CN114573980B - Polyamide composition and application thereof - Google Patents
Polyamide composition and application thereof Download PDFInfo
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- CN114573980B CN114573980B CN202111545597.4A CN202111545597A CN114573980B CN 114573980 B CN114573980 B CN 114573980B CN 202111545597 A CN202111545597 A CN 202111545597A CN 114573980 B CN114573980 B CN 114573980B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention relates to the technical field of polymers, and particularly discloses a polyamide composition and application thereof. The polyamide composition disclosed by the invention comprises the following components in parts by weight: 50 to 80 parts of polyamide resin, 10 to 35 parts of impact modifier, 5 to 20 parts of high-density polyethylene, 0.5 to 5 parts of epoxy resin and 0.5 to 5 parts of polytetrafluoroethylene. According to the invention, high-density polyethylene, epoxy resin and polytetrafluoroethylene with good fluidity and dispersibility are simultaneously introduced into a toughened polyamide resin system, so that the breaking elongation and the cantilever beam notch impact strength of the prepared polyamide resin composition are greatly improved, and the fatigue cycle times can meet the use requirements of a terminal product.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a polyamide composition and application thereof.
Background
Polyamide, commonly called nylon, is an important thermoplastic engineering plastic, and is widely applied to the fields of automobiles, mechanical parts, electronics, electrical appliances and the like because of the excellent performances of high strength, good self-lubricity, wear resistance, oil resistance, easiness in molding and processing and the like. However, nylon also has the problems of low notch impact, low temperature, easy brittle fracture under dry conditions and the like, so that the application of the nylon is greatly limited, and therefore, the nylon is often required to be toughened and modified.
The physical blending toughening is realized by adding toughening modifier such as plasticizer and elastomer, and the chemical toughening modification is realized by chemical reaction, so that the molecular structure is changed to achieve the aim of improving toughness such as block, grafting, copolymerization and crosslinking. Although the notch impact strength, elongation at break, low-temperature impact and the like of the nylon toughened and modified material are improved, the tensile strength, modulus, hardness, fluidity and the like are reduced, which generally causes the problems of deformation, wear resistance, poor processability and the like of the product, and the fatigue failure cycle number is reduced under the same stress amplitude.
The toughened nylon 6 material is widely used in the electric tool industry, the vibration bracket in the sanding machine is required to be made of high-toughness polyamide with balanced rigidity and fatigue resistance, but the toughened nylon commonly used in the market at present has poor rigidity and poor fatigue performance, so that the sanding machine is unstable in the use process, or the vibration bracket is broken, potential safety hazards are easily caused, while the long carbon chain nylon, such as PA12 and the like, has better balanced rigidity and toughness and fatigue resistance, but has too high cost to limit the application of the nylon in the electric tool industry.
Disclosure of Invention
The present invention aims to overcome the above-mentioned disadvantages of the prior art and to provide a polyamide composition having excellent elongation at break, notched impact strength and fatigue resistance and its use.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polyamide composition, which comprises the following components in parts by weight:
50 to 80 parts of polyamide resin, 10 to 35 parts of impact modifier, 5 to 20 parts of high-density polyethylene, 0.5 to 5 parts of epoxy resin and 0.5 to 5 parts of polytetrafluoroethylene.
The invention introduces high-density polyethylene with crystallinity of 80% -95%, modulus of 800MPa-950MPa, water absorption of less than 0.01%, high crystallinity, high rigidity and low water absorption, so that the polyamide resin system has higher tensile strength; epoxy resin is added into the polyamide resin system, so as to chain-extend the polyamide resin and prevent the reduction of the viscosity of the resin in the processing process and the reduction of notch impact strength; polytetrafluoroethylene with good fluidity and dispersibility is added into a polyamide resin system, and fibers are easy to form after the polytetrafluoroethylene is sheared, so that the notch impact strength of the polyamide composition can be improved without reducing the tensile strength of the polyamide resin, and the fatigue resistance of the composition can be improved.
