CN117209999B - Polyamide composite material and preparation method and application thereof - Google Patents
Polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN117209999B CN117209999B CN202311392456.2A CN202311392456A CN117209999B CN 117209999 B CN117209999 B CN 117209999B CN 202311392456 A CN202311392456 A CN 202311392456A CN 117209999 B CN117209999 B CN 117209999B
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Abstract
本发明属于工程塑料技术领域，具体涉及一种聚酰胺复合材料及其制备方法和应用。所述聚酰胺复合材料，包括以下重量份计的组分：尼龙树脂50‑100份、环氧树脂1‑10份、多元醇0.1‑5份、锌离子离聚物2‑10份、玻璃纤维5‑30份。本发明制得的聚酰胺复合材料，能够有效提高材料的热稳定性以及避免材料在高温下发生降解，使复合材料在高温高湿环境下依旧能够保持较高的熔接痕强度以及优异的回弹性能、机械性能，具有更广阔的材料应用空间。The present invention belongs to the technical field of engineering plastics, and specifically relates to a polyamide composite material and a preparation method and application thereof. The polyamide composite material comprises the following components in parts by weight: 50-100 parts of nylon resin, 1-10 parts of epoxy resin, 0.1-5 parts of polyol, 2-10 parts of zinc ion ionomer, and 5-30 parts of glass fiber. The polyamide composite material prepared by the present invention can effectively improve the thermal stability of the material and avoid the degradation of the material at high temperature, so that the composite material can still maintain a high weld mark strength and excellent resilience and mechanical properties under high temperature and high humidity environment, and has a broader material application space.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a polyamide composite material and a preparation method and application thereof.
Background
Nylon engineering materials are widely applied in various fields, and with the continuous improvement of the technical level, the variety of products is more and more, however with the development of modern high technology, the products with complicated durability, chemical resistance and structural design are gradually increased, and higher requirements are put on the comprehensive properties of the materials. The nylon material has the advantages of meeting the characteristics of high strength, high heat resistance and the like, meeting the requirements of maintaining good comprehensive performance under the conditions of high temperature, high humidity, high stress and the like, and being one of the representatives of the high-strength high heat resistance material, and has the defects of easy water absorption, different degree of reduction of the thermal stability, the dimensional stability and the performance retention rate of the material after water absorption, certain resistance during use, and different related researches in the industry in order to further expand the application of the nylon material.
Chinese patent CN110791085A discloses that a carboxyl compound is used to increase the weld mark strength in glass fiber reinforced nylon material, but because the carboxyl compound is an acidic substance, there is a great influence on the strength of the material. Chinese patent CN115536798a discloses a method for preparing polyurethane composite material by using polyol as reaction component, but the injection weld mark of the prepared polyurethane composite material and polyamide material is very different.
Therefore, materials which can meet the requirement of high weld mark and high rebound resilience in specific environments are rarely met in polyamide modification, and the technical scheme is provided for solving the technical blank in the prior art.
Disclosure of Invention
The invention aims to provide a polyamide composite material, and a preparation method and application thereof. The polyamide composite material prepared by the invention can maintain good weld mark strength and excellent material rebound resilience after being subjected to high-temperature and high-humidity environment.
In order to achieve the aim, the technical scheme is that the polyamide composite material comprises, by weight, 50-100 parts of nylon resin, 1-10 parts of epoxy resin, 0.1-5 parts of polyol, 2-10 parts of zinc ion ionomer and 5-30 parts of glass fiber.
Preferably, the polyamide composite material comprises 68-80 parts by weight of nylon resin, 5-8 parts by weight of epoxy resin, 1.0-1.5 parts by weight of polyol, 5-7 parts by weight of zinc ion ionomer and 20-25 parts by weight of glass fiber.
Preferably, the content of the terminal amino groups of the nylon resin is 45-110 mmol/kg.
Preferably, the content of the terminal amino groups of the nylon resin is 45-85 mmol/kg.
The method for testing the terminal amino content of the nylon resin comprises the steps of dissolving the nylon resin in 2.2.2-trifluoroethanol, and titrating an amino group by using a 0.02mol/L hydrochloric acid aqueous solution.
Preferably, the nylon resin has a relative viscosity of 2.6 to 2.7. The nylon resins of the present invention were tested for relative viscosity according to ISO 307 (dissolution at room temperature using concentrated sulfuric acid as solvent).
Preferably, the nylon resin comprises at least one of PA66, PA610, PA 1010.
