CN114381115B - High-weather-resistance and precipitation-resistance polyamide composite material for bio-based automobile and preparation method thereof - Google Patents
High-weather-resistance and precipitation-resistance polyamide composite material for bio-based automobile and preparation method thereof Download PDFInfo
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- CN114381115B CN114381115B CN202111597526.9A CN202111597526A CN114381115B CN 114381115 B CN114381115 B CN 114381115B CN 202111597526 A CN202111597526 A CN 202111597526A CN 114381115 B CN114381115 B CN 114381115B
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- polyamide composite
- antioxidant
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 33
- 229920002647 polyamide Polymers 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 239000004611 light stabiliser Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920006021 bio-based polyamide Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a polyamide composite material with high weather resistance and precipitation resistance for a bio-based automobile and a preparation method thereof, wherein the polyamide composite material comprises the following components in percentage by weight: 50-90% of polyamide, 0-30% of glass fiber, 1-15% of fumed silica, 0.05-5% of light stabilizer, 0.1-1.5% of antioxidant, 0-1% of lubricant and 0-1% of other auxiliary agent. The invention adopts an anti-oxidation system with good compatibility with the polyamide material and an ageing system compounded by an illumination system to improve the weather resistance of the polyamide material, is different from the traditional polyamide light stabilization system, and introduces fumed silica into the formula to increase the light stability of the system, thereby achieving good weather resistance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyamide composite material with high weather resistance, precipitation resistance and biological base for automobiles and a preparation method thereof.
Background
With the trend of light weight of automobiles, the proportion of plastics in automobiles is larger and larger, the automobile plastic industry has become a great trend of current automobile manufacturing industry, and the demands of the automobile market have been shifted to sport-utility vehicles, multi-function vehicles and other light vehicles with lighter weight, which also promote the development of engineering plastics such as polyamide and the like to better performance. Experiments show that the weight of the automobile is reduced by 10%, the oil consumption is reduced by 6-8%, the emission is reduced by 4%, meanwhile, the weight reduction of the automobile is favorable for improving the specific power of the automobile, the safety performance of the automobile is improved, and the weight reduction of the automobile is an important measure for reducing the emission and the oil consumption and improving the safety performance. The energy-saving environment-friendly policy is beneficial to the promotion, and the industries of energy-saving environment-friendly, new energy automobiles and related parts in the future are new investment growing points and are the development directions of the automobile industry in the future.
The bio-based PA56 material is derived from natural green crop-corn starch, the consumption of non-renewable energy sources is greatly reduced in the production and processing process, and the bio-based PA56 material is green and environment-friendly and has good social and economic benefits.
The fumed silica has extremely strong ultraviolet absorption function, so that the dosage of the photo-organic stabilizer is reduced; the silanol groups existing on the surfaces among the fumed silica particles generate hydrogen bonding action to form an aggregate network, and the silanol groups and the aggregate network structure have effective adsorption and migration inhibition effects on the organic light stabilizer, so that the migration of the organic light stabilizer to the surface of the product is reduced. Meanwhile, the fumed silica has excellent lubricating effect, so that the adding amount of the lubricant can be effectively reduced, the uniform distribution of glass fibers is facilitated, and the precipitation risk caused by excessive addition of additives can be reduced.
The polyamide material is easy to generate yellowing under the condition of high temperature or ultraviolet irradiation, and parts of the inner and outer chambers of the automobile have weather-proof requirements, so that the high temperature yellowing limits the application of the polyamide material.
Disclosure of Invention
The invention aims to provide a preparation method of a polyamide composite material with high weather resistance, precipitation resistance and bio-based for automobiles, which solves the problems of high temperature and ultraviolet yellowing of the polyamide material and improves the weather resistance through compounding an auxiliary agent system.
The aim of the invention is achieved by the following technical scheme.
A polyamide composite material with high weather resistance and precipitation resistance for a bio-based automobile comprises the following raw materials in percentage by weight:
polyamide resin: 50 to 90 percent,
glass fiber: 0 to 30 percent,
fumed silica: 1 to 15 percent,
light stabilizer 944:0.05 to 5 percent,
an antioxidant: 0.1 to 1.5 percent,
and (3) a lubricant: 0 to 1 percent,
other auxiliaries: 0 to 1 percent.
The polyamide is an environment-friendly bio-based PA56 material.