According to the invention, the high-density polyethylene, the epoxy resin and the polytetrafluoroethylene are simultaneously introduced and compounded into the toughened polyamide resin system, so that the breaking elongation and the cantilever notched impact strength of the prepared polyamide resin composition are greatly improved, and the fatigue cycle times can meet the use requirements of the terminal product.
As a preferred embodiment of the polyamide composition according to the invention, the polyamide composition comprises the following components in parts by weight:
58.9 to 70.4 parts of polyamide resin, 15 to 25 parts of impact modifier, 10 to 15 parts of high-density polyethylene, 1 to 5 parts of epoxy resin and 0.5 to 3 parts of polytetrafluoroethylene.
When the polyamide composition is preferably the components in parts by weight, the prepared polyamide composition has better elongation at break and notched Izod impact strength, better fatigue resistance, low cost and better comprehensive performance.
As a preferred embodiment of the polyamide composition according to the invention, the high-density polyethylene has a melt index of 5-14g/10min according to ISO1133-1 2011 at a temperature of 190℃and a test weight of 2.16 kg.
The invention is selected from high-density polyethylene with high crystallinity, high rigidity and low water absorption, can effectively improve the tensile strength and the elongation at break of the polyamide composition, has more fatigue cycle times, can obviously improve the elongation at break and the notch impact strength of the cantilever beam when being compounded with epoxy resin and polytetrafluoroethylene, and can meet the use requirement of a terminal product.
As a preferred embodiment of the polyamide composition of the present invention, the epoxy resin is a bisphenol A type epoxy resin having an epoxy equivalent weight of 450 to 700. The epoxy equivalent is the molecular weight of the epoxy resin/2.
The bisphenol A epoxy resin with the epoxy equivalent weight of 450-700 is specifically selected, wherein the epoxy equivalent weight is related to the molecular weight of the epoxy resin and the concentration of the epoxy groups, and the epoxy groups with the excessively high and excessively low concentration are both unfavorable for toughening, so that the toughening effect can be effectively improved by selecting the epoxy resin with the proper epoxy equivalent weight. The epoxy resin of the invention can be used for chain extension of polyamide resin, so that the reduction of the notch impact strength caused by the reduction of the viscosity of the resin in the processing process can be prevented, the cycle times can be increased, and the fatigue resistance can be further improved.
Preferably, the epoxy resin is bisphenol a type epoxy resin having an epoxy equivalent weight of 450 to 700.
As a preferred embodiment of the polyamide composition of the present invention, the polytetrafluoroethylene has a number average molecular weight of 380 to 850 tens of thousands.
The invention selects the polyamide composition with ultra-high molecular weight to improve notch impact strength and fatigue resistance without reducing the tensile strength of the polyamide composition; when the molecular weight of the polytetrafluoroethylene is not in the range, the effect is that: when the number average molecular weight of the polytetrafluoroethylene is lower than 380 ten thousand, the polytetrafluoroethylene cannot form a fiberization network, the impact on notch impact strength and fatigue performance is not great, and when the number average molecular weight of the polytetrafluoroethylene is higher than 850 ten thousand, the polytetrafluoroethylene is not easy to disperse during mixing, so that the performance of a product is poor.
As a preferred embodiment of the polyamide composition according to the present invention, the polyamide resin is a condensation product of one or more dicarboxylic acids and one or more diamines, or the polyamide resin is a condensation product of one or more aminocarboxylic acids, or the polyamide resin is a ring-opening polymerization product of one or more cyclic lactams, preferably the polyamide resin is at least one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212, more preferably the polyamide resin is polyamide 6.
More preferably, the concentrated sulfuric acid solution containing polyamide resin at a concentration of 0.01g/mL has a relative viscosity of 2.4 to 3.2 as measured at 25 ℃.
As a preferred embodiment of the polyamide composition of the present invention, the impact modifier is at least one of a maleic anhydride grafted ethylene-octene copolymer, a maleic anhydride grafted ethylene-propylene-diene rubber, an acrylonitrile-butadiene-styrene copolymer, a styrene-ethylene-butadiene copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-butyl acrylate. Preferably, the impact modifier is a maleic anhydride grafted ethylene-octene copolymer having a grafting ratio of 0.5% to 1.2%.
