CN112724667A - Polyamide molding composition and preparation method and application thereof - Google Patents
Polyamide molding composition and preparation method and application thereof Download PDFInfo
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- CN112724667A CN112724667A CN202011482613.5A CN202011482613A CN112724667A CN 112724667 A CN112724667 A CN 112724667A CN 202011482613 A CN202011482613 A CN 202011482613A CN 112724667 A CN112724667 A CN 112724667A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
- G02B7/18—Mountings, adjusting means, or light-tight connections, for optical elements for prisms; for mirrors
- G02B7/182—Mountings, adjusting means, or light-tight connections, for optical elements for prisms; for mirrors for mirrors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a polyamide molding composition, a preparation method and application thereof, wherein the polyamide molding composition comprises the following components: 100 parts of polyamide resin; 0.1-2 parts of hyperbranched polyamide; 0-100 parts of reinforcing filler. By adding a specific amount of the amino-terminated hyperbranched polyamide to the polyamide molding composition of the invention, the crystallization temperature and the crystallization rate of the material can be significantly increased. Under the condition of cold die forming, the polyamide composition material can crystallize at a higher temperature, namely, can crystallize and cool earlier, and finish crystallization and complete cooling at a higher speed, and the problems of die sticking, material belt drawing and the like are not easy to occur when a part is produced and demoulded; the forming and cooling period can be shortened, the production efficiency is improved, and the method is suitable for the development trend of LED reflection support thinning and multiple mold cavities.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a polyamide molding composition, and a preparation method and application thereof.
Background
The polyamide has good mechanical property, abrasion resistance, chemical resistance and self-lubricating property, and low friction coefficient, so that the polyamide is widely suitable for being filled, reinforced and modified by glass fibers and other fillers. However, ordinary polyamides such as PA6 and PA66 have a melting point of 260 ℃ or lower, and are insufficient in high-temperature resistance, and cannot be used in fields where the use temperature is high. Semi-aromatic polyamides have been developed in recent years with emphasis on their low water absorption and high temperature resistance.
The LED reflecting support needs to be subjected to high-temperature processing technologies such as a reflow soldering technology and the like, the materials are required to have higher thermal deformation temperature and melting point, and a series of semi-aromatic polyamides such as PA10T, PA9T and PA6T copolymers become mainstream materials of the LED reflecting support. With the increase of the demand of consumers, the size of the LED lamp bead is gradually reduced, and the LED reflecting bracket gradually develops towards small size and thin wall; in order to improve the production efficiency and reduce the production energy consumption, the injection molding factory gradually increases the number of the mold cavities of the LED reflecting support from below 1000 to above 2000, and cold mold forming replaces high mold temperature forming. However, the existing semi-aromatic polyamide material has low crystallization temperature, slow crystallization rate, long cooling time during cold die forming, and can not be formed quickly, and the problems of sticking a product to a die, pulling a material belt and the like are easily caused by incomplete cooling. Therefore, how to improve the crystallization temperature, crystallization rate and fluidity of the material and shorten the molding cooling period so as to improve the production efficiency, so as to adapt to the development trend of thinning and multi-cavity of the LED reflection bracket, which is the main research direction of the invention.
Disclosure of Invention
In order to overcome the disadvantages of the prior art described above, it is an object of the present invention to provide a polyamide molding composition whose crystallization temperature, crystallization rate and flowability are significantly increased.
Another object of the present invention is to provide a process for the preparation of the above-mentioned polyamide molding compositions.
The invention is realized by the following technical scheme:
a polyamide molding composition comprises the following components in parts by weight:
100 parts of polyamide resin;
0.1-2 parts of hyperbranched polyamide;
0-100 parts of reinforcing filler.
The polyamide resin is prepared by the polycondensation of diamine and diacid; the polyamide resin is selected from any one of PA10T, PA10T/10I, PA10T/6T or PA 6T/66.
