CN112143242A - Physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 and preparation method thereof - Google Patents
Physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and discloses physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 and a preparation method thereof. The low-temperature high-strength wear-resistant nylon 66 comprises PA66, epoxy resin, an antioxidant, a wear-resistant agent, a lubricant and glass fibers, and the preparation method comprises the following steps: (1) placing PA66, epoxy resin and an antioxidant in a double-screw extruder, and further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat to obtain a low-temperature high-strength PA66 material; (2) and (2) uniformly mixing the low-temperature high-strength PA66 material prepared in the step (1) with a wear-resistant agent, a lubricant and an antioxidant, and adding the mixture into a double-screw extruder from a main feeding port of the double-screw extruder to obtain the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon. According to the invention, the PA66 is toughened by using the epoxy resin as a toughening agent through chemical modification, so that the reduction of the low-temperature wear resistance of the PA66 composite material caused by the addition of a physical modified elastomer is avoided.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 and a preparation method thereof.
Background
Nylon 66, known by the chemical name polyhexamethylene adipamide and abbreviated to PA66 in the industry, is a translucent or opaque opalescent resin, and 66 in the name represents the number of carbon atoms of acid and amine in a unit chain respectively. PA66 contains polar amido bonds, can form hydrogen bonds among molecular chains, easily orients molecules, has high crystallinity, excellent mechanical properties such as tensile property, bending property and compressive strength, good corrosion resistance, oil resistance, heat resistance and the like, and is engineering plastic with wide application. In the prior art, Glass Fiber (GF) is mostly used as a reinforcing material to prepare a PA66/GF composite material, and the material has high strength and high hardness and is applied to track fasteners such as a track gauge block, a sleeve, a baffle seat and the like. However, with the construction and development of the rail transit in northern cold areas in China, the rail facilities are in a low-temperature environment for a long time, and the requirements of higher strength and wear resistance are put forward for the rail fastener prepared from PA66/GF composite material, and the notch impact strength of the low-temperature simple supporting beam at-50 ℃ needs to reach 18kJ/m2The abrasion loss is not more than 8 mg.
Chinese invention patent CN201911379186.5 discloses a high-strength wear-resistant nylon composite material which is prepared from the following componentsThe raw materials in parts by weight are as follows: 40-70 parts of nylon resin, 20-40 parts of fiber reinforced material, 5-20.5 parts of wear-resisting agent, 0.2-0.5 part of lubricating agent and 0.2-0.5 part of antioxidant, and the low-temperature strength and wear resistance of the nylon composite material prepared by the invention do not meet the requirements of a track fastener. In addition, in the aspect of material strength enhancement, the Marshall et al select ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) as a toughening agent, and when the mass fraction of the POE-g-MAH is 30%, the notch impact strength of the toughened PA66 at the temperature of-50 ℃ reaches 16.1kJ/m27.7 times of pure PA66, but the hardness of the elastomer is lower in a low-temperature environment, which can significantly reduce the wear resistance of the material. Therefore, the nylon 66/GF composite material with low temperature, high strength and high wear resistance is still an important research direction in the field of low temperature nylon products.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 and a preparation method thereof, epoxy resin is used as a modifier to perform ring-opening reaction with PA66 to generate a high-toughness nylon material, and a wear-resistant agent is added to further improve the wear-resistant performance of the material, so that the nylon 66 is toughened, the problem that the wear resistance of the material is reduced due to the addition of an elastomer in physical modification is avoided, and the low-temperature service life of the product is further prolonged due to the addition of the wear-resistant agent.
For the purpose of the invention, the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 comprises PA66, epoxy resin, an antioxidant, a wear-resistant agent, a lubricant and glass fibers.
Further, the epoxy resin is one or more of 1, 7-octadiene diepoxide, 3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, bisphenol a diglycidyl ether, polypropylene glycol diglycidyl ether, and 1, 4-butanediol diglycidyl ether, and is preferably polypropylene glycol diglycidyl ether.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 168 and antioxidant H3336.
Further, the wear-resisting agent is one or more of polytetrafluoroethylene micro powder, molybdenum disulfide, aramid fiber powder, silicone master batch, graphite, ultra-high molecular weight polyethylene and wollastonite.
Further, the lubricant is one or more of ethylene bis stearamide, polyethylene wax, E wax and calcium stearate.
Preferably, in some embodiments of the present invention, the mass ratio of the PA66 to the epoxy resin in the physicochemical synergistically modified low-temperature high-strength wear-resistant nylon 66 is 80 to 89.8: 10-20, wherein the mass ratio of the wear-resisting agent to the lubricant to the glass fiber is 10-20: 0.1-0.5: 25-40.
