Wear-resistant anti-aging PVC (polyvinyl chloride) material and preparation method thereof

Abstract

The invention relates to the technical field of polyvinyl chloride materials, and discloses a wear-resistant anti-aging PVC (polyvinyl chloride) material and a preparation method thereof, the PVC material is prepared by taking polyvinyl chloride as a base material and a functional additive and the like as auxiliary materials through mixing and extrusion granulation processes, the preparation method comprises the following steps: firstly, loading nano-diamond on the surface of a halloysite nanotube to prepare the functional additive, and due to the existence of an intermediate agent, the compatibility of the functional additive and a polyvinyl chloride matrix can be improved, the functional additive can efficiently exert own advantages, and the enhancement of a polyvinyl chloride material is realized; according to the present invention, the nano-diamond can produce slight relative slippage on the halloysite nanotube surface to form the ball effect, reduce the friction coefficient and improve the wear resistance of the material, and in addition, the intermediate agent structure contains the hindered phenol anti-oxidation structure so as to improve the anti-oxidation aging performance of the polyvinyl chloride by capturing the free radical and interrupting the chain reaction.

Description

Technical Field

[0001] This invention relates to the field of polyvinyl chloride (PVC) materials technology, specifically to a wear-resistant and anti-aging PVC material and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is the world's third-largest general-purpose plastic in terms of production volume, after polyethylene and polypropylene. Since its industrial production, it has occupied a core position in various fields due to its unique molecular structure and performance advantages. The strongly polar chlorine atoms in its molecular chain endow the material with high rigidity, flame retardancy, and chemical corrosion resistance. However, a large amount of plasticizers, stabilizers, and other additives must be added during processing to improve its performance. These characteristics determine that PVC faces two major challenges in long-term use: insufficient abrasion resistance and the risk of oxidative degradation, which directly restricts the expansion of its application scenarios and the extension of its service life.

[0003] In existing technologies, the performance of polyvinyl chloride (PVC) is generally improved by adding additives. For example, adding nanomaterials can reduce the coefficient of friction and improve the wear resistance of PVC, while adding antioxidants can improve the antioxidant aging resistance of PVC. However, the main problem with additive modification is the compatibility issue between the additives and the PVC matrix. For example, nanomaterials have poor compatibility with PVC and are prone to agglomeration, making it difficult for the reinforcing effect of nanomaterials to be effectively exerted. Small molecule antioxidants may migrate, making it difficult to ensure the long-term effectiveness of antioxidant properties. Based on this, the present invention provides a PVC composite material that can solve the problems existing in the prior art. Summary of the Invention

[0004] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide a wear-resistant and anti-aging PVC material and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A wear-resistant and anti-aging PVC material, comprising the following components measured in parts by weight:

[0007]

[0008] The functional additive is boron nitride with nanodiamonds loaded on its surface.

[0009] As a further aspect of the present invention, the functionalized additive is prepared by the following method:

[0010] Step 1: Disperse halloysite nanotubes ultrasonically in an ethanol-water solution to form a halloysite nanotube dispersion.

[0011] Step 2: Disperse the nanodiamonds in an ethanol-water solution to form a nanodiamond dispersion.

[0012] Step 3: Add the intermediate agent to the halloysite nanotube dispersion, stir and mix evenly, then adjust the pH to 3-5, then raise the temperature to 60-70℃, and continue to keep warm and stir for 3-6 hours. Then add the nanodiamond dispersion. After the addition is complete, raise the temperature to 75-80℃, continue to keep warm for 6-9 hours, stop heating, cool down and discharge the material.

[0013] As a further aspect of the present invention, in step one, the mass fraction of the halloysite nanotube dispersion is 20-30%.

[0014] As a further aspect of the present invention, in step two, the mass fraction of the nanodiamond dispersion is 10-20%.

[0015] As a further aspect of the present invention, in step three, the intermediate agent is prepared by the following method:

[0016] Step A: Add 2,2'-thiobis(4-methyl-6-tert-butylphenol) to toluene, stir and mix well, place in an ice bath environment, then add diallyl carbamoyl chloride and triethylamine. After the addition is complete, remove from the ice bath and mechanically stir at 30-40℃ for 3-6 hours. Evaporate to remove the solvent, collect the crude product, purify it, and obtain the intermediate.

[0017] Step B: Add the intermediate and 3-mercaptopropyltrimethoxysilane to tetrahydrofuran. After the addition is complete, start stirring and mix thoroughly. Then add the photoinitiator to the mixture and irradiate it with ultraviolet light at a wavelength of 365 nm. Stop irradiation after 30-60 minutes, separate the crude product, and purify it.

