CN114395166A - High-strength wear-resistant composite fender and processing technology thereof - Google Patents
High-strength wear-resistant composite fender and processing technology thereof Download PDFInfo
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- CN114395166A CN114395166A CN202210058234.6A CN202210058234A CN114395166A CN 114395166 A CN114395166 A CN 114395166A CN 202210058234 A CN202210058234 A CN 202210058234A CN 114395166 A CN114395166 A CN 114395166A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/08—Front or rear portions
- B62D25/16—Mud-guards or wings; Wheel cover panels
- B62D25/161—Mud-guards made of non-conventional material, e.g. rubber, plastics
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides a high-strength wear-resistant composite fender and a processing technology thereof, which are light in weight by limiting added component and process design, and the composite fender with high strength, good wear resistance and strong waterproof and anti-fouling capabilities is prepared; modifying the cellulose nanocrystal by reacting hydroxyl on the surface of the cellulose nanocrystal with para-isocyanato of caprolactam, and blocking the cellulose nanocrystal by adopting the caprolactam; the modified cellulose nanocrystal improves the interface compatibility among the anionic polymerization nylon 6, polypropylene and hollow glass beads, and a modified PP layer is prepared by a microcellular foaming injection molding process; limiting the adding amount of the hollow glass beads; the composite fender is prepared by blending and extruding low-density polyethylene, fluorine-containing hyperbranched polymer, modified cellulose nanocrystal and polyphenylene sulfide to obtain protective slurry, and coating the protective slurry on two sides of a modified PP layer to form protective layers, so that the surface hydrophobicity of the composite fender is improved, the composite fender has an anti-fouling and waterproof function, and the service life of the composite fender is greatly prolonged.
Description
Technical Field
The invention relates to the field of mudguards, in particular to a high-strength wear-resistant composite mudguard and a processing technology thereof.
Background
The mudguard is a plate structure arranged behind the outer frame of the wheel, and the material composition of the mudguard is metal, cowhide, plastic, rubber and the like. The vehicle mudguard mainly has the functions of preventing soil from splashing on a vehicle body or a person, improving the attractiveness of the vehicle body and preventing the problem of rusting after the soil is splashed; the fender for the car can also prevent small stones from being clamped in the tire seams and thrown onto the car body when the speed is too high, and the outer paint of the car is damaged.
3 major requirements for the development of the environment-friendly automobile material in China are light weight, green environmental protection, comfort and safety; at present, the lightweight materials of automobiles mainly comprise high-strength steel, magnesium-aluminum alloy and carbon fiber composite materials. However, the materials are generally expensive, easily cause pollution to the environment, and are more and more not in line with the modern green sustainable development strategy.
More and more composite mud guards for vehicles are made of plastics, but the composite mud guards made of the existing common plastics have insufficient wear resistance and limited service life.
Disclosure of Invention
The invention aims to provide a high-strength wear-resistant composite fender and a processing technology thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a high-strength wear-resistant composite fender comprises a modified PP layer and protective layers formed by coating protective slurry on two sides of the modified PP layer, wherein the modified PP layer is formed by microcellular foaming injection molding;
the protective layer comprises the following components in parts by weight: 45-55 parts of low-density polyethylene, 0.16-0.2 part of fluorine-containing hyperbranched polymer, 0.1-0.5 part of modified cellulose nanocrystal and 9-11 parts of polyphenylene sulfide.
According to the invention, anionic polymerization nylon 6, polypropylene and low-density polyethylene are used as processing raw materials to prepare the lightweight high-strength wear-resistant composite fender, the composite fender is of a sandwich structure, the middle layer is a modified PP layer, and the composite fender is formed by carrying out microcellular foaming injection molding on the composite fender after the anionic polymerization nylon 6, hollow glass beads, polypropylene, modified cellulose nanocrystals and antioxidant 1010 are co-extruded; the composite fender is prepared by blending and extruding low-density polyethylene, fluorine-containing hyperbranched polymer, modified cellulose nanocrystal and polyphenylene sulfide to obtain protective slurry, coating the protective slurry on two sides of a modified PP layer to form protective layers, so that the composite fender is light in weight, high in mechanical strength, good in wear resistance and hydrophobic in surface, has an anti-fouling and waterproof function, and greatly prolongs the service life of the composite fender.