On the basis of the technical scheme, the invention also provides a preparation method of the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon, which comprises the following steps:
(1) placing PA66, epoxy resin and an antioxidant in a double-screw extruder, further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain a low-temperature high-strength PA66 material;
(2) uniformly mixing the low-temperature high-strength PA66 material prepared in the step (1) with a wear-resistant agent, a lubricant and an antioxidant, adding the mixture into a double-screw extruder from a main feed inlet of the double-screw extruder, adding glass fiber from a side feed inlet, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, and extruding, cooling, drying and granulating to obtain the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon.
Preferably, in some embodiments of the present invention, in the step (1), the PA66, the epoxy resin and the antioxidant are placed in a twin-screw extruder with a vacuum degree of-0.07 to-0.03 MPa and a rotation speed of 60 to 120rpm, and the temperature of the twin-screw extruder is 250 to 300 ℃.
Further preferably, in some embodiments of the present invention, in the step (1), the PA66, the polypropylene glycol diglycidyl ether and the antioxidant are placed in a twin-screw extruder with a temperature of 260 to 280 ℃, a rotation speed of 95 to 105rpm and a vacuum degree of-0.03 MPa, and the mass ratio of the PA66, the polypropylene glycol diglycidyl ether and the antioxidant 1010 is 84 to 85: 14.5-15.5: 0.25-0.35.
Preferably, in some embodiments of the present invention, after the low-temperature high-strength PA66 material prepared in step (1) is uniformly mixed with the anti-wear agent, the lubricant and the antioxidant in step (2), the mixture is fed into a twin-screw extruder at 250-300 ℃ and a vacuum degree of-0.07-0.03 Mpa from a main feeding port of the twin-screw extruder, and the glass fiber is fed into the twin-screw extruder from a side feeding port at a rotation speed of 60-120 rpm.
Further preferably, in some embodiments of the present invention, after the low-temperature high-strength PA66 material prepared in step (1) is uniformly mixed with graphite, ethylene bis stearamide and an antioxidant in step (2), the mixture is fed into a twin-screw extruder at 250-300 ℃ and a vacuum degree of-0.04-0.03 Mpa from a main feeding port of the twin-screw extruder, and glass fibers are fed into the twin-screw extruder from a side feeding port at a rotation speed of 85-95 rpm, wherein a mass ratio of the low-temperature high-strength PA66 material to the graphite, the ethylene bis stearamide, the antioxidant and the glass fibers is 53-57: 9-11: 0.27-0.33: 0.18-0.22: 34-35.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the PA66 is toughened by using epoxy resin as a toughening agent through chemical modification, the reduction of the low-temperature wear resistance of the PA66 composite material caused by the addition of a physical modified elastomer is avoided, and the low-temperature wear resistance of the PA66 composite material can be further improved by the addition of a wear-resistant agent;
(2) the invention completes the preparation of the low-temperature high-strength high-wear-resistance PA66 by melt blending extrusion, and is suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Furthermore, descriptions of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like described herein mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
In the invention, the low-temperature high strength means that the notch impact strength of the simply supported beam at the low temperature of-50 ℃ reaches 18kJ/m2And the abrasion loss is not more than 8 mg.
