CN110684351A - Wear-resistant nylon composite engineering plastic for railway tracks and preparation method thereof - Google Patents
Wear-resistant nylon composite engineering plastic for railway tracks and preparation method thereof Download PDFInfo
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract
The invention belongs to the field of engineering plastic materials, and relates to wear-resistant nylon composite engineering plastic for a railway track and a preparation method thereof.
Description
Technical Field
The invention relates to the field of engineering plastic materials, in particular to wear-resistant nylon composite engineering plastic for railway tracks and a preparation method thereof.
Background
The nylon resin, namely polyamide, has excellent mechanical strength, wear resistance, self-lubricating property, corrosion resistance and better processing and forming performance, and is a basic resin with the largest output, the largest variety, the widest application and excellent comprehensive performance in five general engineering plastics at present. The nylon is used in the field of rail transit fasteners, can effectively solve the problems of shaking, high noise and the like of a locomotive, can ensure the stability of the wheelbase, reduces the maintenance frequency, has good shock resistance, and is very important for ensuring the stable operation of the railway locomotive. With the continuous acceleration of railway locomotives, the corresponding performance requirements on railway products are higher and higher, and especially the requirements on the railway products in perennial low-temperature cold freezing areas are extremely strict. The fasteners (including nylon sleeves, gauge blocks and baffle seats) on ordinary railways, high-speed rails and subways at home and abroad use nylon as a main raw material, and have poor low-temperature toughness, low wear resistance and high production cost.
Glass fiber (original English name: glass fiber) is an inorganic non-metallic material with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittleness and poor wear resistance. The hair-care fiber is made of seven kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding, weaving and the like, wherein the diameter of each monofilament ranges from several micrometers to twenty micrometers, the monofilament is equivalent to 1/20-1/5 of one hair, and each bundle of fiber precursor consists of hundreds of even thousands of monofilaments. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and other various fields of the national economy.
The glass fiber is a common additive material applied to fiber reinforced nylon materials, has the advantages of low cost, no combustion, heat resistance, good chemical corrosion resistance, high tensile strength and impact strength, small elongation at break and the like, and is widely applied to the high and new technical fields of traditional industry, agriculture, building industry, electronics, communication, aviation, aerospace, weapons, naval vessels and the like at present. Therefore, the modified glass fiber/nylon composite material is used for replacing the glass fiber/nylon composite material, which is a necessary trend.
Chinese patent application No. 201610960086.1, research on long glass fiber-nylon composite material, discloses a long glass fiber-nylon composite material and a preparation method thereof, wherein the preparation method comprises the following steps of adding 100 parts of nylon resin, 20 ~ 30 parts of long glass fiber, 3 ~ 10 parts of toughening agent, 0.5 ~ 2 part of flowing agent, 1 ~ 2 parts of antioxidant and 2 ~ 4.5.5 parts of heat stabilizer into a stirrer, stirring to form a uniform first mixture, drying the first mixture for 4 ~ 6 hours at 110 ~ 120 ℃, adding the first mixture into a double-screw extruder, controlling the rotation speed of a screw and the temperature of the double-screw extruder, adding 20-30 parts of long glass fiber at a screw fiber adding hole of the double-screw extruder, melting the long glass fiber and the first mixture under the conditions that the rotation speed of the screw is 35-48Hz and the temperature is 265-310 ℃, and uniformly mixing and extruding to obtain a long nylon resin composition.
Chinese patent No. 200510026733.3, high surface finish glass fiber reinforced nylon composite and its preparation method, discloses a high surface finish glass fiber reinforced nylon composite and its preparation method, the preparation method is that nylon 45wt% ~ 85wt%, surface modifier 0.5wt% ~ 8wt%, antioxidant 0.4wt% ~ 2wt% are dry mixed in a high speed mixer, then mixed with 10wt% ~ 40wt% glass fiber 6 ~ 17 micron diameter in a double screw extruder, and then melted, extruded and granulated.
Chinese patent No. 201910469239.6, entitled "A conductive glass fiber and conductive glass fiber reinforced nylon Material and its preparation method", discloses a conductive glass fiber and conductive glass fiber reinforced nylon Material and its preparation method. The conductive glass fiber reinforced nylon material contains nylon, conductive glass fiber, an antioxidant and a lubricant, and the conductive glass fiber is prepared by the following method: s1, uniformly mixing glass fibers and aniline monomers in a first acidic aqueous solution under the ultrasonic oscillation condition, wherein the mass ratio of the aniline monomers to the glass fibers is 1: 1-1: 5, and thus obtaining a glass fiber-aniline composite solution; s2, dissolving an initiator in a second acidic aqueous solution under the ultrasonic oscillation condition to obtain an initiator solution; s3, mixing the glass fiber-aniline composite solution and the initiator solution uniformly under the ultrasonic oscillation condition, then reacting for 1-24 h at the temperature of-5-25 ℃, carrying out solid-liquid separation, and drying the obtained solid product to obtain the conductive glass fiber.