The polypropylene is a general plastic with the largest output, has better comprehensive performance compared with other general plastics, has the characteristic of low density, but is directly used as a baffle, and has insufficient mechanical strength and poor high-temperature stability; the anionic polymerization nylon 6 has the advantages of chemical resistance, oil resistance, high mechanical strength and the like, but the amide group of the main chain has strong polarity, so that the hygroscopicity is strong and the water resistance is poor; and the polypropylene and the anionic polymerization nylon 6 are directly blended and have poor compatibility, and a phase separation structure is easy to generate.
According to the invention, the modified cellulose nanocrystal is used for preparing the anionic polymerization nylon 6, and the blend modification is carried out on the anionic polymerization nylon 6, the polypropylene and the hollow glass beads, so that the interface compatibility of the anionic polymerization nylon 6 and the polypropylene and the hollow glass beads is improved, and the composite fender with high thermal stability is obtained.
Further, the preparation of the modified cellulose nanocrystal comprises the following steps:
(1) vacuumizing the cellulose nanocrystal for 48h at the temperature of 100-;
(2) vacuumizing caprolactam at 110 ℃ for 30min in nitrogen atmosphere, and adding toluene to obtain a toluene solution of caprolactam; and in the nitrogen atmosphere, vacuumizing the cellulose nanocrystal mixed solution for 30min, heating to 90 ℃, adding a toluene solution of caprolactam, reacting, centrifuging, cleaning with toluene, and drying in vacuum to obtain the modified cellulose nanocrystal.
Further, the molar ratio of caprolactam to toluene diisocyanate was 2: 1.
In the step S1, the tetrahydrofuran mixed solution content of the ethylmagnesium bromide is 1mol/L, and the content of the diacylated lactam-1, 6-hexanediamine is 2 mol/kg.
Cellulose nanocrystals are used as reinforcing agents for polyurethanes, polylactic acids, epoxy thermosets and the like because of their surface rich in hydroxyl groups, but due to their hydrogen bonding and stability of surface charged colloids, most applications of cellulose nanocrystals are limited to aqueous treatment media, such as solution casting of polymer emulsions, water-soluble polymers, in order to achieve a uniformly dispersed state; the cellulose nanocrystals are prone to agglomeration during the traditional melt extrusion process.
According to the invention, the cellulose nanocrystals are modified, so that when the cellulose nanocrystal nanoparticles are dispersed in the anionic polymerization nylon 6 and polypropylene to reach the nanoscale, excellent reinforcing and toughening effects are synchronously achieved on the composite fender, and the prepared composite fender has low density and excellent mechanical properties.
According to the method, ethyl magnesium bromide is used as an initiator by adopting an anionic polymerization method, cellulose nanocrystalline grafted with a acylated caprolactam matrix is used as an activator to prepare the composite material, hydroxyl on the surface of the cellulose nanocrystalline reacts with para-isocyanate of caprolactam to modify the cellulose nanocrystalline, but the isocyanate easily reacts with moisture and carbon dioxide in the air, so that the caprolactam is required to be used for blocking to prepare the cellulose nanocrystalline grafted caprolactam.
Firstly, the cellulose nanocrystalline is vacuumized for 40 hours at the temperature of 100-105 ℃, so that the moisture adsorbed on the surface of the cellulose nanocrystalline is completely removed, and the hydroxyl on the surface is exposed, thereby being beneficial to the cellulose nanocrystalline to participate in the subsequent reaction. In order to reduce the consumption of residual isocyanic acid radical caused by the reaction of the cellulose nanocrystalline grafted caprolactam with moisture and carbon dioxide in the air as much as possible, in the preparation process of the cellulose nanocrystalline grafted caprolactam, the modified cellulose nanocrystalline is continuously prepared without drying after centrifugation.
But side reaction can occur in the cellulose nanocrystalline grafted caprolactam, partial ortho-isocyanate can also participate in the reaction, and in order to inhibit the side reaction, the molar ratio of TDI/CNC is controlled to be 2, and the ratio of the cellulose nanocrystalline and toluene is controlled to prevent the influence on the subsequent preparation.
