CN109666291B - High-rigidity low-water-absorption nylon 6 composite material - Google Patents
High-rigidity low-water-absorption nylon 6 composite material Download PDFInfo
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a high-rigidity low-water-absorption nylon 6 composite material which is characterized in that: the feed comprises the following raw materials in parts by weight: 120 parts of nylon 6100-containing material, 10-30 parts of barrier nylon, 3-5 parts of nano montmorillonite, 30-50 parts of alkali-free glass fiber, 1-2 parts of silane coupling agent solution, 3-5 parts of nano layered silicate, 5-10 parts of acrylonitrile-butadiene-styrene-terpolymer, 1-10 parts of polytetrafluoroethylene, 3-5 parts of toughening agent, 1-5 parts of compatilizer, 0.1-1 part of heat-resistant agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The invention still keeps better rigidity under water environment.
Description
Technical Field
The invention relates to the technical field of nylon modification, in particular to a high-rigidity low-water-absorption nylon 6 composite material.
Background
Polyamide fiber is commonly called nylon, called PA for short, thermoplastic resin containing repeated amide groups on a molecular main chain is generally called polyamide 6 (polycaprolactam) which is one of the most common polyamide fibers, also called nylon 6, the melting point of the polyamide fiber is lower, the process temperature range is wider, the impact resistance and the anti-solubility are better than those of nylon 66 plastic, the polyamide fiber is widely used in the industrial fields of petrochemical industry, national defense industry, machinery, textile and the like, and is an important engineering plastic, but the nylon absorbs water greatly, so that the rigidity of the material is greatly reduced, the defect exists in the aspect of mechanical strength, the moisture absorption rate is high, the forming shrinkage rate is larger, the dimensional stability of the product is influenced, and some nylon products which are in contact with water, such as internal parts of bathrooms and irrigation housing products, the water absorption is large after the nylon fiber is in contact with water for a long time, the rigidity of the material is reduced, and the nylon fiber is easy to crack.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a nylon 6 composite material with high rigidity and low water absorption, which has low water absorption rate and good rigidity retention rate.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that: a high-rigidity low-water-absorption nylon 6 composite material comprises the following raw materials in parts by weight: 120 parts of nylon 6100-containing material, 10-30 parts of barrier nylon, 3-5 parts of nano montmorillonite, 30-50 parts of alkali-free glass fiber, 1-2 parts of silane coupling agent solution, 3-5 parts of nano layered silicate, 5-10 parts of acrylonitrile-butadiene-styrene-terpolymer, 1-10 parts of polytetrafluoroethylene, 3-5 parts of toughening agent, 1-5 parts of compatilizer, 0.1-1 part of heat-resistant agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant.
The silane coupling agent solution is prepared from gamma-aminopropyltriethoxysilane and methanol or ethanol in a mass ratio of 1: 3;
the compatilizer is an ethylene elastomer which is difunctional by maleic anhydride and acrylate;
the antioxidant is one or more of hindered phenols, phosphites and sulfur-containing antioxidants;
the toughening agent is a maleic anhydride grafted ethylene-octene copolymer;
the lubricant is silicone master batch.
Further, the barrier nylon is poly m-xylylene adipamide. MXD6 (MXD 6) is a crystalline aromatic nylon and a high-barrier nylon material, so compared with other nylons, MXD6 has the advantages of high strength, high rigidity, high thermal deformation temperature and small thermal expansion coefficient; the glass fiber reinforced plastic has the advantages of good dimensional stability, low water absorption, small dimensional change after water absorption, small mechanical strength change, greatly improved mechanical properties after glass fiber reinforcement, small influence of temperature and humidity on the mechanical properties, and capability of keeping high strength and rigidity in a wide temperature or/and humidity range. The barrier property of MXD6 is not affected by temperature and humidity, so that the MXD6 is especially suitable for high temperature and humid occasions, and still maintains excellent high strength, high modulus, heat resistance and high barrier property.
Further, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
Furthermore, the glass fiber is chopped glass fiber with monofilament diameter of 10 μm.
Furthermore, the fineness of the nano montmorillonite is 300-1000 meshes, and the specific surface area is 50-60 m2/g。
Furthermore, the fineness of the nano montmorillonite is 500 meshes, and the specific surface area is 55m2/g。
Furthermore, the heat-resistant agent is one or more of an inorganic phosphate heat stabilizer, an amine heat stabilizer and a copper salt heat stabilizer, the heat-resistant agents can be purchased from the market, for example, the inorganic phosphate heat stabilizer is Bulugman H10 produced by Germany Bulugman chemical company, the amine heat stabilizer is Bulugman H20, and the copper salt heat stabilizer is Bulugman HS-03.