However, the glass fiber reinforced nylon 66 of the glass fiber composite nylon material prepared by the method has the obvious defect that the glass fiber is easily exposed on the surface of a product due to the fact that the two-phase interfaces of the glass fiber and the nylon 66 are not easy to be well combined, so that the surface of the product is rough and has a flower, and the application of the raw material to the product with high requirements on surface smoothness or wear resistance is limited.
The polyoxyethylene wax containing carbonyl functional groups disclosed in the patent of invention 'high surface smoothness glass fiber reinforced nylon composite material and preparation method thereof' can be used as a modifier for the surface smoothness and glossiness of glass fiber reinforced polyester nylon, and glass fibers exposed on the surface of a product can be well covered by the modifier, so that the purpose of improving the surface of the glass fiber reinforced nylon product and enabling the product to have high smoothness and good glossiness is achieved. However, this only serves as a covering and does not essentially solve the problem, affecting wear resistance and service life.
Disclosure of Invention
Aiming at the problem that the abrasion resistance and the service life are affected due to the fiber exposure phenomenon of the conventional glass fiber/nylon 66 composite material, the invention provides the abrasion-resistant nylon composite engineering plastic for the railway track and the preparation method thereof, so that the fiber exposure phenomenon of the glass fiber/nylon 66 composite material is obviously improved, the abrasion resistance is improved, and the service life is prolonged.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of wear-resistant nylon composite engineering plastic for railway tracks comprises the following steps:
(1) uniformly dispersing carboxylated graphene in an organic solvent to obtain a graphene liquid;
(2) mixing graphene liquid, 5-amino isophthalic acid and triphenyl phosphite, heating to 90 ~ 120 ℃ under the protection of nitrogen or inert gas to react for 0.6 ~ 2 hours, heating to 140 ~ 160 ℃, adding glass fiber, continuing to react for 0.6 ~ 2 hours, stopping introducing inert gas or nitrogen, adding acetic acid, vacuumizing, reacting for 0.3 ~ 1 hours under vacuum to obtain a pre-product, and placing the pre-product in a vacuum drying oven for solid phase polymerization for 10 ~ 18 hours to obtain the hyperbranched polyamide/glass fiber composite material, wherein the molar ratio of carboxylated graphene, 5-amino isophthalic acid, triphenyl phosphite, glass fiber and acetic acid is 0.1 ~ 0.5:1 ~ 3:2 ~ 6:0.5-0.8:10 ~ 15;
(3) the hyperbranched polyamide/glass fiber composite material, nylon 66, a toughening agent, an antioxidant and a flame retardant are mixed, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Aiming at the problem that the abrasion resistance and the service life of the glass fiber/nylon 66 composite material of the shock-absorbing fastening material used in the railway track are affected by the exposure of the glass fiber at present, the graphene rich in carboxyl is dispersed in a hyperbranched polyamide precursor in advance, the graphene is easy to reside in a cavity inside the hyperbranched polyamide due to a nano structure, the carboxyl contained in the graphene is easy to combine with Si-OH in the glass fiber, and the graphene rich in carboxyl is similar to a rivet so as to firmly combine the glass fiber with the hyperbranched polyamide; the combination of the two groups improves the compatibility, obviously improves the fiber exposure phenomenon of the glass fiber/nylon 66 composite material, improves the abrasion resistance and prolongs the service life.
In step (2), the monomer 5-amino isophthalic acid is light brown powder with molecular formula C8H7NO4Relative molecular mass 181.15; a condensing agent triphenyl phosphite with the molecular formula of C18H15O3P, relative molecular mass 310.29; catalyst acetic acid with molecular formula of CH3COOH, relative molecular mass 60.05.