The polyamide resin of the present invention may be commercially available, or may be obtained by the following conventional polymerization method, specifically: adding diamine and diacid into a pressure kettle which is provided with a magnetic coupling stirring device, a condensing pipe, a gas phase port, a feeding port and a pressure explosion-proof port according to a proportion; adding benzoic acid, a catalyst sodium hypophosphite and deionized water; the amount of the benzoic acid substance is 1.0-3.0% of the total amount of the decamethylene diamine and the diacid, the weight of the sodium hypophosphite is 0.1-0.3% of the weight of the materials except the deionized water, and the weight of the deionized water is 20-40% of the total weight of the materials; vacuumizing, filling high-purity nitrogen as protective gas, heating to 220-230 ℃ within 2 hours under stirring, stirring the reaction mixture for 1 hour, and then raising the temperature of reactants to 240-250 ℃ under stirring; and (2) continuing the reaction for 1-3 hours at constant temperature and constant pressure, removing the formed water to keep the pressure constant, discharging after the reaction is finished, and performing vacuum drying on the prepolymer for 24 hours at 80 ℃ to obtain a prepolymerization product, wherein the prepolymerization product is subjected to solid phase tackifying for 6-12 hours at 250-270 ℃ under the vacuum condition of 10-100 Pa to obtain the polyamide resin.
The present invention aims to modify polyamide resins, and therefore the present invention does not require the specification parameters of polyamide resins. Generally, the relative viscosity of the polyamide resin used for the LED reflecting support is 2.0-2.4; the relative viscosity is measured from polyamide at a concentration of 0.25g/dL in 98% concentrated sulfuric acid at 25. + -. 0.01 ℃ according to standard GB 12006.1-89.
According to the invention, the research shows that the addition of the hyperbranched polyamide containing the terminal amino groups can obviously improve the crystallization temperature, the crystallization rate and the fluidity of the polyamide composition. The terminal amino group of the hyperbranched polyamide can react with the carboxyl at the tail end of the polyamide molecular chain and is grafted into the polyamide molecular chain. Due to the fact that the hyperbranched polyamide is large in size, after the molecular chains of the polyamide are connected, the distance between the molecular chains is enlarged, the mobility of the molecular chains is improved, the molecular chains are more easily arranged into crystal lattices in the cooling process, crystallization can be carried out at a higher temperature, and crystallization can be completed more quickly, so that the material has a higher crystallization temperature and a higher crystallization rate; on the other hand, since the mobility of the molecular chain is increased, the molecular chain slippage is more likely to occur during melt processing, and the fluidity of the material is increased.
Preferably, the hyperbranched polyamide is 0.5-1.5 parts by weight.
The terminal amino group of the hyperbranched polyamide is 3-16 mol/mol, and the number average molecular weight is 350-2200 g/mol. The content of the terminal amino group is too low to react with the tail ends of enough polyamide molecular chains, so that the effect of improving the mobility of the molecular chains is limited; the number of the terminal amino groups is too high, the terminal amino groups react with the tail ends of too many polyamide molecular chains to form a cross-linked structure, the mobility of the molecular chains is greatly reduced, the crystallization temperature is reduced, the crystallization rate is reduced, and the fluidity is poor. Preferably, the terminal amino group of the hyperbranched polyamide is 7-9 mol/mol, and the number average molecular weight is 800-1000 g/mol.
The reinforcing filler is at least one selected from fibrous reinforcing fillers and non-fibrous reinforcing fillers. Specifically, the fibrous reinforcing filler is selected from at least one of glass fiber, potassium titanate fiber, metal-clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal cured fiber, asbestos fiber, alumina fiber, silicon carbide fiber, gypsum fiber or boron fiber, aramid fiber or carbon fiber; the non-fibrous reinforcing filler is selected from one or more of potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silica, magnesia, zirconia, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.
According to the requirement of material performance, the polyamide molding composition can also comprise 0-1 part of an auxiliary agent in parts by weight; the auxiliary agent comprises an antioxidant; specifically, the antioxidant is N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxyphenyl propionamide);
the polyamide molding composition of the invention may further comprise 0 to 40 parts by weight of a pigment. Often, a certain amount of pigment is added to the LED reflecting support to enhance the reflecting effect. However, the examples and comparative examples in the present application use pigments as a means of characterization, and whether pigments are added or not is not a limitation to the technical solution of the present invention.