The hollow glass beads are added to improve the phenomena of floating fiber exposure, shrinkage deformation rate reduction and product warping of the composite fender, the flame retardance, the wear resistance and the scratch resistance of the composite fender are synergistically improved, the light weight requirement is met, the adding amount of the hollow glass beads is limited to 5.6% -8.7%, when the adding amount of the hollow glass beads exceeds 8.7%, a large number of cavities can be generated in the combustion process, the compactness of a carbon layer is affected, and the LOI value of the composite fender is reduced. The modified cellulose nanocrystal enables the anionic polymerization nylon 6 and the polypropylene to have excellent interface combination, so that the hollow glass beads can be better wrapped and protected by resin in the double-screw extrusion and injection molding processes, the bead breaking proportion of the hollow glass beads is reduced, and the prepared composite fender has lower density, better rigidity and toughness.
The low-density polyethylene has the characteristics of low cost, no toxicity, no odor and the like, but the contact angle of the surface of the common low-density polyethylene and water is usually less than 110 degrees, and the common low-density polyethylene does not have self-cleaning performance.
Further, the preparation of the fluorine-containing hyperbranched polymer comprises the following steps: mixing and stirring the hyperbranched polymer, 2,3,4, 5-tetrafluorobenzoic acid and toluene, adding p-toluenesulfonic acid, performing ultrasonic stirring, reacting at the temperature of 100 ℃ and 110 ℃ for 6 hours, and vacuumizing to obtain the fluorine-containing hyperbranched polymer.
Further, the molar ratio of the hyperbranched polymer to the 2,3,4, 5-tetrafluorobenzoic acid is 6: 1.
The fluorine-containing hyperbranched polyester is introduced into the linear low-density polyethylene resin through melt blending, the surface hydrophobicity of the composite fender is improved, F atoms provide lower surface energy for the composite fender, the F atoms are increased along with the increase of the fluorine-containing hyperbranched polyester, so that the surface energy in a system is further reduced, but the mechanical strength of the linear low-density polyethylene can be correspondingly reduced, therefore, the low-density polyethylene, the fluorine-containing hyperbranched polymer, the modified cellulose nanocrystal and the polyphenylene sulfide are blended and extruded, the mechanical strength of the composite fender is improved, meanwhile, the composite fender has the superhydrophobic performance, a cavitation layer is formed between a solution and the surface of a coating, the contact of a corrosive solution is effectively reduced, the service life of the composite fender is prolonged to the maximum, and the maintenance cost is saved.
The modified cellulose nanocrystalline is added into the protective layer, mutual diffusion and entanglement of macromolecular chains are increased, and mechanical strength and wear resistance of the composite fender are greatly improved.
Further, the processing technology of the high-strength wear-resistant composite fender comprises the following steps:
s1: heating caprolactam to 110-;
s2: adding anionic polymerization nylon 6, hollow glass beads and polypropylene through a main feeding port of a double-screw extruder, adding modified cellulose nanocrystals and an antioxidant 1010 through an auxiliary feeding port of the double-screw extruder, carrying out melt blending extrusion, simultaneously discharging water vapor through an exhaust port on a charging barrel of the double-screw extruder, and carrying out extrusion, cooling and granulation to obtain a composite material;
s3: putting the composite material into a micropore foaming injection molding machine with a screw temperature of 220 ℃ for plasticizing and melting, injecting supercritical nitrogen with the pressure of 15-17MPa by using supercritical fluid equipment to obtain a polymer melt, injecting the polymer melt into a cavity of a mold, and carrying out pressure maintaining, mold opening and closing, foaming, cooling and molding to obtain a modified PP layer;
s4: and (2) blending and extruding low-density polyethylene, fluorine-containing hyperbranched polymer, modified cellulose nanocrystal and polyphenylene sulfide to obtain protective slurry, and coating the protective slurry on two sides of the modified PP layer to form protective layers to obtain the high-strength wear-resistant composite fender.
Further, the composite material in the step S2 comprises the following components in parts by weight: 620-25 parts of anion polymerization nylon, 4-8 parts of hollow glass beads, 40-50 parts of polypropylene, 1-5 parts of modified cellulose nanocrystals and 10100.5-4 parts of antioxidant.
Further, in the step S1, the molar ratio of the tetrahydrofuran mixed solution of the ethyl magnesium bromide to the diacylated lactam-1, 6-hexanediamine is 2: 1; the weight part ratio of the modified cellulose nanocrystalline to the caprolactam is 3%.
Further, the mass fraction of the supercritical nitrogen in the step S3 in the polymer melt is 0.65-0.85%.
Further, the speed of injecting the supercritical nitrogen in the step S3 is 200-250 mm/S; in step S3, the temperature of the die is 60-85 ℃, the speed of opening and closing the die is 15-25mm/S, and the cooling time is 0.5-2 min.
