CN112694748A - High-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and preparation method thereof - Google Patents
High-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and preparation method thereof Download PDFInfo
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
The invention relates to a high-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and a preparation method thereof. The composite material comprises the following components in parts by weight: 62.9-75 parts of PA66 resin; 25-35 parts of flat glass fiber; 0.5-1.5 parts of a long-acting heat stabilizer; 0.1 to 1 percent of colorant; 0.2-1.5 parts of other additives. The composite material has excellent alcoholysis resistance and laser transmittance.
Description
Technical Field
The invention belongs to the field of PA66 materials, and particularly relates to a high-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and a preparation method thereof.
Background
The repeating units on the molecular chain of the nylon 66(PA66) contain polar amide groups, can form intermolecular hydrogen bonds, has regular structure, crystallinity and large intermolecular interaction force, so the polyamide has the main characteristics of excellent mechanical property, high strength, high rigidity and good toughness; the lubricating grease has self-lubricating property and good friction resistance; wide application temperature range, good electric insulation performance, high volume resistivity and breakdown voltage resistance, and good oil resistance and chemical stability. In addition, the amido group in the molecular chain is easy to form hydrogen bonds with water molecules, so that the water absorption rate is high, and the dimensional stability of the product is influenced to a certain extent.
Automotive cooling systems are an important component of engine systems and function to ensure that the engine operates within a proper temperature range. At present, a water-cooling type cooling system is commonly adopted for an automobile engine, a part through which cooling liquid flows comprises a water pump, a cooling water pipe, a radiator, a thermostat and a connecting pipeline, redundant heat of the engine is removed, and the redundant heat is dissipated to the surrounding environment through the radiator, and plastic parts are in long-term contact with the cooling liquid in the use process, and are required to have better alcoholysis resistance and are not allowed to generate stress cracking. For example, after the common standard VW52682 material or part is placed in a 100% glycol solution for 48 hours at the constant temperature of 135 ℃, the surface of the product has no cracking phenomenon, and other main engine plants also put forward a clear requirement on the alcoholysis resistance of the water chamber material of the automobile radiator.
Chinese patent CN 104448813B discloses a glass fiber reinforced nylon 66 composite material, which is composed of the following raw materials in percentage by weight; nylon 6650-79%; 20-49% of glass fiber, 0.1-2% of coupling agent, 0.5-5% of compatilizer, 0.1-2% of main antioxidant, 0.1-2% of auxiliary antioxidant, 0.1-2% of lubricant and 0.1-3% of anti-alcoholysis agent; the glass fiber is alkali-free glass fiber with the monofilament diameter range of 5-9 mu m; the alcoholysis resisting agent is polycarbodiimide. According to the preparation method, alkali-free glass fiber reinforced PA66 with a relatively thin monofilament diameter is adopted, and other technical means such as an alcoholysis resistance agent are combined, so that a better alcoholysis resistance performance can be obtained, and the glass fiber reinforced nylon 66 composite material can be used for preparing an air inlet manifold of an automobile engine. Although the patent is excellent in mechanical properties, the long-term high-temperature alcoholysis resistance is still not ideal.
Chinese patent CN 108948738A relates to modified nylon material, and discloses a modified nylon 66 material for hydrolysis and alcoholysis resistance for automobile water chambers and a preparation method thereof, wherein the raw materials comprise 120 parts of nylon 66100-one, 48-72 parts of reinforcing agent, 9-18 parts of water blocking agent, 0.4-4 parts of antioxidant and 0.5-1 part of silane coupling agent; the reinforcing agent comprises 40-60 parts of glass fiber, and the water-blocking agent comprises 6-10 parts of fluorinated graphene and 3-8 parts of styrene-vinylphenol copolymer; weighing raw materials according to parts by weight, drying, mixing, adding into a screw extruder, heating, melting and extruding for granulation to obtain modified nylon 66 material granules, wherein the tensile property and bending property of the modified nylon 66 material are improved, and the modified nylon 66 material has hydrolysis resistance, alcoholysis resistance and good dimensional stability, is not easy to deform in size at high temperature, and meets the use conditions and environments of automobile water chambers. Although the combination has improved tensile property and bending property and good dimensional stability, the long-term high-temperature alcoholysis resistance is still not ideal.
Chinese patent CN 110776734A discloses a wear-resistant hydrolysis-resistant alcohol-depolymerized polyamide-based composite material, which comprises the following raw materials in percentage by mass: 60-68% of polyamide resin, 29-31% of glass fiber, 2-5% of wear-resisting agent, 0.5-1.2% of compound hydrolysis-resisting agent, 0.2-0.4% of lubricant, 0.2-0.4% of antioxidant, 0.1-0.3% of flow modifier and 0-0.5% of laser master batch. According to the method, the characteristic of low water absorption of long carbon chain nylon is utilized, the synergistic effect of the compound hydrolysis resistant agent, the low-surface-energy wear-resistant agent and the fluorine-containing lubricant is added, the obtained composite material has excellent hydrolysis and alcoholysis resistance and wear resistance, and the laser marking performance is given to the composite material, so that the application requirements of water contact application fields such as an automobile cooling system, a junction temperature sensor, a temperature control valve, a pump bearing and the like can be met. The composite material has good alcoholysis resistance and wear resistance, and although the mechanical property is excellent, compared with PA66, the price of the used long carbon chain nylon is higher.