As a preferred embodiment of the polyamide composition of the present invention, the polyamide composition further comprises 0.1 to 3 parts of an additive comprising one or both of a heat stabilizer and a lubricant.
As a preferred embodiment of the polyamide composition of the present invention, the heat stabilizer is at least one of a hindered phenol stabilizer, a phosphite stabilizer, a cuprous halide complex stabilizer, and a stabilizer of a compound having a benzophenone functional group. More preferably, the heat stabilizer is a hindered phenol stabilizer; the hindered phenol stabilizer comprises one or more of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], and the lubricant is hydrocarbon, ester, alcohol, fatty acid amide and metal soap, preferably ester lubricant, comprising fatty acid ester, polyol ester and polyethylene glycol ester.
The invention also provides application of the polyamide composition in an electric tool. The electric tool comprises at least one of a sander, an angle grinder, an electric hammer, an electric pick, an electric drill, an electric planer, a circular saw, a cutting machine and an edge trimmer.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, high-density polyethylene, epoxy resin and polytetrafluoroethylene with good fluidity and dispersibility are simultaneously introduced into a toughened polyamide resin system, so that the breaking elongation and the cantilever beam notch impact strength of the prepared polyamide resin composition are greatly improved, and the fatigue cycle times can meet the use requirements of a terminal product.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used, unless otherwise specified, were all commercially available.
The raw material sources of the following examples and comparative examples are as follows:
polyamide resin 1: PA6 HY2800 with relative viscosity of 2.8 and manufactured by Jiangsu sea-yang chemical fiber;
polyamide resin 2: PA 6M 2400, relative viscosity 2.4, manufacturer Guangdong Xinhuimeida;
polyamide resin 3: PA6 BL40H with relative viscosity of 4.0 is manufactured by Baling petrochemical industry;
impact modifier 1: n406, maleic anhydride grafted ethylene-octene copolymer with grafting rate of 0.8% and manufacturer's light;
impact modifier 2: KT-7, maleic anhydride grafted ethylene-propylene-diene rubber with grafting ratio of 0.6% and manufacturer Shenyang Kong;
high density polyethylene 1: HDPE FL8008 is produced by the manufacturer for fujianization, and has a melt index of 8g/10min under the conditions of 190 ℃ and a test weight of 2.16kg according to ISO1133-1 2011;
high density polyethylene 2: HDPE 2200J, manufactured by Yanshan petrochemical industry, has a melt index of 5g/10min under the conditions of 190 ℃ and a test weight of 2.16kg according to ISO1133-1 2011;
high density polyethylene 3: HDPE 1300J, manufactured by Yanshan petrochemical industry, has a melt index of 14g/10min under the conditions of 190 ℃ and a test weight of 2.16kg according to ISO1133-1 2011;
high density polyethylene 4: HDPE DMDB8920 manufactured by Guangzhou petrochemical industry has a melt index of 20g/10min at 190 ℃ and a test weight of 2.16kg according to ISO 1133-12011;
epoxy resin 1: epoxy equivalent is 450-500, CYD-011, manufacturer is Yueyang Baling petrochemical;
epoxy resin 2: the epoxy equivalent is 600-700, the brand is CYD-012, and the manufacturer is Yueyang Baling petrochemical;
epoxy resin 3: the epoxy equivalent is 710-875, the brand is CYD-014U, and the manufacturer is Yueyang Baling petrochemical;
epoxy resin 4: the epoxy equivalent is 230-280, the brand is E-44, and the manufacturer is Yueyang Baling petrochemical;
polytetrafluoroethylene 1: f208, number average molecular weight of 570 ten thousand, manufacturer DAIKIN;
polytetrafluoroethylene 2: f302, the number average molecular weight is 850 ten thousand, and the manufacturer is DAIKIN;
polytetrafluoroethylene 3: f201, the number average molecular weight is 380 ten thousand, and the manufacturer is DAIKIN;
polytetrafluoroethylene 4: f303, the number average molecular weight is 1300 ten thousand, and the manufacturer is DAIKIN;
polytetrafluoroethylene 5: f-5AEX with a number average molecular weight of 50 ten thousand and Solvay;
heat stabilizer: n, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine;
and (3) a lubricant: fatty acid ester lubricant TR044W; in each of the examples and comparative examples, the heat stabilizer and the lubricant were the same commercially available products.