The glass fiber is a glass fiber with the diameter of 10 mu m and the short cut length of 3mm, and the surface of the glass fiber is coated with a silane-based impregnating compound and applied to a polyamide material.
The lubricant is polyamide wax.
The antioxidant is an organic copper salt antioxidant. Preferably, the antioxidant is antioxidant H3386.
The fumed silica has a specific surface area of 400m 2 /g、200m 2 One or two of the compositions per gram.
The preparation method of the polyamide composite material for the bio-based automobile, which has high weather resistance and precipitation resistance, comprises the following steps:
(1) Weighing the components according to the weight percentage;
(2) The mixed raw materials are added through a main feeding port of a double-screw extruder, glass fibers are added from a side feeding port of the double-screw extruder, the mixture is melt-blended and extruded at 270-290 ℃ for granulation, the rotating speed of the screw is 400-500rpm, and the temperature of a water tank is 30-60 ℃.
The fumed silica has extremely strong ultraviolet absorption function, so that the dosage of the photo-organic stabilizer is reduced; the silanol groups existing on the surfaces among the fumed silica particles generate hydrogen bonding action to form an aggregate network, and the silanol groups and the aggregate network structure have effective adsorption and migration inhibition effects on the organic light stabilizer, so that the migration of the organic light stabilizer to the surface of the product is reduced.
The invention has the advantages that:
1. the thermal oxidation aging system adopts organic copper salt, compared with a hindered phenol aging system, the thermal oxidation aging system has better stabilizing effect on polyamide molecular chains under high temperature conditions, and compared with inorganic copper salt, the thermal oxidation aging system is not easy to change color.
2. The fumed silica used in the invention can reduce the use of the organic light stabilizer, and has adsorption and inhibition effects on the organic light stabilizer, so that the risk of migration of the light stabilizer to the surface to be separated out after the product is exposed for a long time is reduced.
3. The PA56 bio-based polyamide resin is green, environment-friendly, accords with the sustainable development concept and has good economic benefit.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effect to be solved by the method more clear, the invention will be further described in detail with reference to specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
PA66 resin: EPR27, shenma Hibisci
PA56 resin: commercial grade, commercially available
Glass fiber: 301HP, diameter 10 μm, chongqing International
Photostabilizer: 944, commercially available
Antioxidant Bruggolen H3386, bulgermann, germany
Fumed silica: commercial grade, commercially available
And (3) a lubricant: polyamide waxes, technical grade, commercially available
The material performance testing method comprises the following steps:
1. tensile strength: A170X 10X 4mm spline was produced by injection molding, and the tensile speed was 5mm/min according to International Standard ISO 527.
2. Flexural strength: 80X 10X 4mm bars were produced by injection moulding and tested according to International Standard ISO 178 at a test speed of 2mm/min.
3. Notched impact properties: 80X 10X 4mm bars were produced by injection moulding and tested according to the International Standard ISO 179.
4. Light aging: PV1303 standard, 5P, spline size: 150 x 100 x 3.2mm by illumination
The change of the color difference (delta E) before and after aging is evaluated, and the smaller delta E shows the better weather resistance.
The comprehensive mechanical properties of the materials are judged by testing the values of the notch impact strength, the tensile strength and the bending strength. The material formulations of examples 1-4 and comparative examples 1, 2, 3 are shown in Table 1,
table 1 examples 1-4 comparative examples 1, 2, 3 materials formulation table (wt%)
TABLE 2 Material Properties Table of examples 1-4 and comparative examples 1, 2 and 3
From the data in Table 2, it can be seen that the color difference of example 1, example 2, example 3, example 4 is < 3.0 under the light conditions of PV1303 and 5P, thus demonstrating that the weathering formulation is effective. Comparative example 2 and comparative example 1 illustrate that antioxidant H3386 provides good weatherability. From example 2 and comparative example 3, it can be derived that: the addition of the fumed silica can inhibit the precipitation of the light stabilizer, reduce the possibility of 'white frost' defect on the surface of a workpiece, and is obviously superior to the traditional hindered amine light stabilizer, so that the excellent light resistance is obtained. From comparison of examples 1 to 4 with comparative examples 1 and 2, it was found that the mechanical properties were slightly lowered as the content of fumed silica increased, but when the content was higher, the dispersion effect was affected. In conclusion, the fumed silica with ultraviolet absorption capacity is added into the polyamide, so that the polyamide composite material has more excellent light resistance when the fumed silica is compounded with the organic light stabilizer for use.