The pigment is titanium dioxide subjected to surface treatment by using a silicone compound; other types of pigments may also be selected as desired.
The invention also provides a process for the preparation of the above polyamide molding composition, comprising the steps of: uniformly mixing the components according to the proportion, and carrying out melt blending and extrusion granulation by a double-screw extruder to obtain a polyamide molding composition; wherein the temperature of the double-screw extruder is set to be 280-340 ℃.
The invention also provides application of the polyamide molding composition in the field of LED reflecting supports.
Compared with the prior art, the invention has the following beneficial effects:
by adding a specific amount of the amino-terminated hyperbranched polyamide into the polyamide molding composition, the crystallization temperature, the crystallization rate and the fluidity of the material can be remarkably improved, namely the material can have the crystallization temperature and the melt index which are as high as possible and the half height width of the crystallization peak which is as small as possible. Under the condition of cold die forming, the polyamide composition material can crystallize at a higher temperature, namely, can crystallize and cool earlier, and finish crystallization and complete cooling at a higher speed, and the problems of die sticking, material belt drawing and the like are not easy to occur when a part is produced and demoulded; the method can obviously shorten the molding cooling period, improve the production efficiency and adapt to the development trend of LED reflecting support thinning and multiple mold cavities.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
diamine (b): 1, 10-decamethylenediamine, 1, 6-hexanediamine, commercially available;
diacid: terephthalic acid, isophthalic acid, 1, 6-adipic acid, commercially available;
hyperbranched polyamide 1: HyPer N101, Wuhan super-branched resin science and technology Limited, 3-4 mol/mol of terminal amino and 350-370 g/mol of molecular weight;
hyperbranched polyamide 2: HyPer N102, Wuhan super-branched resin science and technology Limited, terminal amino groups 7-9 mol/mol, and molecular weight 800-1000 g/mol;
hyperbranched polyamide 3: HyPer N103, Wuhan super-branched resin science and technology Limited, terminal amino groups 12-16 mol/mol, and molecular weight 1900-2200 g/mol;
hyperbranched polyamide 4: HyPer HPN202, Wuhan super-branched resin science and technology Limited, terminal hydroxyl group 12 mol/mol, molecular weight 2700 g/mol;
reinforcing materials: glass fiber, commercially available;
pigment: titanium dioxide, commercially available;
antioxidant: n, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyphenyl-propionamide), commercially available;
the preparation method of the polyamide resin comprises the following steps: adding diamine and diacid into a pressure kettle which is provided with a magnetic coupling stirring device, a condensing pipe, a gas phase port, a feeding port and a pressure explosion-proof port according to the proportion shown in the table 1; adding benzoic acid, a catalyst sodium hypophosphite and deionized water; the amount of benzoic acid material is 2.5 percent of the total amount of diamine and diacid, the weight of sodium hypophosphite is 0.1 percent of the weight of other materials except deionized water, and the weight of the deionized water is 30 percent of the total material weight; vacuumizing, filling high-purity nitrogen as protective gas, heating to 220 ℃ within 2 hours under stirring, stirring the reaction mixture for 1 hour, and then heating the reactants to 240 ℃ under stirring; the reaction is continued for 2 hours at constant temperature and constant pressure, the pressure is kept constant by removing the formed water, the material is discharged after the reaction is finished, the prepolymer is dried in vacuum for 24 hours at 80 ℃ to obtain a prepolymerization product, and the prepolymerization product is tackified in a solid phase for 10 hours at 250 ℃ under the vacuum condition of 50 Pa to obtain the polyamide resin.
Examples and comparative examples the preparation of polyamide moulding compositions: uniformly mixing the components according to the mixture ratio shown in the table 2-5, and carrying out melt blending and extrusion granulation by using a double-screw extruder to obtain a polyamide molding composition; wherein the temperature of the double-screw extruder is set to be 280-340 ℃.
Test methods or standards for each property:
relative viscosity of polyamide resin: test methods the relative viscosity, as measured in 98% concentrated sulfuric acid at 25. + -. 0.01 ℃ from polyamides with a concentration of 0.25g/dL, is referred to GB 12006.1-89.
