Wear-resistant PVC (Polyvinyl Chloride) composite material for binding galvanized iron wires and preparation process of wear-resistant PVC composite material

Abstract

The invention provides a wear-resistant PVC composite material for binding galvanized iron wires and a preparation process, and belongs to the technical field of PVC material preparation. The preparation process comprises the following steps: preparing mesoporous hollow carbon nanospheres; preparing a double-wall microcapsule; preparing a wear-resistant compound; and preparing the wear-resistant composite material. A single-wall microcapsule is prepared by dipping PAO6 loaded with oil-soluble copper nanoparticles in mesoporous hollow carbon nanospheres, and then the double-wall microcapsule prepared by wrapping the single-wall microcapsule with a melamine-formaldehyde / zinc oxide nanorod composite wall material is of a sea urchin-like structure. The PVC composite material prepared by adding the double-wall microcapsule effectively improves the wear resistance of the composite material.

Description

Technical Field

[0001] The invention relates to the technical field of PVC material preparation, and in particular to a wear-resistant PVC composite material for galvanized iron wire ties and a preparation process thereof. Background Art

[0002] In modern industrial production and daily life, galvanized iron wire ties are widely used in many fields, including construction, packaging, agriculture, and gardening, due to their excellent strength and corrosion resistance. For example, in the construction industry, they are often used to tie and secure steel bars; in the packaging field, they are used to bundle various types of goods; and in agriculture and gardening, they are used to support plant growth.

[0003] Currently, polyvinyl chloride (PVC) is often used to coat galvanized wire ties to further enhance their performance. However, existing PVC materials used for galvanized wire ties generally suffer from poor wear resistance. In actual use, due to frequent friction, such as friction with other building materials during construction and friction between packaged goods during transportation, the surface of the PVC composite material is prone to wear, scratches, and even damage. This not only reduces the aesthetics of the wire tie but also seriously affects its service life and performance, increasing usage costs and maintenance frequency.

[0004] As the requirements for the use of galvanized iron wire ties in various industries continue to increase, it has become extremely urgent to develop a PVC composite material with excellent wear resistance for galvanized iron wire ties. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a wear-resistant PVC composite material for galvanized iron wire ties and a preparation process.

[0006] A preparation process of a wear-resistant PVC composite material for galvanized iron wire ties, comprising the following steps:

[0007] S1: Preparation of mesoporous hollow carbon nanospheres

[0008] S2: Preparation of double-walled microcapsules

[0009] PAO6 containing oil-soluble copper nanoparticles was loaded into mesoporous hollow carbon nanospheres to obtain single-wall microcapsules. The single-wall microcapsules were treated with dopamine hydrochloride and then reacted with a prepolymer prepared from melamine and formaldehyde and zinc oxide nanorods to obtain double-wall microcapsules.

[0010] S3: Preparation of wear-resistant composites

[0011] Carbon nanofibers were modified with PDA and then reacted with ethyl orthosilicate and tridecafluorooctyltriethoxysilane to prepare a wear-resistant composite.

[0012] S4: Preparation of wear-resistant composite materials

[0013] The wear-resistant composite material is prepared by using 100-120 parts by weight of polyvinyl chloride resin, 20-30 parts by weight of chlorinated polyvinyl chloride, 20-30 parts by weight of calcium carbonate, 5-8 parts by weight of double-wall microcapsules, 12-27 parts by weight of wear-resistant composite, 5-10 parts by weight of titanium dioxide, 10-12 parts by weight of plasticizer, 0.5-1 part by weight of antioxidant, 0.5-1 part by weight of anti-ultraviolet absorber and 2-3 parts by weight of zinc stearate.

[0014] Furthermore, step S1 of preparing mesoporous hollow carbon nanospheres specifically includes the following steps:

[0015] S1.1: Add 350-380 parts by weight of ethanol to 50-70 parts by weight of deionized water, then add aqueous ammonia to adjust the pH to 8.5, and stir for 20-30 minutes. Then, add 14-16 parts by weight of tetraethyl orthosilicate, and stir again for 20-30 minutes to obtain a mixed solution;

[0016] S1.2: Add 2-3 parts by weight of dopamine hydrochloride to the mixed solution, then stir and react for 12-14 hours. After the reaction is completed, filter and wash alternately with ethanol and deionized water for 3-5 times. Dry the washed product at 80-85°C for 12-14 hours, and finally calcine at 800-820°C in a nitrogen atmosphere for 2-3 hours. Etch the calcined product with 2M sodium hydroxide solution to obtain mesoporous hollow carbon nanospheres.