The conventional linear polycaprolactam melt has insufficient strength and low viscosity, and the wall of a bubble hole is easy to thin and break under the stretching action in the bubble growth process of the micropore injection molding foaming process, so that the bubble fusion is serious, and the foaming effect is poor. According to the invention, polycaprolactam is modified through the cellulose nanocrystals, and then a long-chain branched structure is introduced through blending modification, so that the melt strength is effectively enhanced, and the foaming performance is improved; improve melt viscoelasticity and provide nucleation sites for the foaming agent, promote nucleation in the foaming process, accelerate nucleation rate, improve crystallization temperature, lead to the increase of cell density and the reduction of cell size.
The invention has the beneficial effects that:
the invention provides a high-strength wear-resistant composite fender and a processing technology thereof, which are light in weight by limiting added component and process design, and the composite fender with high strength, good wear resistance and strong waterproof and anti-fouling capabilities is prepared;
modifying the cellulose nanocrystal by reacting hydroxyl on the surface of the cellulose nanocrystal with para-isocyanato of caprolactam, and blocking the cellulose nanocrystal by adopting the caprolactam; the modified cellulose nanocrystal is used for improving the interface compatibility among the anionic polymerization nylon 6, polypropylene and hollow glass beads, and a modified PP layer is prepared; the modified cellulose nanocrystal enables the anionic polymerization nylon 6 and the polypropylene to have excellent interface combination, so that the hollow glass beads can be better wrapped and protected by resin in the double-screw extrusion and injection molding processes, the bead breaking proportion of the hollow glass beads is reduced, and the prepared composite fender has lower density, better rigidity and toughness; the adding amount of the hollow glass beads is limited, so that the flame retardance, the wear resistance and the scratch resistance of the composite fender are improved in a coordinated mode, and the light weight requirement is met;
the modified PP layer is prepared by a microcellular foaming injection molding process, so that the melt strength is effectively enhanced, the foaming performance is improved, the cellulose nanocrystals also serve as nucleating agents, the stress transfer is effectively borne, and the elongation at break is remarkably improved; the viscoelasticity of the melt is improved, nucleation sites are provided for the foaming agent, nucleation is promoted in the foaming process, the nucleation rate is accelerated, the crystallization temperature is increased, the cell density is increased, and the cell size is reduced;
the composite fender is prepared by blending and extruding low-density polyethylene, fluorine-containing hyperbranched polymer, modified cellulose nanocrystal and polyphenylene sulfide to obtain protective slurry, coating the protective slurry on two sides of a modified PP layer to form protective layers, and introducing the fluorine-containing hyperbranched polyester into linear low-density polyethylene resin through melt blending to improve the surface hydrophobicity of the composite fender, so that the composite fender has an anti-fouling and waterproof function, and the service life of the composite fender is greatly prolonged.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A processing technology of a high-strength wear-resistant composite fender comprises the following steps:
s1: heating 100 parts of caprolactam to 110 ℃ for heating and melting, vacuumizing to remove water until no bubbles exist, adding 3 parts of modified cellulose nanocrystals, vacuumizing to remove water until no bubbles exist, adding 1mol/L tetrahydrofuran mixed solution of ethyl magnesium bromide, heating to 150 ℃, continuously vacuumizing to remove water until no bubbles exist, adding 2mol/kg diacylated lactam-1, 6-hexanediamine for reaction for 25min, quickly casting into a mold preheated to 155 ℃, drying and polymerizing for 1h at constant temperature, and cooling to obtain the anionic polymerized nylon 6;
the preparation of the modified cellulose nanocrystal comprises the following steps:
(1) vacuumizing 6.2mmol of cellulose nanocrystal at 100 ℃ for 48h, ultrasonically treating the cellulose nanocrystal, 18.6mmol of triethylamine, 18.6mmol of toluene diisocyanate and 50mL of anhydrous toluene for 30min under the protection of nitrogen, centrifuging, cleaning with toluene, and repeating for 3 times to obtain a cellulose nanocrystal mixed solution;
(2) in the nitrogen atmosphere, 37.2mmol of caprolactam is vacuumized for 30min at 110 ℃, and toluene is added to obtain a toluene solution of caprolactam; in nitrogen atmosphere, vacuumizing the cellulose nanocrystal mixed solution for 30min, heating to 90 ℃, adding a toluene solution of caprolactam, reacting, centrifuging, cleaning with toluene, and vacuum-drying to obtain modified cellulose nanocrystals;
