CN112341828B - Scratch-resistant noise-reducing PC/ASA resin alloy and preparation method thereof - Google Patents
Scratch-resistant noise-reducing PC/ASA resin alloy and preparation method thereof Download PDFInfo
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- CN112341828B CN112341828B CN202011408441.7A CN202011408441A CN112341828B CN 112341828 B CN112341828 B CN 112341828B CN 202011408441 A CN202011408441 A CN 202011408441A CN 112341828 B CN112341828 B CN 112341828B
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a scratch-resistant noise-reducing PC/ASA resin alloy and a preparation method thereof. According to the invention, the scratch-resistant agent and the noise-reducing auxiliary agent are added, the noise-reducing and scratch-resistant performances of the alloy resin are obviously improved, the alloy resin can replace common PC/ASA alloy materials on parts such as automobile and household appliances, and the scratch grade can be improved and the noise can be reduced.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a scratch-resistant noise-reducing PC/ASA resin alloy and a preparation method thereof.
Background
Polycarbonate resin is colorless and transparent, has excellent heat resistance, high strength and impact resistance, and is dimensionally stable, and belongs to engineering plastics with wide application. ASA is mainly acrylonitrile-styrene-acrylate copolymer, and coordinates the superior properties of the three components, so the ASA has excellent impact strength, good processing property, good weather resistance and chemical stability, easy molding, bright luster of products, toughness and flexibility and excellent comprehensive properties. The polycarbonate and ASA resin alloy combine the advantages of each component resin, and the excellent combination property of the resin is widely used in the industries of automobile industry, electronic and electric appliance industry, light industry and household appliances, textile, building and the like.
In recent years, the automobile industry has more and more high attention to noise and scratches in the automobile, the noise in the automobile mainly comes from extrusion of combined parts in the automobile and friction among the parts, and the noise in the automobile can directly affect physical and mental health of a driver and passengers and even affect driving safety. And the automotive interior trim part is easy to scratch due to long-term contact with people, so that the attractiveness is influenced, and the brand value of the product is influenced.
Patent CN102807725B discloses a scratch-resistant PC/ABS alloy for automobile interior parts and a preparation method thereof, and alloy plastics with excellent scratch resistance are prepared by adding a composite scratch-resistant agent. Patent CN101899204A discloses an antistatic PC/ASA alloy material and a preparation method thereof, wherein an alloy material with excellent performances such as antistatic property and impact resistance is prepared by adding an auxiliary agent such as an antistatic agent. The above patents do not compromise the noise reduction function.
Disclosure of Invention
The invention aims to solve the technical problem of providing a scratch-resistant noise-reducing PC/ASA resin alloy and a preparation method thereof, which can obviously improve the noise-reducing and scratch-resistant performances of the alloy resin, can replace common PC/ASA alloy materials on parts such as automobile household appliances and the like, and can improve the scratch grade and reduce the noise.
The invention provides a scratch-resistant noise-reducing PC/ASA resin alloy, which comprises the following components in percentage by weight:
wherein the scratch resistant agent is polyester modified organic silicon; the noise reduction auxiliary agent is a maleic anhydride grafted SEBS elastomer compound.
The polycarbonate resin is a silicon copolymerized polycarbonate resin.
The ASA rubber powder is a graft copolymer with a shell of methyl methacrylate-acrylonitrile-styrene MMA-AN-St.
The other auxiliary agent is at least one of an antioxidant, a light stabilizer and a lubricant.
The antioxidant is hindered phenol antioxidant and/or phosphite antioxidant.
The light stabilizer is a benzotriazole UV absorbent.
The lubricant is pentaerythritol stearate.
The invention also provides a preparation method of the scratch-resistant noise-reducing PC/ASA resin alloy, which comprises the following steps:
uniformly mixing the raw materials according to a ratio, adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to obtain the product; wherein the melting temperature is 230-260 ℃, and the screw rotating speed is 200-400 r/min.
The invention also provides application of the scratch-resistant noise-reducing PC/ASA resin alloy in automobiles or household electrical appliances.
The scratch-resistant agent and the noise-reducing additive can improve the compatibility of polycarbonate, SAN resin and ASA rubber powder, and in addition, as a large number of silicon-oxygen bonds exist in the silicon-copolymerized PC, the main chain flexibility is good, the compatibility with the scratch-resistant agent is very good, the surface friction coefficient is reduced, and the scratch-resistant effect of the material is improved; in addition, under the action of the noise reduction auxiliary SEBS group, the capability of absorbing external force deformation of the silicon copolymerization PC is improved, the silicon copolymerization PC and the scratch resistant agent cooperate, and a good scratch resistant effect is achieved on the surface of the system, so that the scratch resistant performance of the system is improved. Secondly, each system in the formula is perfectly combined with polycarbonate to form a sea-island structure with the polycarbonate as the sea, so that the prepared PC/ASA resin alloy has the characteristics of noise reduction and scratch resistance and has excellent impact performance.
