Anti-aging resin material and method for preparing the same

Abstract

The application discloses an anti-aging resin material and a preparation method thereof, and relates to the technical field of polymer materials. In the preparation of the anti-aging resin material, the titanium dioxide is reacted with 3-(N-allyl amino) propyl trimethoxysilane to obtain pre-modified titanium dioxide; the pre-modified titanium dioxide is reacted with 2-hydroxy-4-acryloyloxy benzophenone to obtain modified titanium dioxide; the polypropylene powder is reacted with 3-butenyl dichlorophosphate to obtain pre-modified polypropylene; the pre-modified polypropylene is reacted with safrole alcohol to obtain modified polypropylene; and the modified polypropylene is melt-blended with the modified titanium dioxide to be injection molded to obtain the anti-aging resin material. The anti-aging resin material prepared by the application has good anti-aging, flame-retardant and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an anti-aging resin material and its preparation method. Background Technology

[0002] Polypropylene is a high-performance, widely used polyolefin material. It is lightweight, chemically resistant, and easily recyclable. It is one of the most widely used and fastest-growing resins in the world, and is widely used in packaging, electrical appliances, and chemical industries.

[0003] In the polypropylene molecular chain, each repeating unit contains a tertiary carbon atom. Under aerobic conditions, only a small amount of ultraviolet radiation is needed to remove the hydrogen atom from the tertiary carbon atom, creating a highly reactive tertiary carbon free radical, which then undergoes various reactions such as chain growth, degradation, or cross-linking. The C-C bond energy in the polypropylene molecule is 350-400 kJ / mol, while the energy of ultraviolet radiation in sunlight is 300-420 kJ / mol, falling within a similar energy range. Therefore, sunlight exposure can induce polypropylene to form excited-state molecules, leading to molecular chain breakage and changes in its physical and mechanical properties. These changes typically manifest as changes in surface color, loss of luster, surface cracking, and porosity. Simultaneously, tensile strength, elongation at break, and impact strength decrease sharply, significantly shortening its service life. Furthermore, because polypropylene is composed of pure carbon and hydrogen elements, with a linear carbon-carbon single-bond structure, it is highly flammable, with a limiting oxygen index of only 17%.

[0004] Therefore, the present invention prepares an anti-aging resin material with good anti-aging properties and flame retardant properties. Summary of the Invention

[0005] The purpose of this invention is to provide an anti-aging resin material and its preparation method to solve the problems existing in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] An anti-aging resin material is obtained by melt blending modified polypropylene and modified titanium dioxide and then injection molding.

[0008] As an optimization, the modified polypropylene is prepared by reacting pre-modified polypropylene with Murraya paniculata alcohol.

[0009] As an optimization, the pre-modified polypropylene is prepared by reacting polypropylene powder with 3-butenyl dichlorophosphate.

[0010] As an optimization, the modified titanium dioxide is prepared by reacting pre-modified titanium dioxide with 2-hydroxy-4-acryloyloxybenzophenone.

[0011] As an optimization, the pre-modified titanium dioxide is prepared by reacting titanium dioxide with 3-(N-allylamino)propyltrimethoxysilane.

[0012] A method for preparing an anti-aging resin material includes the following preparation steps:

[0013] (1) Pre-modified titanium dioxide, 2-hydroxy-4-acryloyloxybenzophenone and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:(1.2~1.4):(10~12), stirred at 200~300r / min for 4~6h at room temperature, centrifuged at 8000~10000rpm for 10~12min, the precipitate is washed 2~4 times with anhydrous ethanol, and vacuum dried at 40~50℃ for 10~12h to obtain modified titanium dioxide;

[0014] (2) Premodified polypropylene, citronella alcohol, triethylamine and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(2~3):(1~1.5):(10~12), stirred at 60~70℃ and 200~300r / min for 10~12h, N,N-dimethylformamide is removed by rotary evaporation, washed with acetone 2~4 times, and vacuum dried at 40~50℃ for 10~12h to obtain modified polypropylene;

[0015] (3) Modified polypropylene, modified titanium dioxide and azobisisobutyronitrile are mixed evenly in a mass ratio of 1:(0.05~0.07):(0.002~0.004), added to a twin-screw extruder for melt blending, and injection molded using a vertical injection molding machine to obtain an anti-aging resin material.

[0016] As an optimization, the preparation steps of the pre-modified titanium dioxide in step (1) are as follows: titanium dioxide and 3-(N-allylamino)propyltrimethoxysilane hydrolysate are mixed evenly at a mass ratio of 1: (8~10), stirred at 65~75℃ and 200~300r / min for 3~5h, solvent is removed by rotary evaporation, and vacuum dried at 60~70℃ for 10~12h to obtain pre-modified titanium dioxide.

[0017] As an optimization, the preparation steps of the pre-modified polypropylene in step (2) are as follows: polypropylene powder, 3-butenyl dichlorophosphate, benzophenone and acetone are mixed evenly in a mass ratio of 1:(1.5~2):(0.2~0.3):(10~12). A UV lamp with a wavelength of 365nm and a light intensity of 45mW / cm2 is used as the light source. The UV light irradiation distance is 15cm and the irradiation time is 8~10min. The mixture is then centrifuged at 8000~10000rpm for 10~12min. The precipitate is washed 3~5 times with anhydrous ethanol and deionized water, and then vacuum dried at 40~50℃ for 10~12h to obtain the pre-modified polypropylene.