1. Examples 1 to 17
Examples 1 to 17 provide polyamide compositions, the formulation of which in parts by weight is given in Table 1, the preparation method is as follows:
mixing the polyamide resin, the impact modifier, the high-density polyethylene, the epoxy resin, the polytetrafluoroethylene, the heat stabilizer and the lubricant in parts by weight in a high mixer for 1-10 min, adding into a feeding hopper of a double-screw extruder, fully plasticizing, melting, extruding, bracing, cooling and granulating to obtain the polyamide composition.
Wherein, the screw rotating speed of the double screw extruder is 400rpm, the length-diameter ratio is 40:1, and the temperature of each section of screw of the extruder is sequentially set from a feed inlet to a machine head as follows: one 160 ℃, two 250 ℃, three to four 240 ℃, five to seven 220 ℃, eight to nine 230 ℃, ten 260 ℃.
TABLE 1
Note that: in the table "-" means that the component was not added, and the following is the same.
Comparative examples 1 to 8 provide polyamide compositions having the formulation shown in Table 2 in parts by weight, and the preparation method was referred to the preparation methods of examples 1 to 17.
TABLE 2
The materials prepared in examples 1 to 17 and comparative examples 1 to 8 were subjected to performance tests, and the respective performance test methods were as follows:
1) Elongation at break: injecting the material into standard ISO sample bars by an injection molding machine, and then testing according to ISO 527-2 2012;
2) Notched Izod impact Strength: testing the notched Izod impact strength according to ISO 180/1A 2019;
3) Fatigue test: fatigue testing was performed according to ASTM D7791-2017, with a maximum stress of 28MPa, frequency of 10Hz, and cycle number recorded.
The test results are shown in Table 3.
TABLE 3 Table 3
As is clear from the data in Table 3, the polyamide compositions prepared in examples 1 to 17 are excellent in elongation at break, impact strength at cantilever beam and fatigue resistance, and example 5 is the most preferable example.
The polyamide composition prepared in example 8 using the polyamide resin having a relative viscosity of 2.4 to 3.2 is also superior in elongation at break, izod impact strength, fatigue resistance to example 5, but inferior to example 5;
example 9 the polyamide composition prepared with a polyamide resin having a relative viscosity outside the range of 2.4-3.2 was inferior in elongation at break, izod impact strength, fatigue resistance to examples 5, 8.
In comparison with example 5, examples 10 to 11 were each made of polytetrafluoroethylene 2 and 3, example 12 was made of impact modifier 2 (maleic anhydride grafted ethylene-propylene-diene rubber), examples 13 to 14 were made of high density polyethylene 2 and 3, and example 15 was made of polyamide composition prepared with epoxy resin 2, respectively, and the elongation at break, the impact strength at cantilever beam and the fatigue resistance were also better than in example 5.
Examples 16 to 17 used epoxy resins 3 and 4, the epoxy equivalent is not in the range of 450 to 700, the epoxy resin with high epoxy equivalent, the number of epoxy groups is reduced, and the reaction between molecules is insufficient; epoxy resins with low epoxy equivalent weight have increased numbers of epoxy groups and even intermolecular crosslinking, and are prone to defects during injection molding, resulting in reduced performance and cycle times.
The absence of high density polyethylene in the formulation of comparative example 1, with the lowest elongation at break, notched Izod impact strength, and the lowest number of cycles of the composition, compared to example 5, indicates that the presence of high density polyethylene has a greater impact on the above properties of the composition; comparative example 2 lacks epoxy resin and polytetrafluoroethylene at the same time, the elongation at break, notched impact strength of cantilever beam, fatigue resistance of the polyamide composition prepared are poor, but comparative example 2 contains high-density polyethylene, the above-mentioned properties are improved to some extent, especially the cycle number is improved most obviously, but the use requirement of the vibration bracket of the sander is still not met; comparative example 3 and comparative example 4 lack epoxy resin or polytetrafluoroethylene and the polyamide has a greater number of fatigue test cycles than comparative example 2, indicating that the combination of epoxy resin and polytetrafluoroethylene can increase cycle times and contribute to the fatigue resistance of the polyamide composition.