Advantageous effects
According to the invention, the scratch resistant agent and the noise reduction auxiliary agent are added, and the noise reduction and scratch resistance of the alloy resin are obviously improved, so that the alloy resin can replace common PC/ASA alloy materials on parts such as automobile and household appliances, the scratch grade can be improved, the noise can be reduced, and the requirements of Jili Q/JLY J7110536B-2016 can be met.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The examples and comparative examples used the following starting materials:
polycarbonate resin: silicon copolymerized PC, japan sheen, brand PC FG 1760;
phosgene method PC, Japan sheen, brand PC FN 2200;
SAN resin: acrylonitrile-styrene resin, Taiwan, brand SAN 2200 AK;
ASA type rubber powder: graft copolymer with methyl methacrylate-acrylonitrile-styrene (MMA-AN-St) as the shell, eastern sea of anqiu, designation Q350;
scratch resistance agent: polyester modified organosilicon, Zhejiang Jiahua brand
EG；
Anti-noise auxiliary agent: maleic anhydride grafted SEBS elastomer composite, Nanhai Bai Cheng, brand BCD-65 MAH;
antioxidant: the mixture (mass ratio is 1:1) of the hindered phenol antioxidant and the phosphite antioxidant is produced and provided by Ciba company;
light stabilizer: benzotriazole type UV absorbers, Ciba corporation, under the designation Tinuvin 328;
the lubricant is pentaerythritol stearate, LOZA corporation, and is sold under the trademark GLYCOLUBE-P.
The preparation method comprises the following steps:
the raw materials are uniformly mixed according to the proportion, then the mixture is added into a main machine cylinder of a double-screw extruder (the diameter of a screw is 35mm, the length-diameter ratio L/D is 48), the temperature of each section of the main machine cylinder is controlled to be 235 ℃, 240 ℃, 245 ℃, 250 ℃ and 245 ℃ respectively, the rotating speed of the double screws is 300 revolutions per minute, and extruded strips are cooled by a water tank and then cut into particles to obtain the product.
Drying the product in a forced air oven at 80 ℃ for 4 hours, and then performing injection molding on the product by using a plastic injection molding machine to obtain a standard sample bar and a 100mm 3mm sample plate, wherein the injection molding temperature is 250 ℃; the injection molded bars and plaques were tested for performance after standing at 23 ℃ for at least 24 hours at 50% relative humidity.
The product performance test method comprises the following steps:
charpy impact strength, according to ISO 179 standard, test conditions: 1Ae at 23 ℃;
vicat softening point, according to ISO 306 standard, test conditions: b50;
flexural modulus, tested according to ISO 178 standard, test conditions: 2 mm/min;
melt index, measured according to ISO 1133 standard, conditions of measurement: 260 ℃ and 5 KG;
performing scratch resistance test (a tangle-solidup L value), testing according to the Jili Q/JLY J7110536B-2016 standard, setting the scraper speed of an electric grid marking tester to be (1000 +/-50) mm/min, selecting a hanging head with 10N pressure and 1mm, then enabling a grid marking tester scraper to mark parallel scratches with the length of 40mm on the surface of a plastic sample at intervals of 2mm along one direction, marking at least 20 parallel lines, then rotating the sample by 90 degrees, repeating the operation, thus forming a grid, scratching at least three parallel samples, and measuring the color difference value delta L before and after the scratch area test; the noise hazard value was evaluated and tested according to the German Association for automotive industries standards.
TABLE 1 compositional formula (in weight percent)
Table 2 results of performance testing
Note: the noise risk value is 10 sections, 1-3 are low risk, 4-5 are gray areas, and 6-10 are high risk; l is less than 1.5, which can meet the Jili standard.
As shown in Table 2, in comparison with example 2, comparative example 1 has a system without the scratch resistance agent and the noise reduction aid, and is inferior to example 2 in both impact and scratch resistance effects, and even more, the noise value reaches the dangerous range. Compared with the example 2, the scratch resistant effect is still poor under the condition that the scratch resistant agent and the noise reduction aid are not added at the same time in the comparative examples 2 and 3, which shows that the scratch resistant agent, the noise reduction aid and the silicon copolymerized PC have synergistic effect. In comparative example 4, where conventional phosgene-process PC was used, both the L value and the noise value were significantly worse than for the silicon copolymerized PC system. The alloy resin prepared in the embodiments 1 to 6 has the advantages of remarkably improved noise reduction and scratch resistance, simple preparation process and low equipment requirement, and is suitable for being applied to the fields of automobiles, household appliances and the like.
