CN111690254B - Long-term heat-resistant modified polyamide composite material and preparation method thereof - Google Patents
Long-term heat-resistant modified polyamide composite material and preparation method thereof Download PDFInfo
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- CN111690254B CN111690254B CN202010684150.4A CN202010684150A CN111690254B CN 111690254 B CN111690254 B CN 111690254B CN 202010684150 A CN202010684150 A CN 202010684150A CN 111690254 B CN111690254 B CN 111690254B
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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Abstract
The invention discloses a long-term heat-resistant modified polyamide composite material and a preparation method thereof, wherein the polyamide composite material comprises a polyamide matrix, a filler, a lubricant, a chain scission inhibitor, a heat stabilizer, an antioxidant and other auxiliaries which are mixed according to a certain proportion; the preparation method comprises the steps of adding the polyamide matrix, the filler, the lubricant, the chain scission inhibitor, the heat stabilizer and other additives into a double-screw extruder according to a preset proportion, melting, extruding, granulating and drying to obtain the polyamide composite material. The modified polyamide composite material provided by the invention has excellent processing performance, and the addition of the special heat stabilizer, the chain scission inhibitor and the semi-aromatic nylon capable of participating in amide exchange endows the material with excellent long-term high-heat-resistant aging performance, and after being baked at a high temperature of 3000h, the main mechanical property, the tensile strength and the impact strength retention rate of a simply supported beam notch of the product are more than 80%, so that the modified polyamide composite material has strong market competitiveness.
Description
Technical Field
The invention belongs to the field of nylon modified materials, and particularly relates to a long-term heat-resistant modified polyamide composite material and a preparation method thereof.
Background
With the development of modern automobile technology, the development of light weight of automobiles becomes an urgent new subject, and in order to achieve energy conservation, emission reduction and reduction of the weight of the whole automobiles, the use amount of functional parts made of plastics in the automobiles is increasing day by day. With the development of light weight of automobiles, polyamide engineering plastics are widely used in the periphery of automobile engines and power transmission systems because of their easy processing, light weight, durability and other properties.
The polyamide engineering plastic is reinforced and modified and then is often used as a raw material of heat-resistant parts around an engine, the heat-resistant parts around the engine are exposed to a high-temperature and high-oil-stain environment for a long time, the problem of thermal-oxidative aging degradation is often caused, and the service life of parts is shortened. How to overcome and solve the problem that the long-period exposure performance of polyamide in a high-temperature environment is not deteriorated and the service life of a plastic structural part is urgently prolonged.
Currently, high performance heat resistant PA6 materials cannot maintain a high performance state for long periods at temperatures in excess of 180 ℃.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide a long-term heat-resistant modified polyamide composite material and a preparation method thereof.
The invention is realized by the following technical scheme:
a long-term heat-resistant modified polyamide composite material is characterized in that: the polyamide composite material comprises the following components in percentage by mass:
60% -75% of a polyamide matrix;
10% -30% of filler;
0.2% -1% of a lubricant;
0.2 to 1 percent of chain scission inhibitor
3% -8% of a heat stabilizer;
0.2 to 0.8 percent of antioxidant
5% -15% of an auxiliary agent.
In the technical scheme, the polyamide matrix is one or a mixture of more of PA6, PA66 or PA6/66 copolymer.
In the technical scheme, the filler is a mixture of one or more of chopped alkali-free glass fibers, glass beads, wollastonite, kaolin, montmorillonite or barium sulfate; the lubricant is any one or a mixture of more of silicone powder, ethylene bis stearamide, calcium montanate, ethylene acrylic acid copolymer or calcium stearate; the chain scission inhibitor is an ethylene maleic anhydride copolymer or an epoxy functional group copolymer; the auxiliary agent is semi-aromatic nylon capable of undergoing an amide exchange reaction with PA6 and PA 6/66.
In the technical scheme, the filler is hydrolysis-resistant chopped alkali-free glass fiber.
In the above technical scheme, the lubricant is calcium montanate.
In the technical scheme, the chain scission inhibitor is copolymer ADR-4400 with a basf epoxy functional group.
In the technical scheme, the auxiliary agent is PA 6I/6T.
In the above technical scheme, the heat stabilizer is a copper salt heat stabilizer.
In the technical scheme, the antioxidant is a compound of 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and bis (2, 4-di-tert-butyl) pentaerythritol diphosphite in a mass ratio of 1: 1-1: 2.