Melting point, crystallization temperature and half height width of crystallization peak of polyamide composition: reference is made to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning calibration; the melting point T of the polyamide composition was measuredmCrystallization temperature TcCrystal peak full width at half maximum Δ T1/2(ii) a Half height of crystallization peakThe smaller the width, the faster the crystallization rate; the larger the full width at half maximum of the crystallization peak, the slower the crystallization rate.
Melt Mass Flow Rate (MFR) of polyamide composition: the test is carried out according to the standard GB/T3682.1-2018, the test temperature is 330 ℃, and the load is 2.16 kg.
Table 1: the monomer proportion of the polyamide resin
Table 2: the concrete proportions (parts by weight) of the components in examples A1-A6 and comparative examples A1-A3 and the results of various performance tests (the polyamide resin is PA 10T)
As can be seen from the examples and comparative examples in table 2, the present invention can significantly increase the crystallization temperature, crystallization rate and flowability of PA10T compositions by adding specific amounts of hyperbranched polyamides.
In comparison with examples A1-A3, the hyperbranched polyamide in comparative example A1 has a lower crystallization temperature, a higher half height width of the crystallization peak, a slower crystallization rate and a lower flowability.
Comparative example a3, with the addition of hydroxyl terminated hyperbranched polyamide, did not improve the crystallization temperature, crystallization rate and flowability of the material.
Table 3: the concrete proportions (parts by weight) of the components in examples B1-B6 and comparative examples B1-B4 and the results of the performance tests (the polyamide resin is PA 10T/10I)
As can be seen from the examples and comparative examples in Table 3, the present invention makes it possible to significantly increase the crystallization temperature, the crystallization rate and the flowability of PA10T/10I compositions by adding specific amounts of hyperbranched polyamides.
In comparative example B1, compared with examples B1 to B3, the addition of the hyperbranched polyamide is too large, but the crystallization temperature is lowered, the full width at half maximum of the crystallization peak is obviously increased, the crystallization rate is slow, and the fluidity is poor.
Comparative example B4, with the addition of the hydroxyl terminated hyperbranched polyamide, did not improve the crystallization temperature, crystallization rate and flowability of the material.
Table 4: the concrete proportions (parts by weight) of the components in examples C1-C6 and comparative examples C1-C4 and the results of the performance tests (the polyamide resin is PA 10T/6T)
As can be seen from the examples and comparative examples in Table 4, the present invention makes it possible to significantly increase the crystallization temperature, the crystallization rate and the flowability of PA6T/10T compositions by adding specific amounts of hyperbranched polyamides.
In comparative example C1, compared with example C1, the addition of the hyperbranched polyamide in an excessive amount lowers the crystallization temperature, significantly increases the full width at half maximum of the crystallization peak, slows the crystallization rate, and deteriorates the flowability.
Comparative example C4, with the addition of the hydroxyl terminated hyperbranched polyamide, did not improve the crystallization temperature, crystallization rate and flowability of the material.
Table 5: the concrete proportions (parts by weight) of the components in examples D1 to D6 and comparative examples D1 to D4 and the results of the performance tests (polyamide resin PA 6T/66)
As can be seen from the examples and comparative examples in Table 5, the present invention makes it possible to significantly increase the crystallization temperature, the crystallization rate and the flowability of PA6T/66 compositions by adding specific amounts of hyperbranched polyamides.
Comparative example D1 compared with example D1, the hyperbranched polyamide was added in an excessive amount, but the crystallization temperature was lowered, the full width at half maximum of the crystallization peak was significantly increased, the crystallization rate was slow, and the flowability was poor.
Comparative example D4, the addition of the hydroxyl-terminated hyperbranched polyamide did not improve the crystallization temperature, crystallization rate and flowability of the material.
Claims (10)
1. A polyamide molding composition is characterized by comprising the following components in parts by weight:
100 parts of polyamide resin;
0.1-2 parts of hyperbranched polyamide;
0-100 parts of reinforcing filler.
2. Polyamide moulding composition according to claim 1, characterized in that the polyamide resin is selected from any of PA10T, PA10T/10I, PA10T/6T or PA 6T/66.