[0017] Furthermore, the preparation of double-walled microcapsules in step S2 specifically includes the following steps:

[0018] S2.1: Adding oil-soluble copper nanoparticles to PAO6 and stirring to obtain PAO6 containing 3 wt% of oil-soluble copper nanoparticles, followed by adding 2-3 wt% of mesoporous hollow carbon nanospheres and ultrasonically dispersing for 20-30 minutes. The dispersion is then transferred to a device equipped with a vacuum pump and stirred and impregnated under negative pressure for 20-30 minutes. After impregnation, the dispersion is centrifuged with petroleum ether and anhydrous ethanol, washed, and finally dried to obtain single-wall microcapsules;

[0019] S2.2: Add 4-5 parts by weight of zinc acetate, 120-130 parts by weight of anhydrous ethanol, 30-40 parts by weight of polyethylene glycol, and 16-18 parts by weight of sodium hydroxide to a hydrothermal reactor, and react at 120-130°C for 12-15 hours. After natural cooling, the reactants are washed alternately with deionized water and anhydrous ethanol 2-3 times, and dried to obtain zinc oxide nanorods;

[0020] S2.3: 10.4-13.2 parts by weight of melamine, 21.4-23.1 parts by weight of a 37 wt% formaldehyde solution, 1.8-2.3 parts by weight of a 7 wt% triethanolamine solution, and 62.3-64.8 parts by weight of deionized water are mixed and stirred for 20-30 minutes, and then the pH is adjusted to 8.5-9, followed by stirring and reacting at 70-75° C. for 1-2 hours to obtain a prepolymer;

[0021] S2.4: Add single-walled microcapsules and dopamine hydrochloride in a mass ratio of 1-2:0.4-0.6 to a Tris buffer solution with a pH of 8.5. The concentration of dopamine hydrochloride in the Tris buffer solution is 4-5 mg / mL. After stirring and mixing for 20-24 hours, adjust the pH to neutral. At 50-55°C, add prepolymer at a rate of 1-2 drops / s. The mass ratio of prepolymer to single-walled microcapsules is 1-1.5:1. After reacting for 45-50 minutes, adjust the pH to 5.4-6.2. Continue to react for 20-30 minutes, then add zinc oxide nanorods and react for 3-4 hours. The mass ratio of zinc oxide nanorods to single-walled microcapsules is 0.3-0.5:1. After the reaction is completed, filter, wash, and dry to obtain double-walled microcapsules.

[0022] Furthermore, step S3 of preparing the wear-resistant composite material specifically includes the following steps:

[0023] S3.1: Dispersing 1-2 parts by weight of carbon nanofibers in 100-120 parts by weight of deionized water, then adding 1-2 parts by weight of PDA, adjusting the pH to 8.5 with Tris alkaline buffer, polymerizing under magnetic stirring at room temperature for 24-28 hours, and then washing with anhydrous ethanol 2-3 times to obtain modified carbon nanofibers;

[0024] S3.2: Disperse 1-2 parts by weight of modified carbon nanofibers in 40-50 parts by weight of anhydrous ethanol, then add 2-3 parts by weight of ammonia water, ultrasonicate for 20-30 minutes, then magnetically stir at 30-34°C for 20-30 minutes, then dropwise add 2.1-2.2wt% of ethyl orthosilicate and 0.01-0.02 parts by weight of tridecafluorooctyltriethoxysilane to react for 5-6 hours, then add 0.02-0.03 parts by weight of tridecafluorooctyltriethoxysilane to react for 3-4 hours to obtain a wear-resistant composite.

[0025] Furthermore, step S4 of preparing the wear-resistant composite material specifically includes the following steps:

[0026] S4.1: 100-120 parts by weight of polyvinyl chloride resin, 20-30 parts by weight of chlorinated polyvinyl chloride, 20-30 parts by weight of calcium carbonate, 5-8 parts by weight of double-wall microcapsules, 12-27 parts by weight of wear-resistant composite, 5-10 parts by weight of titanium dioxide, 10-12 parts by weight of plasticizer, 0.5-1 part by weight of antioxidant, 0.5-1 part by weight of anti-ultraviolet absorber, and 2-3 parts by weight of zinc stearate are mixed to obtain a mixed material;

[0027] S4.2: Place the mixed material into a high-speed mixer and stir it at a temperature of 80-90°C for 5-10 minutes. The stirred material is extruded into a mold through an extruder. The temperature of the extruder is set to 170-190°C and the screw speed is 20-30 r / min. The extruded material is cooled and pelletized to obtain a wear-resistant composite material.

[0028] Furthermore, in step S4.1, the plasticizer is a calcium zinc stabilizer.

[0029] Furthermore, the antioxidant in step S4.1 is a mixture of antioxidant 1010 and antioxidant 1024 in a mass ratio of 1:2-3.

[0030] Furthermore, the anti-ultraviolet absorber in step S4.1 is anti-ultraviolet absorber UV-531.

[0031] A wear-resistant PVC composite material for galvanized iron wire ties is prepared by any of the above-mentioned preparation processes for the wear-resistant PVC composite material for galvanized iron wire ties.

[0032] Compared with the prior art, the present invention has at least the following beneficial effects:

[0033] 1. The present invention prepares single-wall microcapsules by impregnating PAO6 loaded with oil-soluble copper nanoparticles into mesoporous hollow carbon nanospheres. The double-wall microcapsules prepared by wrapping the single-wall microcapsules with a melamine-formaldehyde / zinc oxide nanorod composite wall material have a "sea urchin-like" structure and can be uniformly dispersed in a PVC composite material. Under the action of friction stress and shear, the oil-soluble copper nanoparticles and PAO6 in the microcapsules are released at the friction interface, thereby forming a tribochemical transfer film with a gradient chemical composition structure at the friction interface. That is, the upper layer is mainly an amorphous carbon film formed by the tribochemical reaction of PVC-based wear debris and PAO6 released from the nanocapsules, while the lower layer, in addition to the amorphous carbon film, also includes a tribochemical transfer film composed of Cu cores exposed by organic chain breakage, zinc oxide, and nano-sized silica shells. This tribochemical reaction film with a special structure effectively improves the wear resistance of the composite material.