A preparation method of a long-term heat-resistant modified polyamide composite material comprises the steps of adding a polyamide matrix, a filler, a lubricant, a chain scission inhibitor, a heat stabilizer, an antioxidant and an auxiliary agent into a double-screw extruder in proportion, melting, extruding, granulating and drying to obtain the long-term heat-resistant modified polyamide composite material.
The invention has the beneficial effects that:
the invention provides a long-term heat-resistant modified polyamide composite material and a preparation method thereof, the modified polyamide composite material has excellent processing performance, the addition of a special heat stabilizer endows the material with excellent long-term high-temperature-resistant aging performance, and after 3000h high-temperature baking, the product performance retention rate is over 80 percent, and the long-term heat-resistant modified polyamide composite material has strong market competitiveness. According to the material, a special heat stabilizer is added, so that the activity of the material during high-temperature oxidation is passivated, and the thermal oxidation aging resistance of the material is obviously improved; special heat stabilizer is compounded with high temperature resistant antioxidants 1790 and 9228 to improve the free radical oxidation capability of the product; the broken nylon chains oxidized and broken at high temperature are re-crosslinked to form polymer chains through the chain breakage inhibitor, so that the reduction of the product performance caused by the reduction of the molecular weight of the material due to high-temperature oxidation is avoided. In addition, semi-aromatic nylon continuously performs amide exchange reaction with a matrix at high temperature and in an aging process, so that the overall temperature resistance of the material is improved in the aspect of improving the temperature resistance of a molecular chain.
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the technical scheme of the long-lasting heat-resistant modified polyamide composite material and the preparation method thereof of the invention are further described by the following specific embodiments.
A long-term heat-resistant modified polyamide composite material is characterized in that: the polyamide composite material comprises the following components in percentage by mass:
60% -75% of a polyamide matrix;
10% -30% of filler;
0.2% -1% of a lubricant;
0.2 to 1 percent of chain scission inhibitor
3% -8% of a heat stabilizer;
0.2 to 0.8 percent of antioxidant
5% -15% of other additives.
The polyamide matrix is PA6, PA66, PA6/66 copolymer or any mixture thereof.
The filler is one or a mixture of more of chopped alkali-free glass fibers, glass beads, wollastonite, kaolin, montmorillonite or barium sulfate, and preferably hydrolysis-resistant chopped alkali-free glass fibers.
The lubricant is any one or a mixture of more of silicone powder, ethylene bis stearamide, calcium montanate, ethylene acrylic acid copolymer or calcium stearate, and is preferably calcium montanate.
The chain scission inhibitor is an ethylene maleic anhydride copolymer or an epoxy functional copolymer, preferably a basf epoxy functional copolymer ADR-4400.
The heat stabilizer is a copper salt heat stabilizer BRUGGOLENN TP-H1805.
The antioxidant is a compound of 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (antioxidant 1790, RIANOX 1790) and bis (2, 4-di-tert-butyl) pentaerythritol diphosphite (antioxidant 9228, Doverphos S-9228), and the compound ratio is 1: 1-2.
The auxiliary agent is semi-aromatic nylon capable of undergoing an amide exchange reaction with PA6 and PA6/66, and is preferably PA 6I/6T.
A preparation method of a long-term heat-resistant modified polyamide composite material comprises the steps of adding a polyamide matrix, a filler, a lubricant, a chain scission inhibitor, a heat stabilizer, an antioxidant and an auxiliary agent into a double-screw extruder according to a preset proportion, melting, extruding, granulating and drying to obtain the long-term heat-resistant modified polyamide composite material.
Example 1
Weighing 54.4 parts of polyamide 6 (with a relative viscosity of 3.8), 20 parts of hydrolysis-resistant short glass fiber T435TM, 0.5 part of lubricant calcium montanate, 0.5 part of chain scission inhibitor ADR-4400, 7 parts of heat stabilizer (TP-H1805), 15 parts of semi-aromatic nylon PA6I/6T, 0.6 part of antioxidant and 2 parts of black master batch.
The components except the glass fiber are placed in a high-speed mixer to be uniformly mixed, then the mixture is added into a double-screw extruder from a main feeding port (the extrusion temperature is 220-275 ℃, the temperatures are different according to different extrusion conditions, the temperature from one zone to three zones is relatively low, and the temperature from eight zone to ten zone is relatively high), the glass fiber is added into the extruder from a side feeding port to be extruded and granulated, the obtained particles are dried in a blast oven at 105 ℃ for 6 hours, and then injection molding is carried out to obtain ISO standard sample bars, and tensile and impact performance tests are carried out according to ISO527 and ISO 179.