In the prior art, most alcoholysis-resistant materials achieve alcoholysis resistance by adding alcoholysis-resistant glass fibers or alcoholysis-resistant agents, and although the alcoholysis-resistant property of the materials at low temperature (not more than 130 ℃) is improved, the alcoholysis-resistant requirement of more than 130 ℃ is still difficult to meet.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and a preparation method thereof, so as to overcome the defect of poor high-temperature alcoholysis resistance of polyamide materials in the prior art.
The invention also provides a PA66 composite material, which comprises the following components in parts by weight:
wherein, the concentration of the terminal amino group of the PA66 resin is more than 50 meq/kg.
Preferably, in the composite material, the concentration of the terminal amino groups of the PA66 resin is more than 70 meq/kg.
Preferably, in the composite material, the diameter of the filaments on the short side of the flat glass fiber is 5-10 μm, and the average profile ratio is 2-6.
Preferably, in the above composite material, the flat glass fibers are present in the form of chopped fiber bundles having a length of 2 to 50 mm.
Preferably, in the composite material, the long-acting heat stabilizer is an aromatic amine heat stabilizer or a copper salt heat stabilizer.
Preferably, in the composite material, the colorant is one or more of linear quinacridone red, naphthone red, complex red, azo orange, azo complex yellow, perylene yellow, anthraquinone violet, anthraquinone blue, methine orange, phthalocyanine blue, azo orange and phthalocyanine green.
Preferably, in the composite material, the other additive is one or more of a light stabilizer, a lubricant, a mold release agent and an antistatic agent.
The invention also provides a preparation method of the high-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material, which comprises the following steps: the PA66 composite material is prepared by premixing PA66 resin, a long-acting heat stabilizer, a coloring agent and other additives in a certain proportion, plasticizing by a double-screw extruder, adding flat glass fibers in a side feeding manner in a certain proportion, and carrying out traction, cooling, grain cutting and drying.
The temperature of the double-screw extruder is 220-270 ℃, and the rotating speed of the screw is 300-500 r/min.
The invention also provides application of the high-temperature alcoholysis laser-resistant laser transmission reinforced PA66 composite material in automobile parts or laser welding. For example, radiator tanks for automobiles, automobile thermostats.
Advantageous effects
According to the invention, the high-end amino PA66 resin and the long-acting heat stabilizer are compounded, so that the PA66 composite material has excellent alcoholysis resistance, and meanwhile, the flat glass fiber and the colorant are compounded, so that the laser transmittance of the material is obviously improved, and the PA66 composite material has excellent initial mechanical properties.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The examples and comparative examples relate to the following starting materials, but are not limited to the following:
PA66 resin: high-end amino PA66, PA66 EP-158NH, Huafeng group, wherein the concentration of the end amino is 83 meq/kg;
conventional PA66 resin: PA66 EP-158, Huafeng group, with a terminal amino group concentration of 45 meq/kg;
flat glass fibers: ECS301HP-3-M4, Chongqing composite International, the diameter of the short-side monofilament is 6-8 μ M, the average profile ratio is 4.0, and the length is 3 mm;
round glass fiber: ECS10-3.0-568H, boulder group, monofilament diameter 10 um;
aromatic amine heat stabilizer: OKAFLEX EM, OKA-TEC;
copper salt composite heat stabilizer: H328F, broogman;
colorant 1: l308, Shenzhen Dingtai;
colorant 2: h554, basf;
colorant 3, R297, basf;
the colorant is a mixture of colorant 1, colorant 2 and colorant 3 in a weight ratio of 1:1: 1;
carbon black: m717, cabot;
carbodiimide (B): stabaxol P, rhine chemistry;
lubricant: it is commercially available.
The PA66 composite formulations in the examples and comparative examples are shown in table 1.
The preparation method of the PA66 composite material in the examples and the comparative examples comprises the following steps:
mixing the components except the glass fiber according to the weight parts in the table 1, adding the mixture into a double-screw extruder (the temperature of the double-screw extruder is 220-270 ℃, the rotating speed of a screw is 300-500 rpm) for plasticizing, adding the glass fiber in a side feeding manner according to a proportion, and obtaining the PA66 composite material after traction, cooling, grain cutting and drying.
The PA66 composites of the examples and comparative examples were subjected to the following performance tests, the results of which are shown in tables 2-4:
and (3) testing tensile strength: the samples were injection molded (injection molding conditions are conventional in the art) into 150mm by 10mm by 4mm dumbbell bars, and tensile strength was tested according to ISO 527 with a tensile speed of 5 mm/min.
And (3) testing the bending strength: the flexural modulus test was carried out according to ISO 178, the bending speed being 2 mm/min.
Notched impact strength test: the impact strength test was carried out according to ISO 179/1eA at a test temperature of 23 ℃.