s2: adding anionic polymerization nylon 6, hollow glass beads and polypropylene through a main feeding port of a double-screw extruder, adding modified cellulose nanocrystals and an antioxidant 1010 through an auxiliary feeding port of the double-screw extruder, carrying out melt blending extrusion, simultaneously discharging water vapor through an exhaust port on a charging barrel of the double-screw extruder, and carrying out extrusion, cooling and granulation to obtain a composite material;
in step S2, the composite material contains the following components in parts by weight: 620 parts of anionic polymerization nylon, 4 parts of hollow glass beads, 40 parts of polypropylene, 1 part of modified cellulose nanocrystal and 10100.5 parts of antioxidant;
s3: the composite material is placed in a micropore foaming injection molding machine with a screw temperature of 220 ℃ for plasticizing and melting, supercritical nitrogen with the pressure of 15MPa is injected by supercritical fluid equipment to obtain a polymer melt, the polymer melt is injected into a cavity of a mold, and a modified PP layer is obtained through pressure maintaining, mold opening and closing, foaming, cooling and molding;
the mass fraction of supercritical nitrogen in the polymer melt is 0.65%; the speed of injecting supercritical nitrogen is 200 mm/s; the temperature of the die is 60 ℃, the speed of opening and closing the die is 15mm/s, and the cooling time is 0.5 min;
s4: according to parts by weight, 45 parts of low-density polyethylene, 0.16 part of fluorine-containing hyperbranched polymer, 0.1 part of modified cellulose nanocrystal and 9 parts of polyphenylene sulfide are blended and extruded to obtain protective slurry, and the protective slurry is coated on two sides of a modified PP layer to form protective layers, so that the high-strength wear-resistant composite fender is obtained;
the preparation of the fluorine-containing hyperbranched polymer comprises the following steps: mixing and stirring 26g of hyperbranched polymer, 15.4g of 2,3,4, 5-tetrafluorobenzoic acid and 400mL of toluene, adding 3g of p-toluenesulfonic acid, stirring by ultrasonic, reacting for 6h at 105 ℃, and vacuumizing to obtain the fluorine-containing hyperbranched polymer.
Example 2
A processing technology of a high-strength wear-resistant composite fender comprises the following steps:
s1: heating 100 parts of caprolactam to 113 ℃ for heating and melting, vacuumizing to remove water until no bubbles exist, adding 3 parts of modified cellulose nanocrystals, vacuumizing to remove water until no bubbles exist, adding 1mol/L tetrahydrofuran mixed solution of ethyl magnesium bromide, heating to 153 ℃, continuously vacuumizing to remove water until no bubbles exist, adding 2mol/kg diacylated lactam-1, 6-hexanediamine for reaction for 25min, quickly casting into a mold preheated to 158 ℃, drying and polymerizing for 1h at constant temperature, and cooling to obtain the anionic polymerized nylon 6;
the preparation of the modified cellulose nanocrystal comprises the following steps:
(1) vacuumizing 6.2mmol of cellulose nanocrystal at 102 ℃ for 48h, ultrasonically treating the cellulose nanocrystal, 18.6mmol of triethylamine, 18.6mmol of toluene diisocyanate and 50mL of anhydrous toluene for 30min under the protection of nitrogen, centrifuging, cleaning with toluene, and repeating for 4 times to obtain a cellulose nanocrystal mixed solution;
(2) in the nitrogen atmosphere, 37.2mmol of caprolactam is vacuumized for 30min at 110 ℃, and toluene is added to obtain a toluene solution of caprolactam; in nitrogen atmosphere, vacuumizing the cellulose nanocrystal mixed solution for 30min, heating to 90 ℃, adding a toluene solution of caprolactam, reacting, centrifuging, cleaning with toluene, and vacuum-drying to obtain modified cellulose nanocrystals;
s2: adding anionic polymerization nylon 6, hollow glass beads and polypropylene through a main feeding port of a double-screw extruder, adding modified cellulose nanocrystals and an antioxidant 1010 through an auxiliary feeding port of the double-screw extruder, carrying out melt blending extrusion, simultaneously discharging water vapor through an exhaust port on a charging barrel of the double-screw extruder, and carrying out extrusion, cooling and granulation to obtain a composite material;
in step S2, the composite material contains the following components in parts by weight: 622 parts of anionic polymerization nylon, 6 parts of hollow glass beads, 45 parts of polypropylene, 3 parts of modified cellulose nanocrystals and 10102 parts of antioxidant;
s3: the composite material is placed in a micropore foaming injection molding machine with a screw temperature of 220 ℃ for plasticizing and melting, supercritical nitrogen with the pressure of 16MPa is injected by supercritical fluid equipment to obtain a polymer melt, the polymer melt is injected into a cavity of a mold, and a modified PP layer is obtained through pressure maintaining, mold opening and closing, foaming, cooling and molding;