[0018] As a further aspect of the present invention, in step A, the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to diallyl carbamoyl chloride is 1:1.

[0019] As a further aspect of the present invention, in step B, the molar ratio of the intermediate agent and 3-mercaptopropyltrimethoxysilane is 1:2.

[0020] As a further aspect of the present invention, in step three, the volume ratio of the halloysite nanotube dispersion to the nanodiamond dispersion is 1:0.1-0.3.

[0021] It should be noted that in the above technical solution, 2,2'-thiobis(4-methyl-6-tert-butylphenol) and diallyl carbamoyl chloride are first used as raw materials. The hydroxyl groups and acyl chloride substituents in their structures can undergo a condensation reaction under the action of the acid-binding agent triethylamine. By controlling the molar ratio of the two, an intermediate containing two equivalents of unsaturated alkenyl substituents in the structure is obtained. Then, under the action of a photoinitiator, the unsaturated alkenyl substituents of the intermediate undergo a "thiol-alkene" click reaction with the mercapto group in the structure of 3-mercaptopropyltrimethoxysilane to obtain an intermediate containing two equivalents of "trimethoxysilane".

[0022] Under acidic conditions, the methoxysilane of the intermediate agent hydrolyzes to form Si-OH, which condenses with the hydroxyl groups of halloysite nanotubes and nanodiamonds, respectively, thereby achieving the effect of loading nanodiamonds onto the surface of halloysite nanotubes and obtaining functionalized additives.

[0023] As a further embodiment of the present invention, the colorant is any one of calcium carbonate, titanium dioxide, or carbon black; the plasticizer is dioctyl phthalate or di(2-propylheptyl) phthalate; the heat stabilizer is calcium-zinc stabilizer or barium-zinc stabilizer; the lubricant is calcium stearate or polyethylene wax; and the processing aid is processing aid ACR.

[0024] A method for preparing a wear-resistant and anti-aging PVC material includes the following steps:

[0025] Step 1: Weigh all the raw materials according to the specified weight proportions, add them to a high-speed mixer, control the speed to 300-500 r / min, and stir and mix at a temperature of 80-100℃ for 20-40 minutes to obtain the precursor material.

[0026] The second step involves feeding the precursor material into a twin-screw extruder for melt extrusion. The temperatures of each zone are controlled sequentially as follows: Zone 1: 170-180℃, Zone 2: 180-190℃, Zone 3: 190-200℃, and Zone 4: 200-210℃. The screw speed is 50-60 rpm. PVC material can be obtained through the melt extrusion process.

[0027] The beneficial effects of this invention are:

[0028] This invention utilizes an intermediate agent to load nanodiamonds onto the surface of halloysite nanotubes, producing a functionalized additive. Firstly, the presence of the intermediate agent enables the formation of an organic transition layer between the functionalized additive and the polyvinyl chloride (PVC) matrix, improving their compatibility and allowing the functionalized additive to efficiently leverage its advantages as an inorganic additive, thereby reinforcing the PVC material. Secondly, the nanodiamonds exhibit slight relative slippage on the halloysite nanotube surface, creating a "ball bearing" effect, which effectively reduces the coefficient of friction and improves the material's wear resistance. Furthermore, the intermediate agent structure contains a hindered phenolic antioxidant structure, which can capture free radicals, interrupt the chain reaction, and improve the oxidative aging resistance of PVC.

[0029] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0031] Figure 1 This is an infrared analysis test image of the intermediate agent. Detailed Implementation

[0032] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Preparation Example

[0034] Preparation of functional additives:

[0035] Step 1: Disperse halloysite nanotubes ultrasonically in a 50% (v / v) ethanol aqueous solution to form a 20% (w / w) halloysite nanotube dispersion.

[0036] Step 2: Disperse the nanodiamonds in a 50% (v / v) ethanol aqueous solution to form a 10% (w / w) nanodiamond dispersion.

[0037] Step 3: Add 0.3g of intermediate agent to 10mL of halloysite nanotube dispersion, stir and mix evenly, then adjust the pH to 4, then raise the temperature to 65℃, and continue to keep warm and stir for 4h. Then add 2mL of nanodiamond dispersion. After the addition is complete, raise the temperature to 75℃, continue to keep warm for 8h, stop heating, cool down and discharge the material.