Example 1
(1) Preparation of low-temperature high-strength PA66
Placing 80.8 wt% of PA66, 19 wt% of epoxy resin 1, 7-octadiene diepoxy compound and 0.2 wt% of antioxidant 1098 into a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 60rpm and the vacuum degree of 0.03MPa, further carrying out melt reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent polytetrafluoroethylene micro powder, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, extruding, cooling, drying and pelletizing to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 2
(1) Preparation of low-temperature high-strength PA66
Putting 80.8 wt% of PA66, 19 wt% of epoxy resin 3, 3 ', 5, 5' -tetramethyl biphenyl diphenol diglycidyl ether and 0.2 wt% of antioxidant 1098 into a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 60rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent molybdenum disulfide, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 3
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin 1, 7-octadiene diepoxide and 0.3 wt% of antioxidant 1098 into a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 60rpm and the vacuum degree of-0.03 MPa. And under the action of screw shearing and heat, further carrying out melt reaction on the PA66 and the epoxy resin, conveying the mixture to the head of an extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent molybdenum disulfide, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 4
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin 1, 4-butanediol diglycidyl ether and 0.3 wt% of antioxidant H3336 into a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent ultra-high molecular weight polyethylene, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, extruding, cooling, drying and pelletizing to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 5
(1) Preparation of low-temperature high-strength PA66
Placing 89.8 wt% of PA66, 10 wt% of epoxy resin 1, 4-butanediol diglycidyl ether and 0.2 wt% of antioxidant H3336 into a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent graphite, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of shearing force and heat of a screw, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 6
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin polypropylene glycol diglycidyl ether and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and epoxy resin under the action of screw shearing and heat, conveying to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 50 wt% of low-temperature high-strength PA66, 20 wt% of wear-resistant agent polytetrafluoroethylene micro powder, 0.1 wt% of antioxidant 1098 and 0.1 wt% of lubricant polyethylene wax, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 29.8 wt% of glass fiber into the twin-screw extruder at 0.03MPa from a side feed inlet at the rotating speed of 60rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of shearing force and heat of a screw, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 7
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin polypropylene glycol diglycidyl ether and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and epoxy resin under the action of screw shearing and heat, conveying to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 50 wt% of low-temperature high-strength PA66, 20 wt% of wear-resistant agent polytetrafluoroethylene micro powder, 0.2 wt% of antioxidant H3336 and 0.3 wt% of lubricant calcium stearate, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 29.5 wt% of glass fiber into the twin-screw extruder at-0.07 MPa from a side feed inlet at the rotating speed of 70rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 8
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin polypropylene glycol diglycidyl ether and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and epoxy resin under the action of screw shearing and heat, conveying to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 15 wt% of wear-resistant agent polytetrafluoroethylene micro powder, 0.2 wt% of antioxidant H3336 and 0.3 wt% of lubricant calcium stearate, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 29.5 wt% of glass fiber into the twin-screw extruder at-0.07 MPa from a side feed inlet at the rotating speed of 70rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 9
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin polypropylene glycol diglycidyl ether and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and epoxy resin under the action of screw shearing and heat, conveying to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 60 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent graphite, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 29.5 wt% of glass fiber into the twin-screw extruder at a vacuum degree of-0.03 MPa from a side feed inlet at a rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and pelletizing to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Example 10
(1) Preparation of low-temperature high-strength PA66
Placing 84.7 wt% of PA66, 15 wt% of epoxy resin polypropylene glycol diglycidyl ether and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, further carrying out melting reaction on PA66 and epoxy resin under the action of screw shearing and heat, conveying to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain the low-temperature high-strength PA66 material.
(2) Preparation of low-temperature high-strength high-wear-resistance PA66/GF composite material
Uniformly mixing 55 wt% of low-temperature high-strength PA66, 10 wt% of wear-resistant agent graphite, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of shearing force and heat of a screw, conveying the mixture to a machine head of the extruder, and extruding, cooling, drying and granulating to obtain the low-temperature high-strength high-wear-resistant PA66 composite material.
Comparative example 1
Placing 84.7 wt% of PA66, 15 wt% of toughening agent EPDM and 0.3 wt% of antioxidant 1010 in a double-screw extruder with the temperature of 260-280 ℃, the rotating speed of 100rpm and the vacuum degree of-0.03 MPa, and performing extrusion, cooling, drying and dicing to obtain the PA66 composite material.
Comparative example 2
Uniformly mixing 55 wt% of PA66, 10 wt% of wear-resistant agent calcium stearate, 0.2 wt% of antioxidant 1010 and 0.3 wt% of lubricant ethylene bis stearamide, adding the mixture into a twin-screw extruder at 250-300 ℃ from a main feed inlet of the twin-screw extruder, adding 34.5 wt% of glass fiber into the twin-screw extruder at-0.03 MPa from a side feed inlet at the rotating speed of 90rpm, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of shearing force and heat of a screw, conveying the mixture to a machine head of the extruder, extruding, cooling, drying and granulating to obtain the low-temperature (-50 ℃) high-wear-resistant PA66/GF composite material.
TABLE 1 Properties of the examples and comparative examples PA66 composite
As can be seen from table 1, compared to the physical toughener EPDM modified PA66, the toughness of the epoxy resin chemically modified PA66 is significantly improved, and the toughness of the material is gradually improved as the addition amount of the epoxy resin polypropylene glycol diglycidyl ether is increased. When the material is rubbed, the graphite slips due to the wear-resisting agent, so that the wear amount of the material is reduced.
In conclusion, the performance of the composite material is the best in example 10, compared with that of comparative example 1, the normal temperature tensile strength and the normal temperature bending strength are respectively enhanced by 14% and 9%, the low temperature notch impact strength is improved by 50%, the abrasion loss is only 0.2mg, and the low temperature wear resistance is also obviously enhanced while the low temperature strength of the composite material is improved.