The invention has the beneficial effects that: the poly (m-xylylene adipamide) is a crystalline aromatic nylon, has the effect of high barrier property, has the characteristics of high strength, high rigidity, high thermal deformation temperature, small thermal expansion coefficient, good dimensional stability, low water absorption, small dimensional change after water absorption and small mechanical strength change, and on one hand, the poly (m-xylylene adipamide) with high barrier property, polytetrafluoroethylene with water approaching prevention and nylon 6 are blended and compounded, and the poly (m-xylylene adipamide) and the polytetrafluoroethylene synergistically enhance the barrier property of the nylon 6, so that the water absorption of the nylon 6 is reduced, and the poly (m-xylylene adipamide) and the polytetrafluoroethylene have high-temperature resistance, so that the temperature resistance of the composite material is improved; on the other hand, the invention is compounded with inorganic materials such as nano montmorillonite, alkali-free glass fiber and nano layered silicate, the inorganic materials reduce the water absorption rate of the nylon 6, reduce the water absorption capacity, improve the adverse effect of the nylon 6 caused by water absorption, wherein, the nano montmorillonite is used as a nucleating agent, can improve the crystallinity of nylon 6, reduce the amorphous area, reduce the water absorption of the nylon 6, shield the diffusion and the penetration of water molecules by the nano layered silicate, the alkali-free glass fiber has extremely low water absorption and higher rigidity, and after the glass fiber reinforces the nylon 6 and the poly m-xylylene adipamide, can greatly improve the mechanical property, so that the mechanical property of the composite material is less influenced by temperature and humidity, can maintain high strength and rigidity in a wide temperature or/and humidity range, and has better rigidity even in water environment.
Detailed Description
Example one
A high-rigidity low-water-absorption nylon 6 composite material comprises the following raw materials in parts by weight: nylon 6100 parts, poly m-xylylene adipamide 10 parts, nano montmorillonite 3 parts, alkali-free glass fiber 30 parts, silane coupling agent solution 1 part, nano layered silicate 3 parts, acrylonitrile-butadiene-styrene-terpolymer 5 parts, Polytetrafluoroethylene (PTFE)1 part, maleic anhydride grafted ethylene-octene copolymer 3 parts, compatibilizer 1 part, tris (2, 4-di-tert-butylphenyl) phosphite 0.1 part, silicone master batch 0.1 part, and H10 0.1 part.
The silane coupling agent solution is prepared from gamma-aminopropyltriethoxysilane and methanol or ethanol in a mass ratio of 1: 3;
the compatilizer is ethylene elastomer which is difunctional by maleic anhydride and acrylic ester.
The glass fiber is chopped glass fiber with monofilament diameter of 10 mu m;
the fineness of the nano montmorillonite is 300 meshes, and the specific surface area is 50m2/g。
The high-rigidity low-water-absorption nylon 6 composite material of the embodiment is prepared according to the following method:
step 1, uniformly mixing the nano layered silicate, the nano montmorillonite and the alkali-free glass fiber by adopting a silane coupling agent solution in a high-speed stirrer for 2-3min to obtain an auxiliary agent mixture.
And 2, feeding the nylon 6 subjected to pre-drying treatment, poly m-xylylene adipamide, acrylonitrile-butadiene-styrene-terpolymer, polytetrafluoroethylene, maleic anhydride grafted ethylene-octene copolymer, compatilizer, tris (2, 4-di-tert-butylphenyl) phosphite, silicone master batch and H10 into a double-screw extruder to be melted and blended uniformly, wherein the melting temperature is 230-300 ℃.
And 3, feeding the auxiliary agent mixture obtained in the step 1 into a double-screw extruder from a feeding machine positioned on the side edge of the double-screw extruder, extruding, cooling and granulating.
The extrusion temperature of the twin-screw extruder is divided into ten zones, the temperature of the first zone is 230 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 300 ℃, the temperature of the fifth zone is 300 ℃, the temperature of the sixth zone is 300 ℃, the temperature of the seventh zone is 290 ℃, the temperature of the eighth zone is 290 ℃, the temperature of the ninth zone is 290 ℃, the temperature of the tenth zone is 300 ℃ and the rotation speed of the screws is 300 revolutions.