[0038] The intermediate agent is prepared using the following method:

[0039] Step A: Add 0.2 g of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to toluene, stir and mix well, and place in an ice bath environment. Then add 0.09 g of diallyl carbamoyl chloride and 0.05 g of triethylamine. After the addition is complete, remove from the ice bath and mechanically stir at 35°C for 4 h. Evaporate to remove the solvent, collect the crude product, and purify it to obtain the intermediate.

[0040] Step B: Add 0.1g of intermediate and 0.08g of 3-mercaptopropyltrimethoxysilane to tetrahydrofuran. After the addition is complete, start stirring and mix evenly. Then add 0.01g of benzoin dimethyl ether to the mixture and irradiate it with ultraviolet light at a wavelength of 365nm. After 40 minutes, stop irradiation, separate the crude product, and purify it.

[0041] Figure 1 This is the infrared analysis test pattern of the intermediate agent, where 3000–3100 cm⁻¹ -1 The characteristic absorption peak appearing at 1721 cm⁻¹ is attributed to the CH characteristic absorption peak of the benzene ring skeleton. -1 The characteristic absorption peak appearing at 1062 cm⁻¹ is attributed to the C=O characteristic absorption peak of the amine ester group. -1 The characteristic absorption peak appearing at this point is attributed to the characteristic absorption peak of Si-O.

[0042] Example 1

[0043] A wear-resistant and anti-aging PVC material, comprising the following components measured in parts by weight:

[0044]

[0045]

[0046] The method for preparing the PVC material includes the following steps:

[0047] Step 1: Weigh all the raw materials according to the specified weight proportions, add them to a high-speed mixer, control the speed at 300 r / min, and mix them at 80℃ for 40 minutes to obtain the precursor material.

[0048] The second step involves feeding the precursor material into a twin-screw extruder for melt extrusion. The temperatures of each zone are controlled sequentially as follows: Zone 1: 175℃, Zone 2: 185℃, Zone 3: 195℃, and Zone 4: 200℃. The screw speed is 50 rpm. PVC material can be obtained through the melt extrusion process.

[0049] The preparation method for the functional additives is shown in the preparation example, and the same applies to the following examples.

[0050] Example 2

[0051] A wear-resistant and anti-aging PVC material, comprising the following components measured in parts by weight:

[0052]

[0053] The method for preparing the PVC material includes the following steps:

[0054] Step 1: Weigh all the raw materials according to the specified weight proportions, add them to a high-speed mixer, control the speed at 400 r / min, and mix them at 90℃ for 30 minutes to obtain the precursor material.

[0055] The second step involves feeding the precursor material into a twin-screw extruder for melt extrusion. The temperatures of each zone are controlled sequentially as follows: Zone 1: 175℃, Zone 2: 185℃, Zone 3: 195℃, and Zone 4: 200℃. The screw speed is 50 rpm. PVC material can be obtained through the melt extrusion process.

[0056] Example 3

[0057] A wear-resistant and anti-aging PVC material, comprising the following components measured in parts by weight:

[0058]

[0059] The method for preparing the PVC material includes the following steps:

[0060] Step 1: Weigh all the raw materials according to the specified weight proportions, add them to a high-speed mixer, control the speed at 500 r / min, and mix them at 100℃ for 20 minutes to obtain the precursor material.

[0061] The second step involves feeding the precursor material into a twin-screw extruder for melt extrusion. The temperatures of each zone are controlled sequentially as follows: Zone 1: 175℃, Zone 2: 185℃, Zone 3: 195℃, and Zone 4: 200℃. The screw speed is 50 rpm. PVC material can be obtained through the melt extrusion process.

[0062] Comparative Example 1

[0063] A PVC material, which differs from Example 2 in that the functional additives are replaced with a mixture of halloysite nanotubes and nanodiamonds in a mass ratio of 10:1, otherwise the same.

[0064] Comparative Example 2

[0065] A PVC material, which differs from Example 2 in that the functional additives are removed, but otherwise it is the same.

[0066] Test case

[0067] The PVC materials used in the examples and comparative examples were injection molded into test strips that met specifications, and the following performance tests were conducted:

[0068] Tensile properties were tested according to standard GB / T 1040.1-2025; samples from the same batch were placed in an aging chamber at 120℃ and subjected to accelerated aging treatment for 24 hours before tensile properties were tested to evaluate antioxidant aging performance.

[0069] According to standard ASTM D3884, the specimen was placed on a grinding rotary test bench, the rotation speed was set to 60 r / min, the test specimen was rubbed, the load was 1000g, the grinding wheel was SC10, and the wear amount of the test specimen was tested after 5000 revolutions to evaluate the wear resistance.