the mass fraction of supercritical nitrogen in the polymer melt is 0.75%; the speed of injecting supercritical nitrogen is 240 mm/s; the temperature of the die is 75 ℃, the speed of opening and closing the die is 20mm/s, and the cooling time is 1 min;
s4: according to parts by weight, 50 parts of low-density polyethylene, 0.18 part of fluorine-containing hyperbranched polymer, 0.4 part of modified cellulose nanocrystal and 10 parts of polyphenylene sulfide are blended and extruded to obtain protective slurry, and the protective slurry is coated on two sides of a modified PP layer to form protective layers, so that the high-strength wear-resistant composite fender is obtained;
the preparation of the fluorine-containing hyperbranched polymer comprises the following steps: mixing and stirring 26g of hyperbranched polymer, 15.4g of 2,3,4, 5-tetrafluorobenzoic acid and 400mL of toluene, adding 3g of p-toluenesulfonic acid, stirring by ultrasonic, reacting for 6h at 105 ℃, and vacuumizing to obtain the fluorine-containing hyperbranched polymer.
Example 3
A processing technology of a high-strength wear-resistant composite fender comprises the following steps:
s1: heating 100 parts of caprolactam to 115 ℃ for heating and melting, vacuumizing to remove water until no bubbles exist, adding 3 parts of modified cellulose nanocrystals, vacuumizing to remove water until no bubbles exist, adding 1mol/L tetrahydrofuran mixed solution of ethyl magnesium bromide, heating to 155 ℃, continuously vacuumizing to remove water until no bubbles exist, adding 2mol/kg diacylated lactam-1, 6-hexanediamine for reaction for 25min, quickly casting into a mold preheated to 160 ℃, drying and polymerizing for 1h at constant temperature, and cooling to obtain the anionic polymerized nylon 6;
the preparation of the modified cellulose nanocrystal comprises the following steps:
(1) vacuumizing 6.2mmol of cellulose nanocrystal at 105 ℃ for 48h, ultrasonically treating the cellulose nanocrystal, 18.6mmol of triethylamine, 18.6mmol of toluene diisocyanate and 50mL of anhydrous toluene for 30min under the protection of nitrogen, centrifuging, cleaning with toluene, and repeating for 5 times to obtain a cellulose nanocrystal mixed solution;
(2) in the nitrogen atmosphere, 37.2mmol of caprolactam is vacuumized for 30min at 110 ℃, and toluene is added to obtain a toluene solution of caprolactam; in nitrogen atmosphere, vacuumizing the cellulose nanocrystal mixed solution for 30min, heating to 90 ℃, adding a toluene solution of caprolactam, reacting, centrifuging, cleaning with toluene, and vacuum-drying to obtain modified cellulose nanocrystals;
s2: adding anionic polymerization nylon 6, hollow glass beads and polypropylene through a main feeding port of a double-screw extruder, adding modified cellulose nanocrystals and an antioxidant 1010 through an auxiliary feeding port of the double-screw extruder, carrying out melt blending extrusion, simultaneously discharging water vapor through an exhaust port on a charging barrel of the double-screw extruder, and carrying out extrusion, cooling and granulation to obtain a composite material;
in step S2, the composite material contains the following components in parts by weight: 625 parts of anionic polymerization nylon, 8 parts of hollow glass beads, 50 parts of polypropylene, 5 parts of modified cellulose nanocrystals and 10104 parts of antioxidant;
s3: placing the composite material in a micropore foaming injection molding machine with a screw temperature of 220 ℃ for plasticizing and melting, injecting supercritical nitrogen with a pressure of 17MPa by using supercritical fluid equipment to obtain a polymer melt, injecting the polymer melt into a cavity of a mold, and performing pressure maintaining, mold opening and closing, foaming, cooling and molding to obtain a modified PP layer;
the mass fraction of supercritical nitrogen in the polymer melt is 0.85%; the speed of injecting supercritical nitrogen is 250 mm/s; the temperature of the die is 85 ℃, the speed of opening and closing the die is 25mm/s, and the cooling time is 2 min;
s4: 55 parts of low-density polyethylene, 0.2 part of fluorine-containing hyperbranched polymer, 0.5 part of modified cellulose nanocrystal and 11 parts of polyphenylene sulfide are blended and extruded in parts by weight to obtain protective slurry, and the protective slurry is coated on two sides of a modified PP layer to form protective layers, so that the high-strength wear-resistant composite fender is obtained;
the preparation of the fluorine-containing hyperbranched polymer comprises the following steps: mixing and stirring 26g of hyperbranched polymer, 15.4g of 2,3,4, 5-tetrafluorobenzoic acid and 400mL of toluene, adding 3g of p-toluenesulfonic acid, stirring by ultrasonic, reacting for 6h at 105 ℃, and vacuumizing to obtain the fluorine-containing hyperbranched polymer.