It will be understood by those skilled in the art that the foregoing is only exemplary of the present invention, and is not intended to limit the invention, which is intended to cover any variations, equivalents, or improvements therein, which fall within the spirit and scope of the invention.
Claims (10)
1. The physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 is characterized by comprising PA66, epoxy resin, an antioxidant, a wear-resistant agent, a lubricant and glass fibers.
2. The physico-chemically synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 1, wherein the epoxy resin is one or more of 1, 7-octadiene diepoxide, 3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether, and is preferably polypropylene glycol diglycidyl ether.
3. The physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 168 and antioxidant H3336.
4. The physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 1, wherein the wear-resistant agent is one or more of polytetrafluoroethylene micropowder, molybdenum disulfide, aramid powder, silicone masterbatch, graphite, ultra-high molecular weight polyethylene and wollastonite.
5. The physico-chemically synergistic modified low temperature high strength abrasion resistant nylon 66 as claimed in claim 1, wherein said lubricant is one or more of ethylene bis stearamide, polyethylene wax, E wax and calcium stearate; preferably, the mass ratio of the PA66 to the epoxy resin in the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 is 80-89.8: 10-20, wherein the mass ratio of the wear-resisting agent to the lubricant to the glass fiber is 10-20: 0.1-0.5: 25-40.
6. The preparation method of the physicochemical modified low-temperature high-strength wear-resistant nylon 66 as described in any one of claims 1 to 5, wherein the method comprises the following steps:
(1) placing PA66, epoxy resin and an antioxidant in a double-screw extruder, further carrying out melting reaction on PA66 and the epoxy resin under the action of screw shearing and heat, conveying the mixture to the head of the extruder, and carrying out extrusion, cooling, drying and grain cutting to obtain a low-temperature high-strength PA66 material;
(2) uniformly mixing the low-temperature high-strength PA66 material prepared in the step (1) with a wear-resistant agent, a lubricant and an antioxidant, adding the mixture into a double-screw extruder from a main feed inlet of the double-screw extruder, adding glass fiber from a side feed inlet, further melting and mixing the PA66, the wear-resistant agent and the glass fiber under the action of screw shearing force and heat, conveying the mixture to a head of the extruder, and extruding, cooling, drying and granulating to obtain the physical and chemical synergistic modified low-temperature high-strength wear-resistant nylon.
7. The preparation method of the physico-chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 6, wherein in the step (1), the PA66, the epoxy resin and the antioxidant are placed in a twin-screw extruder at 250-300 ℃, the vacuum degree of-0.07-0.03 MPa and the rotating speed of 60-120 rpm.
8. The preparation method of the physico-chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 6, wherein in the step (1), the PA66, the polypropylene glycol diglycidyl ether and the antioxidant are placed in a twin-screw extruder with the temperature of 260-280 ℃, the rotating speed of 95-105rpm and the vacuum degree of-0.03 MPa, and the mass ratio of the PA66 to the polypropylene glycol diglycidyl ether to the antioxidant 1010 is 84-85: 14.5-15.5: 0.25-0.35.
9. The preparation method of the physico-chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 6, wherein in the step (2), the low-temperature high-strength PA66 material prepared in the step (1) is uniformly mixed with a wear-resistant agent, a lubricant and an antioxidant, and then is added into a twin-screw extruder with the temperature of 250-300 ℃ and the vacuum degree of-0.07-0.03 MPa from a main feeding port of the twin-screw extruder, and glass fiber is added into the twin-screw extruder from a side feeding port at the rotating speed of 60-120 rpm.
10. The preparation method of the physico-chemical synergistic modified low-temperature high-strength wear-resistant nylon 66 as claimed in claim 6, wherein in the step (2), the low-temperature high-strength PA66 material prepared in the step (1) is uniformly mixed with graphite, ethylene bis stearamide and an antioxidant, then the mixture is added into a twin-screw extruder with the temperature of 250-300 ℃ and the vacuum degree of-0.04-0.03 MPa from a main feeding port of the twin-screw extruder, glass fiber is added into the twin-screw extruder from a side feeding port at the rotating speed of 85-95 rpm, and the mass ratio of the low-temperature high-strength PA66 material to the graphite to the ethylene bis stearamide to the antioxidant to the glass fiber is 53-57: 9-11: 0.27-0.33: 0.18-0.22: 34-35.
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