Wherein, the invention needs to prepare hyperbranched polyamide first. The hyperbranched polyamide is a hyperbranched polymer. The hyperbranched polymer is a homolog of a dendritic macromolecule, and the structure of the hyperbranched polymer starts from a central core and is gradually extended by a branched monomer ABx, or the hyperbranched polymer is formed by connecting the central core, a plurality of layers of branched units and peripheral groups through chemical bonds. Due to the unique branched molecular structure, the hyperbranched polymer has no entanglement among molecules and contains a large number of end groups, so that the hyperbranched polymer shows special properties which are not possessed by a plurality of linear polymers, such as high solubility, low viscosity, high chemical reaction activity and the like, and the properties enable the hyperbranched polymer to show attractive application prospects in polymer blending, films, high molecular liquid crystals, drug release systems and other aspects. Because the hyperbranched polymer has the unique performance, the glass fiber is stably doped in the hyperbranched polymer through the graphene, so that the exposure phenomenon of the glass fiber is changed.
Preferably, in step (1), the organic solvent is acetone. The purpose of the acetone is to uniformly disperse the carboxylated graphene in the hyperbranched polyamide precursor, so that the graphene can more stably and firmly combine the glass fiber and the hyperbranched polyamide.
Introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask, mixing, placing the three-neck flask into an oil bath kettle, starting magnetic stirring, introducing nitrogen or inert gas to ensure that a reaction system is under the protection of nitrogen or inert gas, heating, reacting for 0.6 ~ 2 hours when the temperature is 90 ~ 120 ℃, heating, adding glass fiber for mixing when the temperature is 140 ~ 160 ℃, continuing to react for 0.6 ~ 2 hours, stopping introducing inert gas or nitrogen, adding catalyst acetic acid, vacuumizing, reacting for 0.3 ~ 1 hours under vacuum to obtain a pre-product, taking out the product, and placing the pre-product in a vacuum drying oven for solid phase polymerization for 10 ~ 18 hours to obtain the hyperbranched polyamide/glass fiber composite material;
the vacuum drying box type number used in the present invention may be DZG-6021.
In order to improve the compressive strength of the prepared wear-resistant nylon composite engineering plastic for the railway track, it is preferable that the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid in the step (2) is 0.2 ~ 0.4:1.5 ~ 2.5.5: 4 ~ 5:0.6-0.7:12 ~ 14.
Preferably, in the step (2), the inert gas is nitrogen or argon; preferably, the inert gas is nitrogen.
Preferably, in the step (2), the graphene liquid, the 5-amino isophthalic acid and the triphenyl phosphite are heated to 100 ℃ for reaction for 1 hour under the protection of nitrogen or inert gas, then heated to 145 ℃, the glass fiber is added, and the reaction is continued for 1 hour.
Preferably, in step (2), the reaction is carried out under vacuum for 0.8 hour.
Preferably, in step (2), the pre-product is subjected to solid phase polymerization in a vacuum oven for 15 hours.
Preferably, in the step (3), a high-speed mixer is adopted as a machine for mixing the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant.
In order to improve the compressive strength of the prepared wear-resistant nylon composite engineering plastic for the railway track, preferably, in the step (3), the weight ratio of the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant is 8 ~ 35:50 ~ 80:0.1 ~ 4:0.1 ~ 4:0.1 ~ 3.
Preferably, in the step (3), the weight ratio of the hyperbranched polyamide/glass fiber composite material to the nylon 66 to the toughening agent to the antioxidant to the flame retardant is 10 ~ 25:60 ~ 70:0.2 ~ 0.5.5: 0.3 ~ 0.7.7: 0.8 ~ 2.
Preferably, the toughening agent comprises at least one of the following components: octene copolymers, ethylene butene copolymers, ethylene propylene copolymers, and styrene butadiene copolymers.
Preferably, the antioxidant comprises at least one of the following components: 4, 4-thiobis (6-tert-butyl-3-methylphenol), phosphite triester (2, 4-di-tert-butylphenyl), pentaerythritol tetrakis (. beta.) (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl (. beta.) (3, 5-tertiary-butyl-4-hydroxyphenyl) propionate, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Preferably, the flame retardant comprises at least one of the following components: diethyl aluminum phosphate, aluminum hypophosphite and iron hypophosphite.
The invention aims to solve the second technical problem of providing the wear-resistant nylon composite engineering plastic for the railway track.
The wear-resistant nylon composite engineering plastic for the railway track is prepared by the preparation method of the wear-resistant nylon composite engineering plastic for the railway track.
Compared with the prior art, the wear-resistant nylon composite engineering plastic for the railway track and the preparation method thereof have the outstanding characteristics and excellent effects that:
1. the method comprises the steps of dispersing graphene rich in carboxyl in a hyperbranched polyamide precursor in advance, and firmly combining glass fiber with hyperbranched polyamide through the graphene rich in carboxyl similar to a rivet; the combination of the two groups improves the compatibility, thereby obviously improving the fiber exposure phenomenon of the glass fiber/nylon 66 composite material.