Comparative example 1
The modified cellulose nanocrystals were replaced with the cellulose nanocrystals using example 2 as a control, and the other steps were normal.
Comparative example 2
With example 2 as a control group, the modified PP layer was prepared directly by melt blending without microcellular foam injection molding, and other processes were normal.
Comparative example 3
Using example 2 as a control, no modified cellulose nanocrystals were added in step S2, and the other steps were normal.
Comparative example 4
The control group of example 2 was used, 10 parts of hollow glass beads were added, and other steps were normal.
Comparative example 5
Using example 2 as a control, the overcoat was made only with low density polyethylene and the other procedures were normal.
And (3) performance testing: the composite mud guard prepared in the examples 1-3 and the comparative examples 1-5 is subjected to performance test, and the composite mud guard prepared in the above way is subjected to test;
performing a tensile property test with reference to ISO 527-1-2012, wherein the tensile rate is 10 mm/min; density is tested with reference to ISO 1183-1-2012; the bending performance test is carried out by referring to ISO 178-2010, and the bending speed is 2 mm/min;
the contact angle is tested by referring to GB/T24368-2009, and the water drop capacity is kept at 4 mu L in the testing process;
performing an oxygen index test by referring to IOS4589-2, and introducing oxygen-nitrogen mixed gas flowing upwards in a laminar flow mode, wherein the temperature of the mixed gas is 20-25 ℃; when the top surface is ignited, the time for the flame to contact the top surface is shorter than 30s, the flame is moved away every 5s, whether the diaphragm burns or not is observed, and the minimum oxygen concentration just needed for maintaining the combustion is the oxygen index; the oxygen index of the combustible material is less than 18; the oxygen index of the combustible material is 18-25; the oxygen index of the flame retardant material is above 25; specific data are shown in table 1;
performing a rub resistance test with reference to ASTM D3884, cutting a sample size to 100mm × 100mm, weighing 500g, 500 mesh sandpaper, defining a wear cycle as 500 cycles, and determining a surface contact angle; performing an aging resistance test by referring to GB/T1865-; specific data are shown in table 2;
TABLE 1
TABLE 2
Examples 1 to 3 are composite mud guard prepared according to the invention, and comparing example 2 with comparative examples 1 to 5, it can be known that various performances of the composite mud guard are greatly improved by modifying cellulose nanocrystals and matching with corresponding process designs;
comparing example 2 with comparative example 2, it can be seen that the material density can be greatly reduced and the weight can be reduced by limiting the raw materials and performing injection molding by a microcellular injection molding foaming process;
comparing example 2 with comparative example 3, it can be seen that the mechanical strength is greatly reduced because no modified cellulose nanocrystals are added during the microcellular injection molding foaming process; comparing example 2 with comparative example 4, it can be seen that the addition of more than a limited amount of glass beads affects the flame retardancy of the composite fender though the density is reduced;
the composite mudguard prepared in examples 1-3 has the contact angle basically unchanged or slightly changed after being worn for 500 cycles and after being subjected to an aging oven for one cycle, which shows that the composite mudguard prepared by the invention has excellent aging resistance and wear resistance.