Preferably, the mass ratio of the epoxy resin, the polyol and the zinc ion ionomer is (1-10): (0.1-5): (2-10).
Preferably, the zinc ion ionomer is a Sha Linji thermoplastic ionomer and the melt flow rate of the zinc ion ionomer under 190 ℃ and 2.16kg test conditions is 0.3-10g/10min. The melt flow rate of the zinc ion ionomers described herein was according to ASTM D1238-2010 version of the test standard.
Preferably, the zinc ion ionomer has a melt flow rate of 0.5 to 1.5g/10min at 190 ℃ under 2.16kg test conditions.
More preferably, the zinc ion ionomer has a melt flow rate of 0.8 to 1.3g/10min at 190 ℃ under 2.16kg test conditions.
Preferably, the epoxy resin has an epoxy equivalent value of 1080-4500g/eq.
Preferably, the epoxy resin has an epoxy equivalent value of 1300-4000g/eq. The epoxy equivalent of the epoxy resin according to the invention was tested according to GB/T4612-2008.
Preferably, the polyol is pentaerythritol and/or dipentaerythritol.
Preferably, the glass fibers are alkali-free glass fibers.
Preferably, the polyamide composite material further comprises 1-5 parts of an auxiliary agent, wherein the auxiliary agent comprises at least one of a lubricant, a nucleating agent, an antistatic agent and an antioxidant. The lubricant selected in the invention can be selected from stearate, the nucleating agent can be selected from sodium fatty acid, the antistatic agent can be selected from ethoxylated fatty amine, the antioxidant can be selected from phenolic antioxidants and other conventional components in the field.
In the polyamide composite material, the content of the nylon resin is not less than 45%.
Preferably, the nylon resin content is 60% or more.
According to the invention, epoxy resin, polyol and zinc ion ionomer are added into a polyamide material, and epoxy groups of the epoxy resin are combined with molecular chain end amino groups of the polyamide resin to form a micro-crosslinking structure, so that the acting force between molecules is improved, the surface compactness of the material is effectively improved, the material is effectively protected from the influence of external environment, the thermal stability of the prepared material is enhanced, hydroxyl groups of the polyol in a formula system can chelate the zinc ion ionomer, the degradation of the nylon resin is inhibited, the self advantages of the material can be exerted, the toughness of the material is improved, the material is effectively protected from the influence of external high-temperature high-humidity environment, and meanwhile, the thermal stability of the polyamide composite material can be better improved under the integral synergistic effect when the material is heated, so that the weld mark strength of the material in the high-temperature high-humidity environment is improved, and the material has excellent rebound resilience.
The invention also claims a preparation method of the polyamide composite material, which comprises the following steps:
All components except the glass fiber are premixed, and then are melt-mixed with the glass fiber, and extrusion granulation is carried out, so that the polyamide composite material is prepared.
Preferably, a double-screw extruder is adopted for the melt mixing, wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48:1.
Preferably, the glass fibers are fed from the side of a twin screw extruder.
Preferably, the temperature of the melt mixing is 230-260 ℃ and the rotating speed is 200-550 rpm.
The invention also claims the application of the polyamide composite material in the fields of electronics and electricity, new energy tolerance and industrial construction. The novel energy high-voltage connector comprises a novel energy high-voltage connector, a photovoltaic end plate, a building heat insulation protection layer and the like.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, through the interaction among nylon resin, epoxy resin, polyol and zinc ion ionomer, the thermal stability of the prepared material can be effectively improved, and degradation of the material at high temperature is avoided, so that the composite material can still maintain higher weld mark strength and excellent rebound performance and mechanical property under high-temperature and high-humidity environment, and has wider material application space.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the antioxidants were obtained commercially and the same antioxidants were used in parallel experiments.
The raw materials used in the examples and comparative examples are described in Table 1.
TABLE 1
Examples 1 to 11 and comparative examples 1 to 5
The polyamide composite materials of examples 1 to 11 and comparative examples 1 to 5 were as shown in tables 2 to 3 in the components and parts by weight.
The preparation methods of the polyamide composite materials of examples 1 to 11 and comparative examples 1 to 5 include the following steps:
Premixing all components except glass fibers, putting the components into a double-screw extruder for melt mixing, feeding the glass fibers at the side, extruding and granulating to obtain the polyamide composite material, wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48:1, the temperature of a screw cylinder is 230-260 ℃, and the rotating speed of the screw is 200-550 rpm.