2. The wear-resistant nylon composite engineering plastic for the railway track, which is prepared by the invention, has the advantages of high compression strength, good wearability and long service life.
3. The invention adopts a one-step method to prepare the hyperbranched polyamide/glass fiber composite material, and has simple and convenient operation and simple process.
4. The wear-resistant nylon composite engineering plastic for the railway track prepared by the method has the advantages of small investment, low cost, no environmental pollution, high yield and obvious market application value.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1 preparation of wear-resistant Nylon composite engineering Plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.3:2:4.5:0.6: 13;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 18:65:0.3:0.6:1 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Example 2 preparation of wear-resistant nylon composite engineering plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.2: 2.5:4:0.7:12;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 18:65:0.3:0.6:1 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Example 3 preparation of wear-resistant Nylon composite engineering Plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.5:1: 6:0.5: 15;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 18:65:0.3:0.6:1 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Example 4 preparation of wear-resistant Nylon composite engineering Plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.3:2:4.5:0.6: 13;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 10:70:0.2:0.7:0.8 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Example 5 preparation of wear-resistant Nylon composite engineering Plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.3:2:4.5:0.6: 13;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 25:60: 0.2:0.7:0.8 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Example 6 preparation of wear-resistant Nylon composite engineering Plastic for railway track
(1) Uniformly dispersing carboxylated graphene in an organic solvent acetone to obtain a graphene liquid; in the graphene liquid, the concentration of the carboxylated graphene is 0.5 mg/mL;
(2) introducing graphene liquid, monomer 5-amino isophthalic acid and condensation agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material; wherein the molar ratio of the carboxylated graphene, the 5-amino isophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.3:2:4.5:0.6: 13;
(3) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 35:50: 0.2:0.7:0.8 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Comparative example 1:
(1) introducing monomer 5-amino isophthalic acid and condensing agent triphenyl phosphite into a three-neck flask for mixing, and placing the three-neck flask into an oil bath pan; and magnetic stirring was turned on. Then introducing nitrogen gas to enable the reaction system to be under the protection of nitrogen gas, heating, reacting for 1 hour when the temperature is 100 ℃, heating to raise the temperature, adding glass fiber to mix when the temperature is 145 ℃, continuing to react for 1 hour, stopping introducing the nitrogen gas, adding a catalyst acetic acid, vacuumizing, and reacting for 0.7 hour under vacuum to obtain a pre-product; taking out the product, and placing the pre-product in a DZG-6021 type vacuum drying oven for solid phase polymerization for 15 hours to obtain the hyperbranched polyamide/glass fiber composite material;
wherein the molar ratio of 5-amino isophthalic acid, triphenyl phosphite, glass fiber and acetic acid is 2:4.5:0.6: 13;
(2) the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant are put into a high-speed mixer according to the weight ratio of 18:65:0.3:0.6:1 for mixing, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
Test example:
the abrasion-resistant nylon composite engineering plastics for railway rails prepared in examples 1 to 6 and comparative example 1 were tested for compressive strength and abrasion resistance.
The specific method is as follows:
1. compressive strength: referring to GBT 1041-.
2. Wear resistance: the nylon composite engineering plastics obtained in the examples 1-6 and the comparative example 1 are pressed into a plate in a hot press, a test sample piece with the thickness of 10cm multiplied by 10cm is cut, the surface of the test sample is rubbed by 100-mesh sand paper under the action of 200N for 50 times, and the condition that the fiber is exposed on the friction surface is observed.
The test results are shown in table 1.
TABLE 1
| Test sample | Compressive Strength (MPa) | Open fiber condition |
| Example 1 | 105 | Smooth surface and no fiber |
| Example 2 | 97 | Smooth surface and no fiber |
| Example 3 | 94 | Smooth surface and no fiber |
| Example 4 | 101 | Smooth surface and no fiber |
| Example 5 | 100 | Smooth surface and no fiber |
| Example 6 | 96 | Smooth surface and no fiber |
| Comparative example 1 | 49 | Surface scratch and fiber exposure |
As can be seen from Table 1, the nylon composite engineering plastic prepared in comparative example 1 has significantly poor compressive strength and wear resistance, because the combination of the glass fiber and the hyperbranched polyamide is not firm due to the lack of the rivet function of the carboxylated graphene, and although the compatibility and dispersibility with nylon can be effectively solved, the combination of the glass fiber and the hyperbranched polyamide is not firm, so that the fiber is easily exposed during molding and use, and the wear resistance is low.
