CN113292844A - Low-temperature-resistant polyamide resin composite material with good flexibility and preparation method thereof - Google Patents
Low-temperature-resistant polyamide resin composite material with good flexibility and preparation method thereof Download PDFInfo
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- CN113292844A CN113292844A CN202110403682.0A CN202110403682A CN113292844A CN 113292844 A CN113292844 A CN 113292844A CN 202110403682 A CN202110403682 A CN 202110403682A CN 113292844 A CN113292844 A CN 113292844A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a low-temperature-resistant polyamide resin composite material with good flexibility and a preparation method thereof, wherein the composite material comprises long-carbon-chain nylon, ABS resin, nano-silica, nano-carbon fiber, a coupling agent, an antioxidant and an auxiliary agent, wherein the preparation method comprises the steps of (1) mixing 40-60wt% of the long-carbon-chain nylon, 10-15wt% of the ABS resin, 12-15wt% of the nano-silica and 8-10wt% of the coupling agent for 5-8min at 200-500 r/min in percentage by weight, and then adding 2-8wt% of the antioxidant and 1-9wt% of the auxiliary agent for continuously mixing for 20-40 min; (2) and adding the mixture into an extruder for melting and extruding, adding 5-8wt% of carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and dicing to obtain the ultra-low temperature resistant composite material.
Description
Technical Field
The invention relates to the technical field of polyamide resin composite materials, in particular to a low-temperature-resistant polyamide resin composite material with good flexibility, and a preparation method of the low-temperature-resistant polyamide resin composite material with good flexibility.
Background
Polyamide resins (PA, colloquially referred to as nylon) were the first resins developed for fibers by DuPont in the united states and were commercialized in 1939. In the 50 th of the 20 th century, injection molded products are developed and produced to replace metals to meet the requirements of light weight and cost reduction of downstream industrial products. Polyamide has many repeating amide groups in its main chain, and is called nylon when used as plastic and nylon when used as synthetic fiber. It has toughness, flexibility, strong binding force, wear resistance, oil resistance, water resistance and enzyme bacterium resistance, but has large water absorption, and is a chemical raw material with excellent performance and wide application.
In order to improve the performance of a high polymer material and expand the application market, the high polymer material is modified so as to improve the comprehensive performance of the material, and the method for exploring various potential functions of the material is the most popular method in the human material industry and is widely applied in many fields.
The invention patent of publication No. CN 102604373A discloses a polyamide toughening formulation, which comprises long-chain polyamide resin, nylon elastomer, plasticizer, antioxidant and lubricant. The invention patent publication No. CN 109943069A also discloses a polyamide toughening formulation which comprises long carbon chain polyamide resin, plasticizer, nylon elastomer and the like. In order to improve the low-temperature impact property of the polyamide resin, the nylon elastomer is added in the formula. This has the negative effect that the compatibility between the nylon elastomer and the nylon matrix resin is limited, the nylon elastomer is not well dispersed in the polyamide resin, and the toughening effect and even the strength of the material are reduced. The invention patent publication No. CN 105838066a discloses toughening formulations that do not use elastomers, but have limited low temperature impact properties. The conventional nylon 66, nylon 610 and nylon 612 have high crystallinity, and show remarkable brittleness although the mechanical strength is ensured in a low-temperature dry state.
Disclosure of Invention
In order to overcome the brittleness problem of the nylon resin at low temperature in the prior art, the nylon resin can not be used at low temperature
The invention provides a low-temperature resistant polyamide resin composite material with good flexibility and a preparation method thereof.
The technical scheme adopted by the invention is as follows: a polyamide resin composite material with good flexibility and low temperature resistance has the innovation points that: the ABS resin comprises 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide, 5-8wt% of nano carbon fiber, 8-10wt% of coupling agent, 2-8wt% of antioxidant and 1-9wt% of auxiliary agent.
In some embodiments, the long carbon chain nylon is 50wt%, the ABS resin is 12wt%, the nano silica is 13wt%, the nano carbon fiber is 6wt%, the coupling agent is 9wt%, the antioxidant is 5wt%, and the auxiliary agent is 5 wt%.