Examples 2 to 5
According to the method of the embodiment 1, different component formulas in the table 1 are adopted respectively to obtain different products of the embodiments 2-5.
The product properties of examples 1 to 5 are compared in Table 2
TABLE 1 formulation compositions for the products of examples 1-5
The materials obtained in examples 1-5 were subjected to performance tests, and the test results are shown in Table 2.
Table 2 examples 1-5 product performance test results
The invention provides a long-term heat-resistant reinforced modified polyamide composite material and a preparation method thereof, the modified polyamide composite material has excellent processing performance, special heat stabilizer, chain scission inhibitor and semi-aromatic nylon capable of participating in amide exchange are added, the material is endowed with excellent long-term high-temperature-resistant aging performance, after being baked at high temperature of 3000h, the product performance retention rate is more than 80%, and the modified polyamide composite material has strong market competitiveness.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (5)
1. A long-term heat-resistant modified polyamide composite material is characterized in that: the polyamide composite material comprises the following components in percentage by mass:
60% -75% of a polyamide matrix;
10% -30% of filler;
0.2% -1% of a lubricant;
0.2 to 1 percent of chain scission inhibitor
3% -8% of a heat stabilizer;
0.2 to 0.8 percent of antioxidant
5% -15% of an auxiliary agent;
the polyamide matrix is one or a mixture of PA6, PA66 or PA6/66 copolymer;
the chain scission inhibitor is copolymer ADR-4400 with a basf epoxy functional group;
the auxiliary agent is PA 6I/6T;
the heat stabilizer is a copper salt heat stabilizer;
the antioxidant is a compound of 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and bis (2, 4-di-tert-butyl) pentaerythritol diphosphite in a mass ratio of 1: 1-1: 2.
2. The long lasting heat resistant modified polyamide composite of claim 1, characterized by: the filler is any one or a mixture of a plurality of chopped alkali-free glass fibers, glass beads, wollastonite, kaolin, montmorillonite or barium sulfate; the lubricant is any one or a mixture of more of silicone powder, ethylene bis stearamide, calcium montanate, ethylene acrylic acid copolymer or calcium stearate.
3. The long lasting heat resistant modified polyamide composite of claim 1, characterized by: the filler is hydrolysis-resistant chopped alkali-free glass fiber.
4. The long lasting heat resistant modified polyamide composite of claim 1, characterized by: the lubricant is calcium montanate.
5. The method for producing a long-lasting heat-resistant modified polyamide composite material as claimed in claim 1, wherein: the method specifically comprises the steps of adding a polyamide matrix, a filler, a lubricant, a chain scission inhibitor, a heat stabilizer, an antioxidant and an auxiliary agent into a double-screw extruder according to a proportion, melting, extruding, granulating and drying to obtain the polyamide composite material.
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| CN111690254B true CN111690254B (en) | 2022-04-22 |
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| CN115124830A (en) * | 2022-06-16 | 2022-09-30 | 天津长芦海晶集团有限公司 | Cold-resistant, wear-resistant, high-adhesive-force and solvent-resistant modified polycaprolactam composite material and preparation method thereof |
Citations (4)
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| CN104212162A (en) * | 2013-05-30 | 2014-12-17 | 上海杰事杰新材料(集团)股份有限公司 | Flame-retardation enhanced high-temperature resistance nylon composite material and preparation method thereof |
| CN107778853A (en) * | 2016-08-29 | 2018-03-09 | 合肥杰事杰新材料股份有限公司 | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof |
| CN108676355A (en) * | 2018-05-23 | 2018-10-19 | 江苏金发科技新材料有限公司 | Low floating fine high glaze fiber glass reinforced polyamide composition |
| CN111073235A (en) * | 2019-09-30 | 2020-04-28 | 浙江工业大学 | Fast-crystallization high-temperature-resistant polylactic acid composition and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212162A (en) * | 2013-05-30 | 2014-12-17 | 上海杰事杰新材料(集团)股份有限公司 | Flame-retardation enhanced high-temperature resistance nylon composite material and preparation method thereof |
| CN107778853A (en) * | 2016-08-29 | 2018-03-09 | 合肥杰事杰新材料股份有限公司 | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof |
| CN108676355A (en) * | 2018-05-23 | 2018-10-19 | 江苏金发科技新材料有限公司 | Low floating fine high glaze fiber glass reinforced polyamide composition |
| CN111073235A (en) * | 2019-09-30 | 2020-04-28 | 浙江工业大学 | Fast-crystallization high-temperature-resistant polylactic acid composition and preparation method thereof |
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