Claims (7)
1. A polyamide composite material with high weather resistance and precipitation resistance for a bio-based automobile is characterized in that: the material comprises the following raw materials in percentage by weight:
polyamide resin: 50 to 90 percent,
glass fiber: 0 to 30 percent,
fumed silica: 1 to 15 percent,
light stabilizer 944: 0.05-5%,
an antioxidant: 0.1 to 1.5 percent,
and (3) a lubricant: 0 to 1 percent,
other auxiliaries: 0-1%;
the antioxidant is an organic copper salt antioxidant.
2. The high weatherability, precipitation resistance, biobased automotive polyamide composite material of claim 1, wherein: the polyamide is an environment-friendly bio-based PA56 material.
3. The high weatherability, precipitation resistance, biobased automotive polyamide composite material of claim 1, wherein: the glass fiber is a glass fiber with the diameter of 10 mu m and the short cut length of 3mm, and the surface of the glass fiber is coated with a silane-based impregnating compound and applied to a polyamide material.
4. The high weatherability, precipitation resistance, biobased automotive polyamide composite material of claim 1, wherein: the lubricant is polyamide wax.
5. The high weatherability, precipitation resistance, biobased automotive polyamide composite material of claim 1, wherein: the antioxidant is antioxidant H3386.
6. The high weatherability, precipitation resistance, biobased automotive polyamide composite material of claim 1, wherein: the fumed silica has a specific surface area of 400m 2 /g、200 m 2 One or two of the compositions per gram.
7. The method for preparing the polyamide composite material for the bio-based automobile with high weather resistance and precipitation resistance according to any one of claims 1 to 6, comprising the following steps:
(1) Weighing the components according to the weight percentage;
(2) The mixed raw materials are added through a main feeding port of a double-screw extruder, glass fibers are added from a side feeding port of the double-screw extruder, the mixture is melt-blended and extruded at 270-290 ℃ for granulation, the rotating speed of the screw is 400-500rpm, and the temperature of a water tank is 30-60 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111597526.9A CN114381115B (en) | 2021-12-24 | 2021-12-24 | High-weather-resistance and precipitation-resistance polyamide composite material for bio-based automobile and preparation method thereof |
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| CN202111597526.9A CN114381115B (en) | 2021-12-24 | 2021-12-24 | High-weather-resistance and precipitation-resistance polyamide composite material for bio-based automobile and preparation method thereof |
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| Publication Number | Publication Date |
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| CN114381115A CN114381115A (en) | 2022-04-22 |
| CN114381115B true CN114381115B (en) | 2023-11-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749432A (en) * | 2018-12-25 | 2019-05-14 | 浙江普利特新材料有限公司 | A kind of high durable, apperance performance, the glass fiber reinforced nylon material of high-performance for automobile and preparation method thereof |
| CN111087695A (en) * | 2019-12-26 | 2020-05-01 | 上海普利特复合材料股份有限公司 | Precipitation-resistant scratch-resistant high-performance low-cost polypropylene composite material and preparation method thereof |
| CN113372714A (en) * | 2021-07-14 | 2021-09-10 | 金旸（厦门）新材料科技有限公司 | Polyamide composite material with low phosphine gas precipitation and high CTI (comparative tracking index) and preparation method thereof |
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- 2021-12-24 CN CN202111597526.9A patent/CN114381115B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749432A (en) * | 2018-12-25 | 2019-05-14 | 浙江普利特新材料有限公司 | A kind of high durable, apperance performance, the glass fiber reinforced nylon material of high-performance for automobile and preparation method thereof |
| CN111087695A (en) * | 2019-12-26 | 2020-05-01 | 上海普利特复合材料股份有限公司 | Precipitation-resistant scratch-resistant high-performance low-cost polypropylene composite material and preparation method thereof |
| CN113372714A (en) * | 2021-07-14 | 2021-09-10 | 金旸（厦门）新材料科技有限公司 | Polyamide composite material with low phosphine gas precipitation and high CTI (comparative tracking index) and preparation method thereof |
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| CN114381115A (en) | 2022-04-22 |
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