Example two
A high-rigidity low-water-absorption nylon 6 composite material comprises the following raw materials in parts by weight: the composite material comprises, by weight, 6110 parts of nylon, 20 parts of poly (m-xylylene adipamide), 4 parts of nano-montmorillonite, 40 parts of alkali-free glass fiber, 1.5 parts of a silane coupling agent solution, 4 parts of nano-layered silicate, 8 parts of acrylonitrile-butadiene-styrene-terpolymer, 5 parts of Polytetrafluoroethylene (PTFE), 4 parts of maleic anhydride grafted ethylene-octene copolymer, 3 parts of a compatilizer, 0.5 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.5 part of silicone master batch and 0.5 part of H20.
The silane coupling agent solution is prepared from gamma-aminopropyltriethoxysilane and methanol or ethanol in a mass ratio of 1:3, in water.
The compatilizer is ethylene elastomer which is difunctional by maleic anhydride and acrylic ester.
The alkali-free glass fiber is a chopped glass fiber with the monofilament diameter of 10 mu m.
The fineness of the nano montmorillonite is 500 meshes, and the specific surface area is 55m2/g。
This example was prepared according to the method steps of example 1.
EXAMPLE III
A high-rigidity low-water-absorption nylon 6 composite material comprises the following raw materials in parts by weight: the modified polyurethane resin is prepared from the following raw materials, by weight, 6120 parts of nylon, 30 parts of poly (m-xylylene adipamide), 5 parts of nano-montmorillonite, 50 parts of alkali-free glass fiber, 2 parts of a silane coupling agent solution, 5 parts of nano-layered silicate, 10 parts of acrylonitrile-butadiene-styrene-terpolymer, 10 parts of Polytetrafluoroethylene (PTFE), 5 parts of maleic anhydride grafted ethylene-octene copolymer, 5 parts of a compatilizer, 1 part of tris (2, 4-di-tert-butylphenyl) phosphite, 1 part of silicone master batch and 1 part of HS-03.
The silane coupling agent solution is prepared from gamma-aminopropyltriethoxysilane and methanol or ethanol in a mass ratio of 1: 3;
the compatilizer is ethylene elastomer which is difunctional by maleic anhydride and acrylic ester.
The glass fiber is chopped glass fiber with monofilament diameter of 10 mu m.
The fineness of the nano montmorillonite is 1000 meshes, and the specific surface area is 60m2/g。
This example was prepared according to the method steps of example 1.
Comparative examples
A nylon 6 composite material comprises the following raw materials in parts by weight: 6100 parts of nylon, 5 parts of acrylonitrile-butadiene-styrene-terpolymer, 1 part of compatilizer, 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1 part of silicone master batch and 0.1 part of H10.
The compatilizer is ethylene elastomer which is difunctional by maleic anhydride and acrylic ester.
The nylon 6 composite of this example was prepared as follows:
step 1, feeding the nylon 6 subjected to pre-drying treatment, the acrylonitrile-butadiene-styrene-terpolymer, the compatilizer, the tris (2, 4-di-tert-butylphenyl) phosphite and the silicone master batch into a double-screw extruder to be melted, blended uniformly, extruded, cooled and cut into granules, wherein the melting temperature is 230-300 ℃.
The extrusion temperature of the twin-screw extruder is divided into ten zones, the temperature of the first zone is 230 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 300 ℃, the temperature of the fifth zone is 300 ℃, the temperature of the sixth zone is 300 ℃, the temperature of the seventh zone is 290 ℃, the temperature of the eighth zone is 290 ℃, the temperature of the ninth zone is 290 ℃, the temperature of the tenth zone is 300 ℃ and the rotation speed of the screws is 300 revolutions.
And (3) performance testing:
(1) tensile strength, elongation at break: testing was performed according to standard IS 0527.
(2) Flexural modulus: the test was carried out according to standard IS 0178.
(3) Notched izod impact strength: the test was performed according to IS0180 (notch type IS type A notch).