[0034] 2. The present invention prepares double-walled microcapsules by oxidizing dopamine hydrochloride and self-depositing it on the surface of single-walled microcapsules. The single-walled microcapsules are then wrapped with a melamine-formaldehyde / zinc oxide nanorod composite wall material. The zinc oxide nanorods extend outward from the melamine-formaldehyde shell to form spikes, presenting a "sea urchin-like" structure with a regular spherical shape. The "sea urchin-like" structure allows the double-walled microcapsules to better bond with the polyvinyl chloride (PVC), enhancing its physical wedging and chemical interface bonding with the substrate. Furthermore, the zinc oxide nanorod spikes on the surface of the double-walled microcapsules with the "sea urchin-like" structure can disperse and transfer friction when the PVC composite material is subjected to friction. On the one hand, the nanorods can withstand a certain amount of frictional force, reducing direct contact and wear between the PVC substrate and the friction surface. On the other hand, the interaction between the nanorods and between the nanorods and the PVC substrate can hinder the expansion of microcracks on the material surface, thereby significantly improving the wear resistance of the composite material.

[0035] 3. The carbon nanofibers in the present invention have excellent properties such as high strength and high modulus. As a micro-nanostructural building block, they can be evenly dispersed in the PVC matrix, playing a role in strengthening the skeleton, bearing part of the external friction, reducing the direct wear of the PVC matrix, and thus improving the wear resistance of the material. Polydopamine forms a coating on the surface of the carbon nanofibers through chemical bonding, which not only improves the interfacial bonding between ANFs and the PVC matrix, allowing stress to be more effectively transferred between the fiber and the matrix, but also provides a stable platform for the subsequent growth of nano-silica. The nano-silica grown in situ on the PDA coating has high hardness and wear resistance, and can form a "grape"-like structure. Nano-silica particles can fill the pores of the PVC matrix, improve the density of the material, and form a hard shell on the surface of the material. When the material is subjected to friction, the nano-silica can bear part of the friction force, play a role in resisting abrasive wear, and further improve the wear resistance of the PVC material. After low surface energy modification by tridecafluorooctyl triethoxysilane, the surface energy of the wear-resistant composite is reduced, which reduces the friction between the external objects and the surface of the material. During the friction process, the surface of the material with low surface energy is less likely to be attached and scratched by wear particles, which helps to improve the wear resistance of the material. Carbon nanofibers and nano-silica particles cooperate with each other, and carbon nanofibers can prevent nano-silica from The agglomeration and movement of silicon dioxide particles under stress enable the nano-silica particles to be evenly dispersed in the material, giving full play to its reinforcing effect. At the same time, the nano-silica particles can limit the deformation of carbon nanofibers and improve the load-bearing capacity of carbon nanofibers. The nano-silica particles are equivalent to "grape" fruits, which increase the roughness of the surface of the wear-resistant composite. Tridecafluorooctyltriethoxysilane introduces low surface energy fluorocarbon chains on the surface of nano-silica through chemical bonding. The rough surface of nano-silica increases the attachment area of tridecafluorooctyltriethoxysilane, allowing tridecafluorooctyltriethoxysilane to be more firmly bound to the material surface, further improving the wear resistance of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, further serve to explain the principles of the invention and to enable one skilled in the art to make and use the invention.

[0037] Figure 1 This is a process flow chart for preparing a wear-resistant PVC composite material for galvanized iron wire ties used in an embodiment of the present invention;

[0038] Figure 2 This is the "sea urchin-like" double-walled microcapsule structure and morphology of Example 1 of the present invention;

[0039] Figure 3This is a schematic diagram of the "grape" shaped wear-resistant composite material of the present invention. DETAILED DESCRIPTION

[0040] The following describes in detail, with reference to the accompanying drawings and specific examples, a process for preparing a wear-resistant PVC composite material for galvanized iron wire ties provided by the present invention. It is also noted that, for the sake of completeness, the following examples are best and preferred embodiments, and those skilled in the art may employ alternative methods for implementing known techniques. Furthermore, the accompanying drawings are intended only to provide a more detailed description of the embodiments and are not intended to limit the present invention.

[0041] Example 1

[0042] A preparation process for wear-resistant PVC composite material for galvanized iron wire tying wire, such as Figure 1 As shown, the following steps are included:

[0043] S1: Preparation of mesoporous hollow carbon nanospheres

[0044] S1.1: 350 parts by weight of ethanol were added to 50 parts by weight of deionized water, followed by addition of aqueous ammonia to adjust the pH to 8.5, and the mixture was stirred for 20 minutes. Then, 14 parts by weight of tetraethyl orthosilicate were added, and the mixture was stirred again for 20 minutes to obtain a mixed solution;

[0045] S1.2: 2 parts by weight of dopamine hydrochloride was added to the mixture, followed by stirring for 12 hours. After the reaction, the mixture was filtered and washed three times with ethanol and deionized water alternately. The washed product was dried at 80°C for 12 hours and finally calcined at 800°C for 2 hours in a nitrogen atmosphere. The calcined product was etched with 2M sodium hydroxide solution to obtain mesoporous hollow carbon nanospheres.