In some embodiments, the coupling agent is a composite coupling agent of silane and titanate.
In some embodiments, the compounding ratio of silane to titanate is 1-3: 2-3.
In some embodiments, the silane is at least one of gamma-aminopropyltriethoxysilane, beta-3, 4 epoxycyclohexyltrimethoxysilane.
In some embodiments, the antioxidants include a primary antioxidant that is an aminic antioxidant and a secondary antioxidant that is antioxidant 1010.
In some embodiments, the primary antioxidant and the secondary antioxidant are added in a ratio of 2: 1.
in some embodiments, the additives include processing aids and plasticizers; the addition ratio of the processing aid to the plasticizer is 1: 1.
In some embodiments, the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The invention also aims to provide a preparation method of the low-temperature resistant polyamide resin composite material with good flexibility, which has the innovation points that:
(1) according to the weight percentage, 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide and 8-10wt% of coupling agent are mixed for 5-8min at 500 r/min, then 2-8wt% of antioxidant and 1-9wt% of auxiliary agent are added and mixed for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding 5-8wt% of carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and dicing to obtain the ultra-low temperature resistant composite material.
Compared with the prior art, the invention has the beneficial effects that: the polyamide resin composite material obtained by the invention has the advantages of low cost, simple process, high strength, remarkably reduced product density and excellent overall performance. The invention adopts the composite coupling agent of silane and titanate for surface treatment, improves the toughening modification impact strength by 17.8 percent compared with the untreated composite material, and obviously improves the tear strength and the elongation at break. In addition, the nano silicon dioxide is uniformly dispersed in the resin to form the modified composite material, so that the modified composite material has ideal mechanical property and water resistance, and the thermal deformation temperature is greatly increased, so that the dimensional stability of the material is improved, and meanwhile, the preparation process is simple, the cost of equipment used for reaction is low, and the energy consumption is low.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a polyamide resin composite material with good flexibility and low temperature resistance, which comprises 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide, 5-8wt% of nano carbon fiber, 8-10wt% of coupling agent, 2-8wt% of antioxidant and 1-9wt% of auxiliary agent.
The polyamide resin composite material obtained by the invention has the advantages of low cost, simple process, high strength, remarkably reduced product density and excellent overall performance. The invention adopts the composite coupling agent of silane and titanate for surface treatment, improves the toughening modification impact strength by 17.8 percent compared with the untreated composite material, and obviously improves the tear strength and the elongation at break. In addition, the nano silicon dioxide is uniformly dispersed in the resin to form the modified composite material, so that the modified composite material has ideal mechanical property and water resistance, and the thermal deformation temperature is greatly increased, so that the dimensional stability of the material is improved, and meanwhile, the preparation process is simple, the cost of equipment used for reaction is low, and the energy consumption is low.
More preferably, the modified ABS resin comprises 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
As a further preferred, the coupling agent is a composite coupling agent of silane and titanate.
As a further preference, the compounding ratio of the silane to the titanate is 1-3: 2-3.
More preferably, the silane is at least one of gamma-aminopropyltriethoxysilane and beta-3, 4-epoxycyclohexyltrimethoxysilane.
More preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant is an amine antioxidant, and the secondary antioxidant is antioxidant 1010.
More preferably, the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
as a further preference, the auxiliaries include processing aids and plasticizers; the addition ratio of the processing aid to the plasticizer is 1: 1.
Further preferably, the processing aid is one or a mixture of two of silicone powder and N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The invention also aims to provide a preparation method of the low-temperature resistant polyamide resin composite material with good flexibility, which has the innovation points that:
(1) according to the weight percentage, 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide and 8-10wt% of coupling agent are mixed for 5-8min at 500 r/min, then 2-8wt% of antioxidant and 1-9wt% of auxiliary agent are added and mixed for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding 5-8wt% of carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and dicing to obtain the ultra-low temperature resistant composite material.