Unnotched impact strength test: the impact strength test was carried out according to ISO 179/1eU at a test temperature of 23 ℃.
And (3) alcoholysis resistance test: adding ethylene glycol into a high-pressure reaction kettle: water 50:50 (volume ratio), the sample piece was immersed in the mixed solution, and then the reaction kettle was placed in an oven set at 130 ℃ or 135 ℃ for 1000 hours to test the above properties, and the surface of the sample piece was observed for cracks.
The laser light transmittance test method comprises the following steps: the test was carried out using LPKF TMG3, the thickness of the panels being 2 mm.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As can be seen from tables 2 to 4, comparative example 1 employs a conventional PA66 resin, and the PA66 composite material has significantly poorer performance after being soaked in a mixed solution of 50:50 ℃ ethylene glycol for 1000 hours than example 3, and the PA66 composite material in comparative example 1 has cracks on the surface after being soaked in a mixed solution of 50: 135 ℃ ethylene glycol for 1000 hours, while the composite material in example 3 has no cracks on the surface. The composite material in the comparative example 2 is obviously poorer in performance after being soaked in a mixed solution of 50:50 parts of ethylene glycol and water at 130 ℃ for 1000 hours than that in the example 3, and cracks are formed on the surface of the composite material in the comparative example 2 after being soaked in a mixed solution of 50:50 parts of ethylene glycol and water at 135 ℃ for 1000 hours. Comparative example 3 no long-acting heat stabilizer was added, the composite material was significantly inferior to example 3 in performance after being soaked in a mixed solution of 50:50 parts by weight of ethylene glycol at 130 ℃ for 1000 hours, and the composite material of comparative example 3 had cracks on the surface after being soaked in a mixed solution of 50:50 parts by weight of ethylene glycol at 135 ℃ for 1000 hours. Comparative example 4 used round glass fibers, example 3 used flat glass fibers, and the laser transmittance of the composite material in example 3 was significantly higher than that of comparative example 5. Comparative example 5 no colorant was added and the laser transmittance of the composite material of comparative example 5 was significantly lower than that of example 3. The PA66 composite material in the examples 1-5 has better initial mechanical properties such as tensile strength, elongation at break, notch impact strength and the like. Therefore, the high-end amino PA66 resin and the long-acting heat stabilizer are compounded, so that the PA66 composite material has excellent alcoholysis resistance, the surface of the material has no cracks after the material is subjected to alcoholysis for 1000 hours at 130 ℃ or 135 ℃, and the material can pass the test requirements of general automobile GMW15468 materials (PA66-GF30 material, the tensile strength is not less than 40MPa after the material is subjected to alcoholysis for 1000 hours at 130 ℃, the elongation at break is not less than 1 percent, and the unnotched impact strength is not less than 20kJ/m2) And flat glass fiber and colorant are compounded simultaneously, so that the laser transmittance of the PA66 composite material is obtainedThe PA66 composite material is remarkably improved, and has excellent initial mechanical properties.
Claims (10)
1. The PA66 composite material is characterized by comprising the following components in parts by weight:
wherein, the concentration of the terminal amino group of the PA66 resin is more than 50 meq/kg.
2. The composite material of claim 1, wherein the PA66 resin has an amino end group concentration > 70 meq/kg.
3. The composite material of claim 1, wherein the flat glass fiber short side filaments have a diameter of 5 to 10 μm and an average profile ratio of 2 to 6.
4. The composite material according to claim 3, wherein the flat glass fibers are present in the form of chopped fiber bundles having a length of 2-50 mm.
5. The composite material of claim 1, wherein the long-acting heat stabilizer is an aromatic amine heat stabilizer or a copper salt heat stabilizer.
6. The composite material of claim 1, wherein the colorant is one or more of linear quinacridone red, naphthone red, complex red, azo orange, azo complex yellow, perylene yellow, anthraquinone violet, anthraquinone blue, methine orange, phthalocyanine blue, azo orange, and phthalocyanine green.
7. The composite material of claim 1, wherein the other additive is one or more of a light stabilizer, a lubricant, a mold release agent, and an antistatic agent.
8. A method of making the composite material of claim 1, comprising the steps of:
the PA66 composite material is prepared by premixing PA66 resin, a long-acting heat stabilizer, a coloring agent and other additives in a certain proportion, plasticizing by a double-screw extruder, adding flat glass fibers in a side feeding manner in a certain proportion, and carrying out traction, cooling, grain cutting and drying.
9. The method of claim 8, wherein the twin screw extruder temperature is 220 to 270 ℃ and the screw rotation speed is 300 to 500 rpm.
10. Use of the composite material according to claim 1 in automotive parts or in laser welding.
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| CN115819967A (en) * | 2022-12-12 | 2023-03-21 | 苏州旭光聚合物有限公司 | Polyamide composite material and preparation method and application thereof |
| CN115926442A (en) * | 2022-10-25 | 2023-04-07 | 汉特工程塑料（浙江）有限公司 | Green environment-friendly weldable hydrolysis-resistant nylon composite material and preparation method thereof |
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