[0046] S2: Preparation of double-walled microcapsules

[0047] S2.1: Add oil-soluble copper nanoparticles to PAO6 and stir to obtain PAO6 containing 3 wt% oil-soluble copper nanoparticles. Then, add 2 wt% mesoporous hollow carbon nanospheres and ultrasonically disperse for 20 minutes. Then, transfer the dispersion to a device equipped with a vacuum pump and stir and impregnate under negative pressure for 20 minutes. After impregnation, centrifuge with petroleum ether and anhydrous ethanol, wash, and finally dry to obtain single-wall microcapsules.

[0048] S2.2: 4 parts by weight of zinc acetate, 120 parts by weight of anhydrous ethanol, 30 parts by weight of polyethylene glycol, and 16 parts by weight of sodium hydroxide were added to a hydrothermal reactor, and the mixture was reacted at 120°C for 12 hours. After natural cooling, the reactants were washed twice with deionized water and anhydrous ethanol alternately, and dried to obtain zinc oxide nanorods;

[0049] S2.3: 10.4 parts by weight of melamine, 21.4 parts by weight of a 37 wt% formaldehyde solution, 1.8 parts by weight of a 7 wt% triethanolamine solution, and 62.3 parts by weight of deionized water were mixed and stirred for 20 minutes, then the pH was adjusted to 8.5, and the mixture was stirred and reacted at 70° C. for 1 hour to obtain a prepolymer;

[0050] S2.4: Single-walled microcapsules and dopamine hydrochloride were added to a Tris buffer solution with a pH of 8.5 in a mass ratio of 1:0.4. The concentration of dopamine hydrochloride in the Tris buffer solution was 4 mg / mL. After stirring and mixing for 20 hours, the pH was adjusted to neutral. Prepolymer was added dropwise at a rate of 1 drop / s at a mass ratio of prepolymer to single-walled microcapsules of 1:1 at 50°C. After reacting for 45 minutes, the pH was adjusted to 5.4. After continuing the reaction for 20 minutes, zinc oxide nanorods were added and reacted for 3 hours. The mass ratio of zinc oxide nanorods to single-walled microcapsules was 0.3:1. After the reaction was completed, the mixture was filtered, washed, and dried to obtain double-walled microcapsules.

[0051] S3: Preparation of wear-resistant composites

[0052] S3.1: Dispersing 1 part by weight of carbon nanofibers in 100 parts by weight of deionized water, followed by adding 1 part by weight of PDA, adjusting the pH to 8.5 with Tris alkaline buffer, polymerizing the mixture under magnetic stirring at room temperature for 24 hours, and then washing twice with anhydrous ethanol to obtain modified carbon nanofibers;

[0053] S3.2: Disperse 1 part by weight of modified carbon nanofibers in 40 parts by weight of anhydrous ethanol, then add 2 parts by weight of aqueous ammonia, sonicate for 20 minutes, and then magnetically stir at 30°C for 20 minutes. Then, dropwise add 2.1 wt% of ethyl orthosilicate and 0.01 parts by weight of tridecafluorooctyltriethoxysilane, and react for 5 hours. Then, add 0.02 parts by weight of tridecafluorooctyltriethoxysilane, and react for 3 hours to obtain a wear-resistant composite.

[0054] S4: Preparation of wear-resistant composite materials

[0055] S4.1: 100 parts by weight of polyvinyl chloride resin, 20 parts by weight of chlorinated polyvinyl chloride, 20 parts by weight of calcium carbonate, 5 parts by weight of double-wall microcapsules, 12 parts by weight of wear-resistant composite, 5 parts by weight of titanium dioxide, 10 parts by weight of calcium zinc stabilizer, 0.5 parts by weight of antioxidant, 0.5 parts by weight of anti-ultraviolet absorber UV-531, and 2 parts by weight of zinc stearate are mixed to obtain a mixed material;

[0056] S4.2: Place the mixed material into a high-speed mixer and stir it at 80°C for 5 minutes. The stirred material is extruded into a mold through an extruder. The temperature of the extruder is set to 170°C and the screw speed is 20 r / min. The extruded material is cooled and pelletized to obtain a wear-resistant composite material.

[0057] The antioxidant is a mixture of antioxidant 1010 and antioxidant 1024 in a mass ratio of 1:2.

[0058] Example 2

[0059] A preparation process for wear-resistant PVC composite material for galvanized iron wire tying wire, such as Figure 1 As shown, the following steps are included:

[0060] S1: Preparation of mesoporous hollow carbon nanospheres

[0061] S1.1: 380 parts by weight of ethanol were added to 70 parts by weight of deionized water, followed by adjusting the pH to 8.5 with aqueous ammonia, and stirring for 20 minutes. Then, 16 parts by weight of tetraethyl orthosilicate were added, and stirring was continued for 20 minutes to obtain a mixed solution.

[0062] S1.2: 3 parts by weight of dopamine hydrochloride was added to the mixture, followed by stirring for 12 hours. After the reaction, the mixture was filtered and washed three times with ethanol and deionized water alternately. The washed product was dried at 80°C for 12 hours and finally calcined at 800°C for 2 hours in a nitrogen atmosphere. The calcined product was etched with 2M sodium hydroxide solution to obtain mesoporous hollow carbon nanospheres.