Example 1
The polyamide resin composite material with good flexibility and low temperature resistance comprises 40wt% of long carbon chain nylon, 15wt% of ABS resin, 15wt% of nano silicon dioxide, 8wt% of nano carbon fiber, 10wt% of coupling agent, 8wt% of antioxidant and 4wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate
Wherein the compounding ratio of the silane to the titanate is 1: 2.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
Preparation method of composite material
(1) Mixing long carbon chain nylon, ABS resin, nano silicon dioxide and coupling agent at the ratio of 200-;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
Example 2
The polyamide resin composite material with good flexibility and low temperature resistance comprises 60wt% of long carbon chain nylon, 10wt% of ABS resin, 12wt% of nano silicon dioxide, 5wt% of nano carbon fiber, 8wt% of coupling agent, 4wt% of antioxidant and 1wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate
Wherein the compounding ratio of the silane to the titanate is 1: 3.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
Preparation method of composite material
(1) According to the mixture ratio, mixing long carbon chain nylon, 10-1 ABS resin, nano silicon dioxide and coupling agent for 5-8min at 500 revolutions per minute, adding antioxidant and auxiliary agent by weight percent, and continuously mixing for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
Example 3
The polyamide resin composite material with good flexibility and low temperature resistance comprises 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate;
wherein the compounding ratio of the silane to the titanate is 3: 2.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The preparation method of the composite material comprises the following steps:
(1) according to the mixture ratio, mixing the long carbon chain nylon, the ABS resin, the nano-silica and the coupling agent for 5-8min at 500 revolutions per minute, adding the antioxidant and the auxiliary agent, and continuously mixing for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
Example 4
The polyamide resin composite material with good flexibility and low temperature resistance comprises 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate
Wherein the compounding ratio of the silane to the titanate is 1: 1.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The preparation method of the composite material comprises the following steps:
(1) according to the mixture ratio, mixing the long carbon chain nylon, the ABS resin, the nano-silica and the coupling agent for 5-8min at 500 revolutions per minute, adding the antioxidant and the auxiliary agent, and continuously mixing for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
Example 5
The polyamide resin composite material with good flexibility and low temperature resistance comprises 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate;
wherein the compounding ratio of the silane to the titanate is 1: 3.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The preparation method of the composite material comprises the following steps:
(1) according to the mixture ratio, mixing the long carbon chain nylon, the ABS resin, the nano-silica and the coupling agent for 5-8min at 500 revolutions per minute, adding the antioxidant and the auxiliary agent, and continuously mixing for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
Example 6
The polyamide resin composite material with good flexibility and low temperature resistance comprises 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
Wherein the coupling agent is a composite coupling agent of silane and titanate;
wherein the compounding ratio of the silane to the titanate is 1: 2.
Wherein the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4-epoxycyclohexyl trimethoxysilane.
The antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
Wherein the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
wherein the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
Wherein the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
The preparation method of the composite material comprises the following steps:
(1) according to the mixture ratio, mixing the long carbon chain nylon, the ABS resin, the nano-silica and the coupling agent for 5-8min at 500 revolutions per minute, adding the antioxidant and the auxiliary agent, and continuously mixing for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding the carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and granulating to obtain the ultra-low temperature resistant composite material.
The composites obtained in examples 1-6 above were tested for properties, and the results are shown in the following table:
| performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile Strength (MPA) | 190 | 195 | 201 | 253 | 232 | 225 |
| Flexural Strength (MPA) | 243 | 256 | 287 | 275 | 273 | 268 |
| IZOD notched impact Strength (25 ℃ C.) (J/m) | 650 | 643 | 662 | 658 | 652 | 647 |
| IZOD notched impact Strength (60 ℃ C.) (J/m) | 301 | 320 | 311 | 345 | 331 | 329 |
Performance test reference standard:
tensile strength test standard reference ASTM D638;
flexural strength test standard reference ASTM D790;
the notched impact strength test standard is referred to ASTM D256.