The epoxy resin in comparative example 5 was added in an amount of up to 15 parts, and the excessive unreactive epoxy resin easily formed stress concentration points in the system, resulting in a decrease in performance and cycle number, and the HDPE in comparative example 6 using a high melt index had poor melt strength and a significant decrease in performance and cycle number. In comparative example 7, high molecular weight polytetrafluoroethylene was difficult to disperse, and in comparative example 8, low molecular weight polytetrafluoroethylene was not formed into a fibrillated network, resulting in a decrease in performance and cycle number;
when the epoxy resin, the high molecular weight polytetrafluoroethylene and the HDPE are used simultaneously, the elongation at break and the notched impact strength of the cantilever beam of the prepared polyamide composition are greatly improved, and the fatigue cycle times can meet the use requirement of a terminal product.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the 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 the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A polyamide composition characterized in that the polyamide composition comprises the following components in parts by weight:
50-80 parts of polyamide resin, 10-35 parts of impact modifier, 5-20 parts of high-density polyethylene, 0.5-5 parts of epoxy resin and 0.5-5 parts of polytetrafluoroethylene;
the melt index of the high-density polyethylene is 5-14g/10min according to ISO1133-1 2011 under the conditions that the temperature is 190 ℃ and the weight of a test weight is 2.16 kg;
the epoxy resin is bisphenol A type epoxy resin with the epoxy equivalent of 450-700;
the number average molecular weight of the polytetrafluoroethylene is 380-850 ten thousand;
the polyamide resin is polyamide resin with relative viscosity of 2.4-3.2;
the impact modifier is at least one of maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-propylene-diene rubber, acrylonitrile-butadiene-styrene copolymer, styrene-ethylene-butadiene copolymer, ethylene-vinyl acetate copolymer and ethylene-butyl acrylate.
2. The polyamide composition of claim 1, wherein the polyamide composition comprises the following components in parts by weight:
58.9 to 70.4 parts of polyamide resin, 15 to 25 parts of impact modifier, 10 to 15 parts of high-density polyethylene, 1 to 5 parts of epoxy resin and 0.5 to 3 parts of polytetrafluoroethylene.
3. The polyamide composition of claim 1 wherein the polyamide resin is a condensation product of one or more dicarboxylic acids and one or more diamines, or the polyamide resin is a condensation product of one or more aminocarboxylic acids, or the polyamide resin is a ring opening polymerization product of one or more cyclic lactams.
4. The polyamide composition of claim 3 wherein the polyamide resin is at least one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212.
5. The polyamide composition of claim 1 further comprising 0.1 to 3 parts of an additive comprising one or both of a heat stabilizer and a lubricant.
6. The polyamide composition of claim 5 wherein the heat stabilizer is at least one of a hindered phenol stabilizer, a phosphite stabilizer, a cuprous halide complex stabilizer, and a stabilizer of a benzophenone-functional compound.
7. Use of the polyamide composition according to any one of claims 1 to 6 in an electric tool.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279963A (en) * | 1989-03-27 | 1989-11-10 | Japan Synthetic Rubber Co Ltd | Polyamide resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279963A (en) * | 1989-03-27 | 1989-11-10 | Japan Synthetic Rubber Co Ltd | Polyamide resin composition |
Non-Patent Citations (5)
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| MBS/纳米BaSO_4协同增韧聚酰胺6复合材料的研究;郭婷;丁筠;王三昭;吴立峰;乔辉;;中国塑料(第12期);全文 * |
| PA6/HDPE合金的制备及其界面相形态分析;王锡军;陈晓东;徐群杰;周军杰;李健博;;塑料工业(第08期);全文 * |
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