[0063] S2: Preparation of double-walled microcapsules

[0064] S2.1: Add oil-soluble copper nanoparticles to PAO6 and stir to obtain PAO6 containing 3 wt% oil-soluble copper nanoparticles. Then, add 3 wt% mesoporous hollow carbon nanospheres and ultrasonically disperse for 20 minutes. Then, transfer the dispersion to a device equipped with a vacuum pump and stir and impregnate under negative pressure for 20 minutes. After impregnation, centrifuge with petroleum ether and anhydrous ethanol, wash, and finally dry to obtain single-wall microcapsules.

[0065] S2.2: 5 parts by weight of zinc acetate, 130 parts by weight of anhydrous ethanol, 40 parts by weight of polyethylene glycol, and 18 parts by weight of sodium hydroxide were added to a hydrothermal reactor, and the mixture was reacted at 120°C for 12 hours. After natural cooling, the reactants were washed twice with deionized water and anhydrous ethanol alternately, and dried to obtain zinc oxide nanorods.

[0066] S2.3: 13.2 parts by weight of melamine, 23.1 parts by weight of a 37 wt% formaldehyde solution, 2.3 parts by weight of a 7 wt% triethanolamine solution, and 64.8 parts by weight of deionized water were mixed and stirred for 20 minutes, then the pH was adjusted to 9, and the mixture was stirred and reacted at 70° C. for 1 hour to obtain a prepolymer;

[0067] S2.4: Single-walled microcapsules and dopamine hydrochloride were added to a Tris buffer solution with a pH of 8.5 in a mass ratio of 2:0.6. The concentration of dopamine hydrochloride in the Tris buffer solution was 5 mg / mL. After stirring and mixing for 20 hours, the pH was adjusted to neutral. Prepolymer was added dropwise at a rate of 1 drop / s at a mass ratio of prepolymer to single-walled microcapsules of 1.5:1 at 50°C. After reacting for 45 minutes, the pH was adjusted to 6.2. After continuing the reaction for 20 minutes, zinc oxide nanorods were added and reacted for 3 hours. The mass ratio of zinc oxide nanorods to single-walled microcapsules was 0.5:1. After the reaction was completed, the mixture was filtered, washed, and dried to obtain double-walled microcapsules.

[0068] S3: Preparation of wear-resistant composites

[0069] S3.1: Dispersing 2 parts by weight of carbon nanofibers in 120 parts by weight of deionized water, adding 2 parts by weight of PDA, adjusting the pH to 8.5 with Tris alkaline buffer, polymerizing under magnetic stirring at room temperature for 24 hours, and then washing twice with anhydrous ethanol to obtain modified carbon nanofibers;

[0070] S3.2: 2 parts by weight of modified carbon nanofibers were dispersed in 50 parts by weight of anhydrous ethanol, followed by the addition of 3 parts by weight of aqueous ammonia, and the mixture was ultrasonicated for 20 minutes, followed by magnetic stirring at 30°C for 20 minutes. Then, 2.2 wt% of ethyl orthosilicate and 0.02 parts by weight of tridecafluorooctyltriethoxysilane were added dropwise and reacted for 5 hours. Then, 0.03 parts by weight of tridecafluorooctyltriethoxysilane was added and reacted for 3 hours to obtain a wear-resistant composite.

[0071] S4: Preparation of wear-resistant composite materials

[0072] S4.1: 120 parts by weight of polyvinyl chloride resin, 30 parts by weight of chlorinated polyvinyl chloride, 30 parts by weight of calcium carbonate, 8 parts by weight of double-wall microcapsules, 27 parts by weight of wear-resistant composite, 10 parts by weight of titanium dioxide, 12 parts by weight of calcium zinc stabilizer, 1 part by weight of antioxidant 1010 and antioxidant 1024 mixed in a mass ratio of 1:2-3, 1 part by weight of anti-ultraviolet absorber UV-531, and 3 parts by weight of zinc stearate are mixed uniformly to obtain a mixture;

[0073] S4.2: Place the mixed material into a high-speed mixer and stir it at 80°C for 5 minutes. The stirred material is extruded into a mold through an extruder. The temperature of the extruder is set to 170°C and the screw speed is 20 r / min. The extruded material is cooled and pelletized to obtain a wear-resistant composite material.

[0074] The antioxidant is a mixture of antioxidant 1010 and antioxidant 1024 in a mass ratio of 1:3.

[0075] Example 3

[0076] A preparation process for wear-resistant PVC composite material for galvanized iron wire tying wire, such as Figure 1 As shown, the following steps are included:

[0077] S1: Preparation of mesoporous hollow carbon nanospheres

[0078] S1.1: 350 parts by weight of ethanol were added to 50 parts by weight of deionized water, followed by addition of aqueous ammonia to adjust the pH to 8.5, and the mixture was stirred for 30 minutes. Then, 14 parts by weight of tetraethyl orthosilicate were added, and the mixture was stirred again for 30 minutes to obtain a mixed solution;

[0079] S1.2: 2 parts by weight of dopamine hydrochloride was added to the mixture, followed by stirring for 14 hours. After the reaction, the mixture was filtered and washed five times with ethanol and deionized water alternately. The washed product was dried at 85°C for 14 hours and finally calcined at 820°C for 3 hours in a nitrogen atmosphere. The calcined product was etched with 2M sodium hydroxide solution to obtain mesoporous hollow carbon nanospheres.