Claims (10)
1. A preparation method of wear-resistant nylon composite engineering plastic for railway tracks is characterized by comprising the following steps:
(1) uniformly dispersing carboxylated graphene in an organic solvent to obtain a graphene liquid;
(2) mixing graphene liquid, 5-amino isophthalic acid and triphenyl phosphite, heating to 90 ~ 120 ℃ under the protection of nitrogen or inert gas to react for 0.6 ~ 2 hours, heating to 140 ~ 160 ℃, adding glass fiber, continuing to react for 0.6 ~ 2 hours, stopping introducing inert gas or nitrogen, adding acetic acid, vacuumizing, reacting for 0.3 ~ 1 hours under vacuum to obtain a pre-product, and placing the pre-product in a vacuum drying oven for solid phase polymerization for 10 ~ 18 hours to obtain the hyperbranched polyamide/glass fiber composite material, wherein the molar ratio of carboxylated graphene, 5-amino isophthalic acid, triphenyl phosphite, glass fiber and acetic acid is 0.1 ~ 0.5:1 ~ 3:2 ~ 6:0.5-0.8:10 ~ 15;
(3) the hyperbranched polyamide/glass fiber composite material, nylon 66, a toughening agent, an antioxidant and a flame retardant are mixed, and then are extruded and granulated by a double-screw extruder to obtain the wear-resistant nylon composite engineering plastic for the railway track.
2. The method for preparing the wear-resistant nylon composite engineering plastic for the railway tracks as claimed in claim 1, wherein in the step (1), the organic solvent is acetone.
3. The method for preparing the wear-resistant nylon composite engineering plastic for the railway tracks as claimed in claim 1, wherein in the step (2), the molar ratio of the carboxylated graphene, the 5-aminoisophthalic acid, the triphenyl phosphite, the glass fiber and the acetic acid is 0.2 ~ 0.4:1.5 ~ 2.5.5: 4 ~ 5:0.6-0.7:12 ~ 14.
4. The method for preparing the wear-resistant nylon composite engineering plastic for the railway tracks as claimed in claim 1, wherein in the step (2), the inert gas is nitrogen or argon.
5. The method for preparing wear-resistant nylon composite engineering plastic for railway tracks as claimed in claim 1, wherein in step (2), graphene liquid, 5-amino isophthalic acid and triphenyl phosphite are heated to 100 ℃ under the protection of nitrogen or inert gas for reaction for 1 hour, then heated to 145 ℃, and then glass fiber is added for reaction for 1 hour.
6. The method for preparing the abrasion-resistant nylon composite engineering plastic for the railway track according to claim 1, wherein in the step (2), the reaction is carried out for 0.8 hour under vacuum.
7. The method for preparing the abrasion-resistant nylon composite engineering plastic for the railway track according to claim 1, wherein in the step (2), the pre-product is placed in a vacuum drying oven for solid-phase polymerization for 15 hours.
8. The preparation method of the wear-resistant nylon composite engineering plastic for the railway track according to claim 1, wherein in the step (3), the weight ratio of the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant is 8 ~ 35:50 ~ 80:0.1 ~ 4:0.1 ~ 4:0.1 ~ 3.
9. The preparation method of the wear-resistant nylon composite engineering plastic for the railway tracks as claimed in claim 8, wherein in the step (3), the weight ratio of the hyperbranched polyamide/glass fiber composite material, the nylon 66, the toughening agent, the antioxidant and the flame retardant is 10 ~ 25:60 ~ 70:0.2 ~ 0.5.5: 0.3 ~ 0.7.7: 0.8 ~ 2.
10. An abrasion-resistant nylon composite engineering plastic for railway tracks, which is characterized by being prepared by the preparation method of the abrasion-resistant nylon composite engineering plastic for railway tracks of any one of claim 1 ~ 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114806162A (en) * | 2022-04-18 | 2022-07-29 | 江阴市宏丰塑业有限公司 | Glass fiber reinforced low-melting-point nylon 56 material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114806162A (en) * | 2022-04-18 | 2022-07-29 | 江阴市宏丰塑业有限公司 | Glass fiber reinforced low-melting-point nylon 56 material and preparation method thereof |
| CN114806162B (en) * | 2022-04-18 | 2023-08-29 | 江苏普非尔塑料科技有限公司 | Glass fiber reinforced low-melting-point nylon 56 material and preparation method thereof |
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Application publication date: 20200114 |