[0070] The test results are shown in the table below:

[0071]

[0072]

[0073] Analysis and testing results show that the PVC material prepared in the embodiments of the present invention has good mechanical, antioxidant aging, and wear resistance properties. Replacing the functional additives with a mixture of halloysite nanotubes and nanodiamonds presents several problems. First, interface issues arise, preventing the inorganic materials from effectively utilizing their advantages and resulting in a poorer reinforcing effect. Second, the role of the intermediate agent is lost, making it difficult for relative slippage between the nanodiamonds and halloysite nanotubes, thus failing to reduce the coefficient of friction. This leads to a decline in the material's wear resistance and a significant reduction in its resistance to thermo-oxidative aging.

[0074] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0075] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A wear-resistant and anti-aging PVC material, characterized in that, Includes the following components measured in parts by weight: The functional additive is boron nitride with nanodiamonds loaded on its surface.

2. The wear-resistant and anti-aging PVC material according to claim 1, characterized in that, The functional additives are prepared using the following method: Step 1: Disperse halloysite nanotubes ultrasonically in an ethanol-water solution to form a halloysite nanotube dispersion. Step 2: Disperse the nanodiamonds in an ethanol-water solution to form a nanodiamond dispersion. Step 3: Add the intermediate agent to the halloysite nanotube dispersion, stir and mix evenly, then adjust the pH to 3-5, then raise the temperature to 60-70℃, and continue to keep warm and stir for 3-6 hours. Then add the nanodiamond dispersion. After the addition is complete, raise the temperature to 75-80℃, continue to keep warm for 6-9 hours, stop heating, cool down and discharge the material.

3. The wear-resistant and anti-aging PVC material according to claim 2, characterized in that, In step one, the mass fraction of the halloysite nanotube dispersion is 20-30%.

4. The wear-resistant and anti-aging PVC material according to claim 2, characterized in that, In step two, the mass fraction of the nanodiamond dispersion is 10-20%.

5. The wear-resistant and anti-aging PVC material according to claim 2, characterized in that, In step three, the intermediate agent is prepared using the following method: Step A: Add 2,2'-thiobis(4-methyl-6-tert-butylphenol) to toluene, stir and mix well, place in an ice bath environment, then add diallyl carbamoyl chloride and triethylamine. After the addition is complete, remove from the ice bath and mechanically stir at 30-40℃ for 3-6 hours. Evaporate to remove the solvent, collect the crude product, purify it, and obtain the intermediate. Step B: Add the intermediate and 3-mercaptopropyltrimethoxysilane to tetrahydrofuran. After the addition is complete, start stirring and mix thoroughly. Then add the photoinitiator to the mixture and irradiate it with ultraviolet light at a wavelength of 365 nm. Stop irradiation after 30-60 minutes, separate the crude product, and purify it.

6. The wear-resistant and anti-aging PVC material according to claim 5, characterized in that, In step A, the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to diallyl carbamoyl chloride is 1:

1.

7. The wear-resistant and anti-aging PVC material according to claim 5, characterized in that, In step B, the molar ratio of the intermediate agent to 3-mercaptopropyltrimethoxysilane is 1:

2.

8. The wear-resistant and anti-aging PVC material according to claim 2, characterized in that, In step three, the volume ratio of the halloysite nanotube dispersion to the nanodiamond dispersion is 1:0.1-0.

3.

9. The wear-resistant and anti-aging PVC material according to claim 1, characterized in that, The colorant is any one of calcium carbonate, titanium dioxide, or carbon black; the plasticizer is dioctyl phthalate or di(2-propylheptyl) phthalate; the heat stabilizer is calcium-zinc stabilizer or barium-zinc stabilizer; the lubricant is calcium stearate or polyethylene wax; and the processing aid is processing aid ACR.

10. A method for preparing the wear-resistant and anti-aging PVC material as described in claim 1, characterized in that, Includes the following steps: Step 1: Weigh all the raw materials according to the specified weight proportions, add them to a high-speed mixer, control the speed to 300-500 r / min, and stir and mix at a temperature of 80-100℃ for 20-40 minutes to obtain the precursor material. The second step involves feeding the precursor material into a twin-screw extruder for melt extrusion. The temperatures of each zone are controlled sequentially as follows: Zone 1: 170-180℃, Zone 2: 180-190℃, Zone 3: 190-200℃, and Zone 4: 200-210℃. The screw speed is 50-60 rpm. PVC material can be obtained through the melt extrusion process.

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