[0080] S2: Preparation of double-walled microcapsules

[0081] S2.1: Add oil-soluble copper nanoparticles to PAO6 and stir to obtain PAO6 containing 3 wt% oil-soluble copper nanoparticles. Then, add 2 wt% mesoporous hollow carbon nanospheres and ultrasonically disperse for 30 minutes. Then, transfer the dispersion to a device equipped with a vacuum pump and stir and impregnate under negative pressure for 30 minutes. After impregnation, centrifuge with petroleum ether and anhydrous ethanol, wash, and finally dry to obtain single-wall microcapsules.

[0082] S2.2: 4 parts by weight of zinc acetate, 120 parts by weight of anhydrous ethanol, 30 parts by weight of polyethylene glycol, and 16 parts by weight of sodium hydroxide were added to a hydrothermal reactor, and the mixture was reacted at 130°C for 15 hours. After natural cooling, the reactants were washed three times with deionized water and anhydrous ethanol alternately, and dried to obtain zinc oxide nanorods.

[0083] S2.3: 10.4 parts by weight of melamine, 21.4 parts by weight of a 37 wt% formaldehyde solution, 1.8 parts by weight of a 7 wt% triethanolamine solution, and 62.3 parts by weight of deionized water were mixed and stirred for 30 minutes, then the pH was adjusted to 8.5, and the mixture was stirred and reacted at 75° C. for 2 hours to obtain a prepolymer;

[0084] S2.4: Single-walled microcapsules and dopamine hydrochloride were added to a Tris buffer solution with a pH of 8.5 in a mass ratio of 1:0.4. The concentration of dopamine hydrochloride in the Tris buffer solution was 4 mg / mL. After stirring and mixing for 24 hours, the pH was adjusted to neutral. Prepolymer was added dropwise at a rate of 2 drops / s at a mass ratio of prepolymer to single-walled microcapsules of 1:1 at 55°C. After reacting for 50 minutes, the pH was adjusted to 5.4. After continuing the reaction for 30 minutes, zinc oxide nanorods were added and reacted for 4 hours. The mass ratio of zinc oxide nanorods to single-walled microcapsules was 0.3:1. After the reaction was completed, the mixture was filtered, washed, and dried to obtain double-walled microcapsules.

[0085] S3: Preparation of wear-resistant composites

[0086] S3.1: Dispersing 1 part by weight of carbon nanofibers in 100 parts by weight of deionized water, adding 1 part by weight of PDA, adjusting the pH to 8.5 with Tris alkaline buffer, polymerizing with magnetic stirring at room temperature for 28 hours, and then washing three times with anhydrous ethanol to obtain modified carbon nanofibers;

[0087] S3.2: Disperse 1 part by weight of modified carbon nanofibers in 40 parts by weight of anhydrous ethanol, then add 2 parts by weight of aqueous ammonia, sonicate for 30 minutes, and then magnetically stir at 34°C for 30 minutes. Then, dropwise add 2.1 wt% of ethyl orthosilicate and 0.01 parts by weight of tridecafluorooctyltriethoxysilane, and react for 6 hours. Then, add 0.02 parts by weight of tridecafluorooctyltriethoxysilane, and react for 4 hours to obtain a wear-resistant composite.

[0088] S4: Preparation of wear-resistant composite materials

[0089] S4.1: 100 parts by weight of polyvinyl chloride resin, 20 parts by weight of chlorinated polyvinyl chloride, 20 parts by weight of calcium carbonate, 5 parts by weight of double-wall microcapsules, 12 parts by weight of wear-resistant composite, 5 parts by weight of titanium dioxide, 10 parts by weight of calcium zinc stabilizer, 0.5 parts by weight of antioxidant 1010 and antioxidant 1024 mixed in a mass ratio of 1:2-3, 0.5 parts by weight of anti-ultraviolet absorber UV-531, and 2 parts by weight of zinc stearate are mixed uniformly to obtain a mixture;

[0090] S4.2: Place the mixed material into a high-speed mixer and stir it at 90°C for 10 minutes. The stirred material is extruded into a mold through an extruder. The temperature of the extruder is set to 190°C and the screw speed is 30 r / min. The extruded material is cooled and pelletized to obtain a wear-resistant composite material.

[0091] The antioxidant is a mixture of antioxidant 1010 and antioxidant 1024 in a mass ratio of 1:2.

[0092] Comparative Example 1

[0093] Compared with Example 1, the difference of Comparative Example 1 is that in Comparative Example 1, PAO6 containing 3 wt% oil-soluble copper nanoparticles in step S2.1 is replaced with paraffin oil, and the other steps remain unchanged to prepare the wear-resistant composite material, which is recorded as Comparative Example 1.

[0094] Comparative Example 2

[0095] Compared with Example 1, Comparative Example 2 is different in that the oil-soluble copper nanoparticles in step S2.1 are removed in Comparative Example 2, and the wear-resistant composite material is prepared with the remaining steps unchanged, which is recorded as Comparative Example 2.

[0096] Comparative Example 3

[0097] Compared with Example 1, the difference of Comparative Example 3 is that steps S2.2-S2.4 are removed in Comparative Example 3, the double-walled microcapsules in step S4.1 are replaced with the single-walled microcapsules described in step S2.1, and the remaining steps remain unchanged to prepare the wear-resistant composite material, which is recorded as Comparative Example 3.