The performance test results are as follows:
as can be seen from the test results in the table above, the high-rigidity low-water-absorption nylon 6 composite material prepared by the invention has the characteristics of high strength, high rigidity and low water absorption, and shows good mechanical properties. Therefore, the poly-m-xylylene adipamide has the effect of high barrier property, has the characteristics of high strength, high rigidity, high thermal deformation temperature, small thermal expansion coefficient, good dimensional stability, low water absorption, small dimensional change after water absorption and small mechanical strength change, on one hand, the poly-m-xylylene adipamide with high barrier property, the polytetrafluoroethylene for preventing water from approaching and the nylon 6 are blended and compounded, and the two synergistically enhance the barrier property of the nylon 6, so that the water absorption of the nylon 6 is reduced, and the poly-m-xylylene adipamide and the polytetrafluoroethylene both have high temperature resistance, so that the temperature resistance of the composite material is improved. On the other hand, the inorganic material of the invention reduces the water absorption rate of nylon 6, reduces the water absorption capacity, and improves the adverse effect of nylon 6 caused by water absorption, wherein, the nano montmorillonite is used as a nucleating agent, can improve the crystallinity of nylon 6, enables the amorphous area to be small, reduces the water absorption of nylon 6, can shield the diffusion and permeation of water molecules by nano layered silicate, and the alkali-free glass fiber has extremely low water absorption and higher rigidity, and can greatly improve the mechanical property after the glass fiber reinforces the nylon 6 and the poly-m-xylylene adipamide, so that the mechanical property of the composite material is less influenced by temperature and humidity, can keep high strength and rigidity in a wide temperature or/and humidity range, and can have better rigidity even in a water environment.
The invention and its embodiments have been described above, without this being limitative. In conclusion, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The high-rigidity low-water-absorption nylon 6 composite material is characterized in that: the feed comprises the following raw materials in parts by weight: 120 parts of nylon 6100-containing material, 10-30 parts of barrier nylon, 3-5 parts of nano montmorillonite, 30-50 parts of alkali-free glass fiber, 1-2 parts of silane coupling agent solution, 3-5 parts of nano layered silicate, 5-10 parts of acrylonitrile-butadiene-styrene-terpolymer, 1-10 parts of polytetrafluoroethylene, 3-5 parts of toughening agent, 1-5 parts of compatilizer, 0.1-1 part of heat-resistant agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant;
the barrier nylon is poly m-xylylene adipamide;
the silane coupling agent solution is a solution prepared from gamma-aminopropyltriethoxysilane and methanol or ethanol in a mass ratio of 1: 3;
the compatilizer is an ethylene elastomer which is difunctional by maleic anhydride and acrylate;
the antioxidant is one or more of hindered phenols, phosphites and sulfur-containing antioxidants;
the toughening agent is a maleic anhydride grafted ethylene-octene copolymer;
the lubricant is silicone master batch.
2. The high-rigidity low-water-absorption nylon 6 composite material as claimed in claim 1, wherein: the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
3. The high-rigidity low-water-absorption nylon 6 composite material as claimed in claim 1, wherein: the glass fiber is chopped glass fiber with monofilament diameter of 10 mu m.
4. The high-rigidity low-water-absorption nylon 6 composite material as claimed in claim 3, wherein: the fineness of the nano montmorillonite is 300-1000 meshes, and the specific surface area is 50-60 m2/g。
5. The high-rigidity low-water-absorption nylon 6 composite material as claimed in claim 4, wherein: the fineness of the nano montmorillonite is 500 meshes, and the specific surface area is 55m2/g。
6. The high-rigidity low-water-absorption nylon 6 composite material according to any one of claims 1 to 5, wherein: the heat-resistant agent is one or more of an inorganic phosphate heat stabilizer, an amine heat stabilizer and a copper salt heat stabilizer.
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| CN110643173A (en) * | 2019-09-25 | 2020-01-03 | 广东格瑞新材料股份有限公司 | High-rigidity nylon composite material and preparation method thereof |
| CN112745663A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | High-strength nylon 6 material and preparation method thereof |
| CN113214642A (en) * | 2021-05-14 | 2021-08-06 | 金旸（厦门）新材料科技有限公司 | Stable-size high-glow-wire halogen-free flame-retardant polyamide composite material and preparation method thereof |
| CN113430668B (en) * | 2021-06-28 | 2023-04-11 | 安踏（中国）有限公司 | Ice-feeling quick-drying fiber and preparation method thereof, and ice-feeling quick-drying fabric and preparation method thereof |
| CN113429779A (en) * | 2021-07-12 | 2021-09-24 | 横店集团得邦工程塑料有限公司 | Reinforced and toughened blending modified PA6/MXD6 composite material and preparation method thereof |
| CN114276674A (en) * | 2021-11-23 | 2022-04-05 | 常州威材新材料科技有限公司 | Nano montmorillonite reinforced PA6 polyolefin elastomer high-toughness alloy and preparation method thereof |
| CN116041695A (en) * | 2022-04-26 | 2023-05-02 | 湖南世博瑞高分子新材料有限公司 | Copolymerization barrier nylon and continuous synthesis method and application thereof |
| CN116875045A (en) * | 2023-05-12 | 2023-10-13 | 江苏金发科技新材料有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
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