatic amine antioxidants and thioether antioxidants. For example tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, butylated reaction products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, benzyl compounds, esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols, esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monohydric or polyhydric alcohols, distearylthiopropionate, dilaurylthiopropionate, alcohol, Ditridecyl thiopropionate, octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) ] propionate, amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, and the like.
Preferably, the lubricant comprises at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bis stearamide, silicone lubricant, pentaerythritol stearate.
Preferably, the toner contains at least one of a pigment and a dye.
Meanwhile, the invention also discloses a preparation method of the acrylonitrile-styrene copolymer material, which comprises the following steps: mixing acrylonitrile-styrene resin, ultrasonic attenuation agent, heat-resistant agent and auxiliary agent uniformly according to a proportion, then putting the mixture into a double-screw extruder for melt blending, extruding and granulating; the extrusion temperature is 200-260 ℃, and the screw rotation speed is 300-700 r/min.
Compared with the prior art, the invention has the beneficial effects that: the invention creatively considers from the material perspective, reduces the risk of false alarm of radar ultrasonic wave induced by rainwater, reduces the requirement on structural design, reduces the processing technology of automobile parts and reduces the cost of the automobile parts on the investment of accessories. The promotion principle is that the damping characteristic of the material is promoted by using the ultrasonic wave attenuating agent, and in the process that the radar ultrasonic wave is transmitted through the material, the friction force consumption generated by the ultrasonic wave due to the vibration of a material molecular chain is converted into heat, so that the phenomenon of false alarm caused by the fact that the ultrasonic wave is reflected back to a radar receiver is avoided.
Drawings
FIG. 1 is a graph of the ultrasonic signal of the acrylonitrile-styrene copolymer material of example 3.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The materials used in the examples and comparative examples are as follows:
acrylonitrile-styrene resin: the melt flow rate is 35g/10min, and the test condition of the melt flow rate is 220 ℃ and 10 kg.
Ultrasonic wave attenuator: 1, an ultrasonic wave attenuator 1, east China sea, wherein the tan delta is 0.04 at 25 ℃, and two peak values of the tan delta within-100-150 ℃ are-40 ℃ and 102 ℃ respectively; 2, the ultrasonic attenuator is brocade lake petrochemical, the tan delta is 0.02 at 25 ℃, and the two peak values of the tan delta within-100-150 ℃ are-60 ℃ and 125 ℃ respectively. tan δ was measured using a dynamic mechanical analyzer, test conditions: frequency 10Hz, strain rate 0.05%.
Heat-resistant agent: styrene-maleic anhydride polymer, Wen.
Antioxidant: tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, Sanfeng chemical.
Lubricant: pentaerythritol stearate, warfarin.
Examples 1 to 6
In the embodiment of the acrylonitrile-styrene copolymer material of the present invention, the formula of the acrylonitrile-styrene copolymer material in embodiments 1 to 6 is shown in table 1, and the preparation method comprises: the acrylonitrile-styrene copolymer, the ultrasonic attenuation agent, the heat-resistant agent and the auxiliary agent are uniformly mixed, and the mixture is put into a double-screw extruder to be melted and blended at 250 ℃ for extrusion and granulation, wherein the screw rotating speed of the double-screw extruder is 500 r/min.
Comparative examples 1 to 2
An acrylonitrile-styrene copolymer material having the formulation shown in Table 1 was prepared in the same manner as in the examples.
TABLE 1 recipe table (parts by weight)
Performance testing
1) Ultrasonic attenuation performance: the material was injection molded into a 100mm x 3mm master. The surface of the sample plate was coated with A layer of ultrasonic coupling agent, available from plain, eastern Wen, model SUWEN-A. An ultrasonic flaw detector probe (Zexu science and technology, model GM28, detection frequency 60KHZ) was placed on the coupling agent, and appropriate pressure was applied to bond it to the sample plate, and an ultrasonic signal was detected, and an ultrasonic signal graph as shown in FIG. 1 was obtained. The formula for calculating the ultrasonic attenuation is as follows:
D＝lg(TW1/TW2)
wherein, Tw1The maximum value of the absolute value of the amplitude of the W1 signal in FIG. 1; t isw2The maximum value of the absolute value of the amplitude of the W2 signal in fig. 1. The larger the value of D, the better the ultrasonic attenuation properties of the material.
2) Heat resistance: the heat distortion temperature is measured according to ISO 75-2-2013, heavy load standard.
3) Mechanical properties: testing the tensile strength according to ISO 527-1-2019 standard, wherein the tensile speed is 50 mm/min; and testing the notch impact strength of the simply supported beam by referring to ISO 180-2019.
4) Fluidity: the melt flow rate was tested with reference to ISO 1133 + 2011, at 220 ℃ under test conditions, 10 kg.
The above-described performance test was performed on examples 1 to 6 and comparative examples 1 to 2, and the test results are shown in table 2.