[0098] Comparative Example 4

[0099] Compared with Example 1, Comparative Example 4 is different in that the wear-resistant composite material in steps S3 and S4.1 is removed from Comparative Example 4, and the wear-resistant composite material is prepared with the remaining steps unchanged, which is recorded as Comparative Example 4.

[0100] Comparative Example 5

[0101] Compared with Example 1, the difference of Comparative Example 5 is that step S3.2 is removed in Comparative Example 5, the wear-resistant composite material in S4.1 is replaced with the modified carbon nanofiber described in step S3.1, and the other steps remain unchanged to prepare the wear-resistant composite material, which is recorded as Comparative Example 5.

[0102] The wear-resistant composite materials prepared in Examples 1-3 and Comparative Examples 1-5 and commercially available polyvinyl chloride plastics were tested using an MZ-4062 reciprocating friction tester with a load of 1 kg, a reciprocating frequency of 60 times / min, and a wear detection interval of 25 minutes to conduct wear resistance tests. The test results are shown in Table 1.

[0103] Table 1. Wear resistance test results of wear-resistant composite materials of Examples 1-3 and Comparative Examples 1-5

[0104] Wear amount / mg Example 1 2.13 Example 2 2.11 Example 3 2.14 Comparative Example 1 3.74 Comparative Example 2 3.14 Comparative Example 3 4.37 Comparative Example 4 4.98 Comparative Example 5 3.87 Commercially available polyvinyl chloride plastic 5.43

[0105] As can be seen from the data in Table 1, the wear-resistant composite material prepared by the present invention has good wear resistance. As can be seen from the data in Comparative Examples 1-2, the wear resistance can be effectively improved by impregnating PAO6 loaded with oil-soluble copper nanoparticles into mesoporous hollow carbon nanospheres.

[0106] From the data of Comparative Example 3 and Figure 2 It can be seen that the prepared double-walled microcapsules have a "sea urchin-like" structure, which can further improve the wear resistance. This is because of its special structure of the tribochemical reaction film, thus effectively improving the wear resistance of the composite material.

[0107] From Comparative Examples 4-5 and Figure 3 It can be seen that the addition of the grape-structured wear-resistant composite material significantly improves the wear resistance of the composite material; the wear-resistant composite material prepared through the interaction between the components can significantly improve its wear resistance.

[0108] The tensile strength and tensile strain at break of the wear-resistant composite materials prepared in Examples 1-3 were tested. The test results are shown in Table 2.

[0109] Table 2. Tensile strength and tensile strain at break test results of Examples 1-3

[0110] Tensile strength MPa Tensile strain at break % Example 1 15.2 164 Example 2 15.3 162 Example 3 15.2 162

[0111] From the data in Table 2, it can be seen that the wear-resistant composite material prepared in the embodiment has a tensile strength greater than 12.5 MPa and a tensile strain at break greater than 150%, which meets the requirements.

[0112] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A preparation process for a wear-resistant PVC composite material for galvanized iron wire ties, characterized in that: The steps include: S1: Preparation of mesoporous hollow carbon nanospheres S2: Preparation of double-walled microcapsules PAO6 containing oil-soluble copper nanoparticles was loaded into mesoporous hollow carbon nanospheres to obtain single-wall microcapsules. The single-wall microcapsules were treated with dopamine hydrochloride and then reacted with a prepolymer prepared from melamine and formaldehyde and zinc oxide nanorods to obtain double-wall microcapsules. S3: Preparation of wear-resistant composites Carbon nanofibers were modified with PDA and then reacted with ethyl orthosilicate and tridecafluorooctyltriethoxysilane to prepare a wear-resistant composite. S4: Preparation of wear-resistant composite materials The wear-resistant composite material is prepared by using 100-120 parts by weight of polyvinyl chloride resin, 20-30 parts by weight of chlorinated polyvinyl chloride, 20-30 parts by weight of calcium carbonate, 5-8 parts by weight of double-wall microcapsules, 12-27 parts by weight of wear-resistant composite, 5-10 parts by weight of titanium dioxide, 10-12 parts by weight of plasticizer, 0.5-1 part by weight of antioxidant, 0.5-1 part by weight of anti-ultraviolet absorber and 2-3 parts by weight of zinc stearate.

2. The preparation process of a wear-resistant PVC composite material for galvanized iron wire ties according to claim 1, characterized in that: Step S1: Preparation of mesoporous hollow carbon nanospheres, specifically comprising the following steps: S1.1: Add 350-380 parts by weight of ethanol to 50-70 parts by weight of deionized water, then add aqueous ammonia to adjust the pH to 8.5, and stir for 20-30 minutes. Then, add 14-16 parts by weight of tetraethyl orthosilicate, and stir again for 20-30 minutes to obtain a mixed solution; S1.2: Add 2-3 parts by weight of dopamine hydrochloride to the mixed solution, then stir and react for 12-14 hours. After the reaction is completed, filter and wash alternately with ethanol and deionized water for 3-5 times. Dry the washed product at 80-85°C for 12-14 hours, and finally calcine at 800-820°C in a nitrogen atmosphere for 2-3 hours. Etch the calcined product with 2M sodium hydroxide solution to obtain mesoporous hollow carbon nanospheres.