As can be seen from the test results of the above examples, the composite material prepared by the present invention has high impact strength even at low temperature of-60 ℃, and thus it is sufficient to show that the composite material of the present invention has good performance at low temperature.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A polyamide resin composite material with good flexibility and low temperature resistance is characterized in that: the ABS resin comprises 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide, 5-8wt% of nano carbon fiber, 8-10wt% of coupling agent, 2-8wt% of antioxidant and 1-9wt% of auxiliary agent.
2. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 1, wherein: 50wt% of long carbon chain nylon, 12wt% of ABS resin, 13wt% of nano silicon dioxide, 6wt% of nano carbon fiber, 9wt% of coupling agent, 5wt% of antioxidant and 5wt% of auxiliary agent.
3. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 2, wherein: the coupling agent is a composite coupling agent of silane and titanate.
4. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 3, wherein: the compounding ratio of the silane to the titanate is 1-3: 2-3.
5. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 4, wherein: the silane is at least one of gamma-aminopropyl triethoxysilane and beta-3, 4 epoxycyclohexyl trimethoxysilane.
6. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 3, wherein: the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is an amine antioxidant, and the secondary antioxidant is an antioxidant 1010.
7. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 5, wherein: the addition ratio of the primary antioxidant to the secondary antioxidant is 2: 1.
8. the polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 4, wherein: the auxiliary agent comprises a processing auxiliary agent and a plasticizer; the addition ratio of the processing aid to the plasticizer is 1: 1.
9. The polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 8, wherein: the processing aid is one or a mixture of two of silicone powder or N, N' -ethylene bis stearamide; the plasticizer is N-butyl benzene sulfonamide.
10. A preparation method of the polyamide resin composite material with good flexibility and low temperature resistance as claimed in claim 1 is characterized in that:
(1) according to the weight percentage, 40-60wt% of long carbon chain nylon, 10-15wt% of ABS resin, 12-15wt% of nano silicon dioxide and 8-10wt% of coupling agent are mixed for 5-8min at 500 r/min, then 2-8wt% of antioxidant and 1-9wt% of auxiliary agent are added and mixed for 20-40 min;
(2) and adding the mixture into an extruder for melting and extruding, adding 5-8wt% of carbon nanofibers through a glass fiber port of a double-screw extruder, and extruding, cooling, drying and dicing to obtain the ultra-low temperature resistant composite material.
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| CN102382452A (en) * | 2010-12-27 | 2012-03-21 | 重庆文理学院 | Nano-modified nylon composite material and preparation method thereof |
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| CN109517368A (en) * | 2018-11-19 | 2019-03-26 | 常熟市强盛冲压件有限公司 | A kind of gear lever pole socket plastic alloy material and preparation method thereof |
| CN110982262A (en) * | 2019-12-20 | 2020-04-10 | 广州市聚赛龙工程塑料股份有限公司 | Wear-resistant reinforced long-carbon-chain nylon PA1012 composite material and preparation method thereof |
| CN111073271A (en) * | 2019-12-29 | 2020-04-28 | 无锡殷达尼龙有限公司 | Low-temperature-resistant polyamide resin composite material with good flexibility and preparation method thereof |
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2021
- 2021-04-15 CN CN202110403682.0A patent/CN113292844A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382452A (en) * | 2010-12-27 | 2012-03-21 | 重庆文理学院 | Nano-modified nylon composite material and preparation method thereof |
| CN102911496A (en) * | 2011-08-05 | 2013-02-06 | 鸿富锦精密工业（深圳）有限公司 | Resin composition and complex prepared by using same |
| CN109517368A (en) * | 2018-11-19 | 2019-03-26 | 常熟市强盛冲压件有限公司 | A kind of gear lever pole socket plastic alloy material and preparation method thereof |
| CN110982262A (en) * | 2019-12-20 | 2020-04-10 | 广州市聚赛龙工程塑料股份有限公司 | Wear-resistant reinforced long-carbon-chain nylon PA1012 composite material and preparation method thereof |
| CN111073271A (en) * | 2019-12-29 | 2020-04-28 | 无锡殷达尼龙有限公司 | Low-temperature-resistant polyamide resin composite material with good flexibility and preparation method thereof |
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Application publication date: 20210824 |