Table 2 results of performance testing
As can be seen from Table 2, examples 1 to 6 all have good performance of promoting ultrasonic attenuation, and also have excellent heat resistance, fluidity and mechanical properties, and the comprehensive performance of examples 2 to 4 is relatively better, and experimental results show that the ratio of the acrylonitrile-styrene copolymer to the ultrasonic attenuator has a large influence on the performance. When the ultrasonic wave attenuating agent is moderate, the ultrasonic wave attenuating agent is dispersed in acrylonitrile-styrene resin, so that on one hand, the damping performance of the material is improved, on the other hand, the phase interface is much more and dense, and the loss of ultrasonic waves is enhanced. In addition, as can be seen from the comparison between example 3 and example 6, the properties of the ultrasonic wave attenuator itself also have a great influence on the performance of the prepared acrylonitrile-styrene copolymer material; when two peak values of the loss tangent tan delta of the ultrasonic wave attenuating agent at-100-150 ℃ respectively appear at-50-30 ℃ and 100-120 ℃, the prepared acrylonitrile-styrene copolymer material has better performance of promoting ultrasonic wave attenuation. The ultrasonic attenuating agents having different tan δ have different intermolecular vibration frequencies, and an ultrasonic attenuating agent having tan δ in the above range has a stronger loss effect on ultrasonic waves.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
1. An acrylonitrile-styrene copolymer material is characterized by comprising the following components in parts by weight: 40-90 parts of acrylonitrile-styrene resin and 10-50 parts of ultrasonic wave attenuating agent; the ultrasonic wave attenuator comprises at least one of acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-styrene-ethylene propylene rubber copolymer, acrylate-styrene-butadiene copolymer and styrene-ethylene-butylene-styrene copolymer.
2. The acrylonitrile-styrene copolymer material of claim 1, comprising the following ingredients in parts by weight: 65-75 parts of acrylonitrile-styrene resin and 25-35 parts of ultrasonic wave attenuating agent.
3. The acrylonitrile-styrene copolymer material according to claim 1, wherein the ultrasonic attenuating agent has a loss tangent tan δ of 0.01 to 0.1, and two peaks of tan δ within-100 to 150 ℃ respectively occur within-70 to-30 ℃ and 100 to 135 ℃.
4. The acrylonitrile-styrene copolymer material according to claim 3, wherein the two peaks of the loss tangent tan δ of the ultrasonic attenuating agent within-100 to 150 ℃ occur within-50 to-30 ℃ and within 100 to 120 ℃, respectively.
5. The acrylonitrile-styrene copolymer material according to claim 1, wherein the melt flow rate of the acrylonitrile-styrene resin is 10 to 60g/10min at 220 ℃ and 10 kg.
6. The acrylonitrile-styrene copolymer material according to claim 1, further comprising 0 to 20 parts of a heat-resistant agent and 0.5 to 2 parts of an auxiliary agent; the auxiliary agent comprises at least one of an antioxidant, a lubricant and toner.
7. The acrylonitrile-styrene copolymer material of claim 6, wherein the heat-resistant agent comprises at least one of N-phenylimide-maleic anhydride-styrene polymer, styrene-maleic anhydride polymer, and N, phenylimide-maleic anhydride-acrylate-styrene polymer.
8. The acrylonitrile-styrene copolymer material of claim 6, wherein the antioxidant comprises at least one of an organophosphate antioxidant, a phenolic antioxidant, a thioester antioxidant, an aromatic amine antioxidant, and a thioether antioxidant.
9. The acrylonitrile-styrene copolymer material of claim 6, wherein the lubricant comprises at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bis stearamide, silicone lubricant, pentaerythritol stearate.
10. The acrylonitrile-styrene copolymer material of claim 6, wherein the toner comprises at least one of a pigment and a dye.
11. A method for preparing an acrylonitrile-styrene copolymer material according to any one of claims 6 to 10, wherein the method comprises: mixing acrylonitrile-styrene resin, ultrasonic attenuation agent, heat-resistant agent and auxiliary agent uniformly according to a proportion, then putting the mixture into a double-screw extruder for melt blending, extruding and granulating; the extrusion temperature is 200-260 ℃, and the screw rotation speed is 300-700 r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429694A (en) * | 2021-06-15 | 2021-09-24 | 广汽本田汽车有限公司 | Resin composition and preparation method and application thereof |
| CN114591585A (en) * | 2022-03-31 | 2022-06-07 | 金发科技股份有限公司 | Ultrasonic isolation acrylonitrile-styrene copolymer and preparation method thereof |
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| CN101857701A (en) * | 2010-03-10 | 2010-10-13 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-acrylate-styrene resin composite and preparation method thereof |
| CN101864140A (en) * | 2010-03-05 | 2010-10-20 | 上海锦湖日丽塑料有限公司 | Dedicated styrene material for spoiler of automobile and preparation method thereof |
| CN109401165A (en) * | 2018-09-25 | 2019-03-01 | 上海锦湖日丽塑料有限公司 | The heat-resisting AES resin combination and its preparation that tiger fur line is reduced or eliminated |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864140A (en) * | 2010-03-05 | 2010-10-20 | 上海锦湖日丽塑料有限公司 | Dedicated styrene material for spoiler of automobile and preparation method thereof |
| CN101857701A (en) * | 2010-03-10 | 2010-10-13 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-acrylate-styrene resin composite and preparation method thereof |
| CN109401165A (en) * | 2018-09-25 | 2019-03-01 | 上海锦湖日丽塑料有限公司 | The heat-resisting AES resin combination and its preparation that tiger fur line is reduced or eliminated |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429694A (en) * | 2021-06-15 | 2021-09-24 | 广汽本田汽车有限公司 | Resin composition and preparation method and application thereof |
| CN114591585A (en) * | 2022-03-31 | 2022-06-07 | 金发科技股份有限公司 | Ultrasonic isolation acrylonitrile-styrene copolymer and preparation method thereof |
| CN114591585B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | Ultrasonic isolation acrylonitrile-styrene copolymer and preparation method thereof |
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