3. The preparation process of a wear-resistant PVC composite material for galvanized iron wire ties according to claim 2, characterized in that: Step S2: Preparation of double-walled microcapsules, specifically comprising the following steps: S2.1: Adding oil-soluble copper nanoparticles to PAO6 and stirring to obtain PAO6 containing 3 wt% of oil-soluble copper nanoparticles, followed by adding 2-3 wt% of mesoporous hollow carbon nanospheres and ultrasonically dispersing for 20-30 minutes. The dispersion is then transferred to a device equipped with a vacuum pump and stirred and impregnated under negative pressure for 20-30 minutes. After impregnation, the dispersion is centrifuged with petroleum ether and anhydrous ethanol, washed, and finally dried to obtain single-wall microcapsules; S2.2: Add 4-5 parts by weight of zinc acetate, 120-130 parts by weight of anhydrous ethanol, 30-40 parts by weight of polyethylene glycol, and 16-18 parts by weight of sodium hydroxide to a hydrothermal reactor, and react at 120-130°C for 12-15 hours. After natural cooling, the reactants are washed alternately with deionized water and anhydrous ethanol 2-3 times, and dried to obtain zinc oxide nanorods; S2.3: 10.4-13.2 parts by weight of melamine, 21.4-23.1 parts by weight of a 37 wt% formaldehyde solution, 1.8-2.3 parts by weight of a 7 wt% triethanolamine solution, and 62.3-64.8 parts by weight of deionized water are mixed and stirred for 20-30 minutes, and then the pH is adjusted to 8.5-9, followed by stirring and reacting at 70-75° C. for 1-2 hours to obtain a prepolymer; S2.4: Add single-walled microcapsules and dopamine hydrochloride in a mass ratio of 1-2:0.4-0.6 to a Tris buffer solution with a pH of 8.

5. The concentration of dopamine hydrochloride in the Tris buffer solution is 4-5 mg / mL. After stirring and mixing for 20-24 hours, adjust the pH to neutral. At 50-55°C, add prepolymer at a rate of 1-2 drops / s. The mass ratio of prepolymer to single-walled microcapsules is 1-1.5:

1. After reacting for 45-50 minutes, adjust the pH to 5.4-6.

2. Continue to react for 20-30 minutes, then add zinc oxide nanorods and react for 3-4 hours. The mass ratio of zinc oxide nanorods to single-walled microcapsules is 0.3-0.5:

1. After the reaction is completed, filter, wash, and dry to obtain double-walled microcapsules.

4. The preparation process of the wear-resistant PVC composite material for galvanized iron wire ties according to claim 3, characterized in that: Step S3: Preparation of the wear-resistant composite material, specifically comprising the following steps: S3.1: Disperse 1-2 parts by weight of carbon nanofibers in 100-120 parts by weight of deionized water, then add 1-2 parts by weight of PDA, then adjust the pH value to 8.5 with Tris alkaline buffer, use magnetic stirring to polymerize at room temperature for 24-28 hours, and then wash with anhydrous ethanol 2-3 times to obtain modified carbon nanofibers; S3.2: Disperse 1-2 parts by weight of modified carbon nanofibers in 40-50 parts by weight of anhydrous ethanol, then add 2-3 parts by weight of ammonia water, ultrasonicate for 20-30 minutes, then magnetically stir at 30-34°C for 20-30 minutes, then add 2.1-2.2wt% of ethyl orthosilicate and 0.01-0.02 parts by weight of tridecafluorooctyltriethoxysilane and react for 5-6 hours, then add 0.02-0.03 parts by weight of tridecafluorooctyltriethoxysilane and react for 3-4 hours to obtain a wear-resistant composite.

5. The process for preparing the wear-resistant PVC composite material for galvanized iron wire ties according to claim 4, characterized in that: Step S4: Preparation of the wear-resistant composite material, specifically comprising the following steps: S4.1: 100-120 parts by weight of polyvinyl chloride resin, 20-30 parts by weight of chlorinated polyvinyl chloride, 20-30 parts by weight of calcium carbonate, 5-8 parts by weight of double-wall microcapsules, 12-27 parts by weight of wear-resistant composite, 5-10 parts by weight of titanium dioxide, 10-12 parts by weight of plasticizer, 0.5-1 part by weight of antioxidant, 0.5-1 part by weight of anti-ultraviolet absorber, and 2-3 parts by weight of zinc stearate are mixed to obtain a mixed material; S4.2: Place the mixed material into a high-speed mixer and stir it at a temperature of 80-90°C for 5-10 minutes. The stirred material is extruded into a mold through an extruder. The temperature of the extruder is set to 170-190°C and the screw speed is 20-30 r / min. The extruded material is cooled and pelletized to obtain a wear-resistant composite material.

6. The process for preparing the wear-resistant PVC composite material for galvanized iron wire ties according to claim 5, characterized in that: The antioxidant in step S4.1 is a mixture of antioxidant 1010 and antioxidant 1024 in a mass ratio of 1:2-3.

7. The process for preparing the wear-resistant PVC composite material for galvanized iron wire ties according to claim 5, characterized in that: The anti-ultraviolet absorber in step S4.1 is anti-ultraviolet absorber UV-531.

8. A wear-resistant PVC composite material for galvanized iron wire ties, characterized in that: The PVC composite material is prepared by the preparation process of the wear-resistant PVC composite material for galvanized iron wire ties according to any one of claims 1 to 7.

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