3. The polyamide molding composition as claimed in claim 1, wherein the polyamide resin has a relative viscosity of 2.0 to 2.4.
4. The polyamide molding composition according to claim 1, wherein the hyperbranched polyamide is present in an amount of 0.5 to 1.5 parts by weight.
5. The polyamide molding composition according to claim 1, wherein the hyperbranched polyamide has 3 to 16mol/mol of terminal amino groups and a number average molecular weight of 350 to 2200 g/mol.
6. The polyamide molding composition according to claim 5, wherein the hyperbranched polyamide has 7 to 9mol/mol of terminal amino groups and a number average molecular weight of 800 to 1000 g/mol.
7. The polyamide molding composition as claimed in claim 1, wherein the reinforcing filler is at least one selected from fibrous reinforcing fillers and non-fibrous reinforcing fillers; the fibrous reinforcing filler is at least one selected from glass fiber, potassium titanate fiber, metal-clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal solidified fiber, asbestos fiber, alumina fiber, silicon carbide fiber, gypsum fiber or boron fiber, aromatic polyamide fiber or carbon fiber; the non-fibrous reinforcing filler is selected from one or more of potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silica, magnesia, zirconia, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.
8. The polyamide molding composition as claimed in claim 1, further comprising 0 to 1 part by weight of an auxiliary; 0-40 parts of pigment; the auxiliary agent comprises an antioxidant.
9. Process for the preparation of a polyamide molding composition according to any one of claims 1 to 8, characterized in that it comprises the following steps: uniformly mixing the components according to the proportion, and carrying out melt blending and extrusion granulation by a double-screw extruder to obtain a polyamide molding composition; wherein the temperature of the double-screw extruder is set to be 280-340 ℃.
10. Use of a polyamide molding composition according to any one of claims 1 to 8 in the field of LED reflective supports.
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| CN202011482613.5A CN112724667B (en) | 2020-12-16 | 2020-12-16 | Polyamide molding composition and preparation method and application thereof |
| PCT/CN2021/119403 WO2022127248A1 (en) | 2020-12-16 | 2021-09-18 | Polyamide moulding composition, preparation method therefor, and application thereof |
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| WO2022127248A1 (en) * | 2020-12-16 | 2022-06-23 | 金发科技股份有限公司 | Polyamide moulding composition, preparation method therefor, and application thereof |
| CN115232467A (en) * | 2022-07-27 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | High-temperature thermal-aging-resistant polyamide composite material and preparation method thereof |
| CN115572480A (en) * | 2022-08-23 | 2023-01-06 | 金发科技股份有限公司 | Polyamide composition and preparation method and application thereof |
| WO2023040942A1 (en) * | 2021-09-18 | 2023-03-23 | 珠海万通特种工程塑料有限公司 | Pa10t molding composite material, and preparation method therefor and application thereof |
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| CN102203187A (en) * | 2008-10-30 | 2011-09-28 | 纳幕尔杜邦公司 | Thermoplastic composition including hyperbranched aromatic polyamide |
| CN102977363A (en) * | 2012-11-27 | 2013-03-20 | 南方医科大学 | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin |
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| WO2022127248A1 (en) * | 2020-12-16 | 2022-06-23 | 金发科技股份有限公司 | Polyamide moulding composition, preparation method therefor, and application thereof |
| WO2023040942A1 (en) * | 2021-09-18 | 2023-03-23 | 珠海万通特种工程塑料有限公司 | Pa10t molding composite material, and preparation method therefor and application thereof |
| CN115232467A (en) * | 2022-07-27 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | High-temperature thermal-aging-resistant polyamide composite material and preparation method thereof |
| CN115232467B (en) * | 2022-07-27 | 2023-04-21 | 金旸（厦门）新材料科技有限公司 | High-temperature heat aging resistant polyamide composite material and preparation method thereof |
| CN115572480A (en) * | 2022-08-23 | 2023-01-06 | 金发科技股份有限公司 | Polyamide composition and preparation method and application thereof |
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| CN112724667B (en) | 2022-06-14 |
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