Claims (8)
1. A scratch-resistant noise-reducing PC/ASA resin alloy is characterized in that: comprises the following components in percentage by weight:
45% -88% of polycarbonate resin;
5-20% of SAN resin;
5-15% of ASA rubber powder;
1-5% of a scratch resistant agent;
2-10% of noise reduction auxiliary agent;
0.5-1.5% of other auxiliary agents;
wherein the scratch resistant agent is polyester modified organic silicon; the noise reduction auxiliary agent is a maleic anhydride grafted SEBS elastomer compound; the polycarbonate resin is silicon copolymerized polycarbonate resin; the sum of the weight percentages of the components is 100 percent.
2. The resin alloy according to claim 1, wherein: the ASA rubber powder is a graft copolymer with a shell of methyl methacrylate-acrylonitrile-styrene MMA-AN-St.
3. The resin alloy according to claim 1, wherein: the other auxiliary agent is at least one of an antioxidant, a light stabilizer and a lubricant.
4. The resin alloy according to claim 3, wherein: the antioxidant is hindered phenol antioxidant and/or phosphite antioxidant.
5. The resin alloy according to claim 3, wherein: the light stabilizer is a benzotriazole UV absorbent.
6. The resin alloy according to claim 3, wherein: the lubricant is pentaerythritol stearate.
7. A method for preparing the scratch resistant and noise reducing PC/ASA resin alloy as claimed in claim 1, comprising: uniformly mixing the raw materials according to a ratio, adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to obtain the product; wherein the melting temperature is 230-260 ℃, and the screw rotating speed is 200-400 r/min.
8. Use of the scratch resistant and noise reducing PC/ASA resin alloy according to claim 1 in automobile or household electrical appliances.
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| WO2002036688A2 (en) * | 2000-10-30 | 2002-05-10 | General Electric Company | Pc/asa composition having improved notched izod and reduced gate blush |
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| CN104497536A (en) * | 2014-12-26 | 2015-04-08 | 深圳华力兴新材料股份有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN104610719A (en) * | 2014-12-26 | 2015-05-13 | 重庆普利特新材料有限公司 | High-heat resistance and low-gloss antistatic PC/ASA alloy material and preparation method thereof |
| CN104629283A (en) * | 2013-11-06 | 2015-05-20 | 殷培花 | High strength abrasion resistant flame retardant polycarbonate material and preparation method thereof |
| CN106751687A (en) * | 2016-12-29 | 2017-05-31 | 上海锦湖日丽塑料有限公司 | A kind of PC/ABS alloy materials of noise-reduction and preparation method thereof |
| CN107418177A (en) * | 2017-05-24 | 2017-12-01 | 武汉理工大学 | A kind of high-toughness halogen-free flame enhancing PC/ASA alloys and preparation method thereof |
| CN109385063A (en) * | 2018-09-30 | 2019-02-26 | 金旸（厦门）新材料科技有限公司 | A kind of wear-resisting PC/ASA alloy material and preparation method thereof |
-
2020
- 2020-12-04 CN CN202011408441.7A patent/CN112341828B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002036688A2 (en) * | 2000-10-30 | 2002-05-10 | General Electric Company | Pc/asa composition having improved notched izod and reduced gate blush |
| CN104629283A (en) * | 2013-11-06 | 2015-05-20 | 殷培花 | High strength abrasion resistant flame retardant polycarbonate material and preparation method thereof |
| CN104448760A (en) * | 2014-12-11 | 2015-03-25 | 苏州禾昌聚合材料股份有限公司 | Scratch-resistant high-light PC/ABS (Polycarbonate/Acrylonitrile-Butadiene-Styrene) material and preparation method thereof |
| CN104497536A (en) * | 2014-12-26 | 2015-04-08 | 深圳华力兴新材料股份有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN104610719A (en) * | 2014-12-26 | 2015-05-13 | 重庆普利特新材料有限公司 | High-heat resistance and low-gloss antistatic PC/ASA alloy material and preparation method thereof |
| CN106751687A (en) * | 2016-12-29 | 2017-05-31 | 上海锦湖日丽塑料有限公司 | A kind of PC/ABS alloy materials of noise-reduction and preparation method thereof |
| CN107418177A (en) * | 2017-05-24 | 2017-12-01 | 武汉理工大学 | A kind of high-toughness halogen-free flame enhancing PC/ASA alloys and preparation method thereof |
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