In conclusion, the composite fender prepared by the invention has excellent mechanical property, high aging resistance and wear resistance and good application prospect.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The processing technology of the high-strength wear-resistant composite fender is characterized by comprising the following steps:
s1: preparing anionic polymerization nylon 6;
s2: adding anionic polymerization nylon 6, hollow glass beads and polypropylene through a main feeding port of a double-screw extruder, adding modified cellulose nanocrystals and an antioxidant 1010 through an auxiliary feeding port of the double-screw extruder, and performing melt blending extrusion, cooling and granulation to obtain a composite material;
s3: putting the composite material into a micropore foaming injection molding machine with a screw temperature of 220 ℃ for plasticizing and melting, injecting supercritical nitrogen with the pressure of 15-17MPa by using supercritical fluid equipment to obtain a polymer melt, injecting the polymer melt into a cavity of a mold, and carrying out pressure maintaining, mold opening and closing, foaming, cooling and molding to obtain a modified PP layer;
s4: and (2) blending and extruding low-density polyethylene, fluorine-containing hyperbranched polymer, modified cellulose nanocrystal and polyphenylene sulfide to obtain protective slurry, and coating the protective slurry on two sides of the modified PP layer to form protective layers to obtain the high-strength wear-resistant composite fender.
2. The processing technology of the high-strength wear-resistant composite mudguard of claim 1, wherein the speed of injecting the supercritical nitrogen in step S3 is 200-250 mm/S; in step S3, the temperature of the die is 60-85 ℃, the speed of opening and closing the die is 15-25mm/S, and the cooling time is 0.5-2 min.
3. The processing technology of a high-strength wear-resistant composite mudguard of claim 1, wherein in step S3, the mass fraction of the supercritical nitrogen in the polymer melt is 0.65-0.85%.
4. The processing technology of the high-strength wear-resistant composite mudguard of claim 1, wherein the preparation of the anionic polymerization nylon 6 in the step S1 comprises the following steps: heating caprolactam to 110-.
5. The processing technology of the high-strength wear-resistant composite mudguard of claim 4, wherein the molar ratio of the tetrahydrofuran mixed solution of the ethyl magnesium bromide to the diacylated lactam-1, 6-hexanediamine is 2: 1; the weight part ratio of the modified cellulose nanocrystalline to the caprolactam is 3%.
6. The processing technology of the high-strength wear-resistant composite mudguard of claim 1, wherein in the step S2, the composite material comprises the following components in parts by weight: 620-25 parts of anion polymerization nylon, 4-8 parts of hollow glass beads, 40-50 parts of polypropylene, 1-5 parts of modified cellulose nanocrystals and 10100.5-4 parts of antioxidant, wherein the weight ratio of the hollow glass beads to the composite material is 5.6-8.7%; in step S4, the protective layer contains the following components in parts by weight: 45-55 parts of low-density polyethylene, 0.16-0.2 part of fluorine-containing hyperbranched polymer, 0.1-0.5 part of modified cellulose nanocrystal and 9-11 parts of polyphenylene sulfide.
7. The processing technology of the high-strength wear-resistant composite fender according to claim 1, wherein the preparation of the modified cellulose nanocrystal comprises the following steps:
(1) vacuumizing the cellulose nanocrystal for 48h at the temperature of 100-;
(2) vacuumizing caprolactam at 110 ℃ for 30min in nitrogen atmosphere, and adding toluene to obtain a toluene solution of caprolactam; and in the nitrogen atmosphere, vacuumizing the cellulose nanocrystal mixed solution for 30min, heating to 90 ℃, adding a toluene solution of caprolactam, reacting, centrifuging, cleaning with toluene, and drying in vacuum to obtain the modified cellulose nanocrystal.
8. The processing technology of the high-strength wear-resistant composite fender according to claim 7, wherein the molar ratio of caprolactam to toluene diisocyanate is 2: 1.
9. The processing technology of the high-strength wear-resistant composite fender according to claim 1, characterized in that the preparation of the fluorine-containing hyperbranched polymer comprises the following steps: mixing and stirring the hyperbranched polymer, 2,3,4, 5-tetrafluorobenzoic acid and toluene, adding p-toluenesulfonic acid, performing ultrasonic stirring, reacting at the temperature of 100 ℃ and 110 ℃ for 6 hours, and vacuumizing to obtain the fluorine-containing hyperbranched polymer; the molar ratio of the hyperbranched polymer to the 2,3,4, 5-tetrafluorobenzoic acid is 6: 1.
10. A high strength wear resistant composite fender, characterized by being manufactured by the process of any one of claims 1 to 9.
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