Table 2 the amounts (parts by weight) of the components in the examples
Table 3 amounts of the components (parts by weight) in the comparative examples
Performance testing
The polypropylene composites prepared in examples 1 to 11 and comparative examples 1 to 5 were subjected to the relevant performance test, the test methods and standards are as follows, and the experimental results are shown in table 4.
Weld mark strength test:
And carrying out injection molding, stretching and welding trace sample bars on the prepared material in an injection molding machine at 275 ℃ and with the rated speed of 55% of a 280T injection molding machine and the pressure of 50 bar. And (3) drying the prepared sample bar at 120 ℃ for 4 hours, performing a tensile weld mark strength test, taking out the sample, placing the sample at 90% humidity, treating the sample in an environment box at 95 ℃ for 200 hours, and then taking out the sample, treating the sample at 23 ℃ and 50% humidity for 0.5 hour to perform the tensile weld mark strength test, wherein the ratio of the sample to the sample is the weld mark performance retention rate of the material.
Test of rebound resilience:
According to UL94-2014 standard, 125 x 10 x 1mm of sample bars are injection molded, after 24 hours of treatment in an environment with 50% humidity and 23 ℃, the sample bars are folded in half by 180 degrees, 5kg weights are placed at two ends of the sample bars, after 100 hours of placement in an environment with 100 degrees, the weights are removed, the angle formed by the sample bars is tested, and the larger the angle is, the better the rebound resilience performance is. Wherein, 0-30 degrees is 1 level, 31-60 degrees is 2 level, and more than 60 degrees is 3 level.
TABLE 4 Performance test results
As can be seen from the data in table 4, the polyamide composite material prepared in the example of the present invention has a higher weld strength retention rate in a high-temperature and high-humidity environment, and also has excellent rebound resilience. Wherein the weld mark strength retention can be maintained in the range of 70-78%, and the rebound resilience can be maintained in the level of 2-3.
The comparative example 1 was unsuitable in weight part of the epoxy resin and comparative example 2 was unsuitable in weight part of the zinc ion ionomer, the prepared polyamide composite material was inferior in weld mark strength retention under high temperature and high humidity environment to that of the example and had poor rebound resilience, the comparative example 3 was free of the zinc ion ionomer, the comparative example 4 was selected to replace the zinc ion ionomer, the prepared polyamide composite material was inferior in weld mark strength retention and rebound resilience to the example, the comparative example 5 was selected to replace the epoxy resin, and the prepared composite material was inferior in weld mark strength retention under high temperature and high humidity environment and had poor rebound resilience.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (9)
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| CN119391173A (en) * | 2024-02-26 | 2025-02-07 | 张家港绿洲新材料科技有限公司 | Method for improving crystallinity of polyamide and polyamide composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1041109A2 (en) * | 1999-03-30 | 2000-10-04 | Ube Industries, Ltd. | Polyamide compositions having good fluidity |
| JP2007204675A (en) * | 2006-02-03 | 2007-08-16 | Toray Ind Inc | Polyamide resin composition for blow molding |
| CN112538260A (en) * | 2020-10-28 | 2021-03-23 | 广东轻工职业技术学院 | Glass fiber reinforced polypropylene/polyamide composite material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8714234D0 (en) * | 1987-06-17 | 1987-07-22 | Du Pont Canada | Extrusion of compositions of polyamides & epoxides |
| CN1204198C (en) * | 2001-11-02 | 2005-06-01 | 上海杰事杰新材料股份有限公司 | Glass fiber reinforced blow molded nylon |
| US20070135586A1 (en) * | 2005-12-09 | 2007-06-14 | Shreyas Chakravarti | Polyamide blend compositions formed article and process thereof |
| CN110791085B (en) * | 2019-10-18 | 2022-05-20 | 广东轻工职业技术学院 | High weld mark strength glass fiber reinforced polyamide composite material and preparation method thereof |
| CN115926450B (en) * | 2022-11-28 | 2024-07-16 | 天津金发新材料有限公司 | Polyamide composite material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1041109A2 (en) * | 1999-03-30 | 2000-10-04 | Ube Industries, Ltd. | Polyamide compositions having good fluidity |
| JP2007204675A (en) * | 2006-02-03 | 2007-08-16 | Toray Ind Inc | Polyamide resin composition for blow molding |
| CN112538260A (en) * | 2020-10-28 | 2021-03-23 | 广东轻工职业技术学院 | Glass fiber reinforced polypropylene/polyamide composite material and preparation method thereof |
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