[0018] As an optimization, the melt blending process parameters in step (3) are: die head temperature 190℃, zone 1 temperature 200℃, zone 2 temperature 210℃, zone 3 temperature 220℃, zone 4 temperature 210℃, zone 5 temperature 220℃, and screw speed 100rpm.

[0019] As an optimization, the injection molding process parameters in step (3) are: zone 1 temperature 180℃, zone 2 temperature 195℃, nozzle temperature 175℃, and injection pressure 5MPa.

[0020] As an optimization, the preparation steps of the 3-(N-allylamino)propyltrimethoxysilane hydrolysate are as follows: 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol are mixed evenly at a mass ratio of 1:(2~3):(8~10), the pH is adjusted to 5 with glacial acetic acid, and hydrolyzed at room temperature for 3~4 hours to obtain the 3-(N-allylamino)propyltrimethoxysilane hydrolysate.

[0021] As an optimization, the titanium dioxide is rutile titanium dioxide with a particle size of 40 nm, purchased from Shanghai Mairui Biochemical Technology Co., Ltd.

[0022] As an optimization, the polypropylene powder is of type M800E and was purchased from Suzhou Zhikai Plastics Co., Ltd.

[0023] As an optimization, the reaction process of the pre-modified titanium dioxide is as follows:

[0024] .

[0025] As an optimization, the reaction process of the modified titanium dioxide is as follows:

[0026] .

[0027] As an optimization, the reaction process of the pre-modified polypropylene is as follows:

[0028] .

[0029] As an optimization, the reaction process of the modified polypropylene is as follows:

[0030] .

[0031] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0032] In preparing the anti-aging resin material, this invention involves reacting titanium dioxide with 3-(N-allylamino)propyltrimethoxysilane to obtain pre-modified titanium dioxide; reacting the pre-modified titanium dioxide with 2-hydroxy-4-acryloyloxybenzophenone to obtain modified titanium dioxide; reacting polypropylene powder with 3-butenyl dichlorophosphate to obtain pre-modified polypropylene; reacting the pre-modified polypropylene with citric acid alcohol to obtain modified polypropylene; and melt-blending the modified polypropylene with modified titanium dioxide and injection molding to obtain the anti-aging resin material.

[0033] First, titanium dioxide, as a nano-UV shielding agent, can stimulate the generation of conduction band electrons and corresponding holes when irradiated with wavelengths less than 387.5 nm. In this excited state, the electrons generated by light can recombine with the holes, converting light energy into heat energy or other forms of energy, thereby improving the material's anti-aging properties. Simultaneously, titanium dioxide, as a nanoparticle, possesses excellent mechanical properties; when mixed with polypropylene, it improves the mechanical properties of the anti-aging resin material. Furthermore, the reaction of titanium dioxide with 3-(N-allylamino)propyltrimethoxysilane improves the dispersibility of titanium dioxide in polypropylene while simultaneously attracting... By incorporating secondary amines, double bonds, and silicon, the secondary amine undergoes a Michael addition reaction with the double bonds on 2-hydroxy-4-acryloyloxybenzophenone, introducing benzophenone-based ultraviolet absorbing groups onto titanium dioxide. This allows the absorbed ultraviolet light to be released as heat, further enhancing the anti-aging properties of the resin material. Furthermore, the double bonds on the modified titanium dioxide react with those on the modified polypropylene under the action of an initiator, forming a cross-linked network structure, which further improves the mechanical properties of the anti-aging resin material. Simultaneously, the silicon in the modified titanium dioxide and the phosphorus in the modified polypropylene synergistically enhance flame retardancy, further improving the flame retardant properties of the anti-aging resin material.

[0034] Secondly, polypropylene powder and 3-butenyl dichlorophosphate undergo an ultraviolet grafting reaction under the action of a photoinitiator, introducing phosphoryl chloride groups onto the polypropylene. The addition of phosphorus improves the flame retardant properties of the anti-aging resin material. At the same time, the phosphoryl chloride groups can react with the hydroxyl groups on the arugula alcohol to introduce coumarin groups onto the polypropylene, which can absorb ultraviolet light in the range of 280~400nm, thereby improving the anti-aging properties of the anti-aging resin material. In addition, the arugula alcohol contains double bond groups, which, after reacting with the pre-modified polypropylene, introduce double bonds onto the polypropylene. These double bonds then react with the double bonds on the modified titanium dioxide to form a cross-linked network structure, thereby improving the mechanical properties of the anti-aging resin material. Detailed Implementation

[0035] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1: A method for preparing an anti-aging resin material, comprising the following preparation steps:

[0037] (1) Mix 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol at a mass ratio of 1:2:8 until homogeneous. Adjust the pH to 5 with glacial acetic acid and hydrolyze at room temperature for 3 hours to obtain a 3-(N-allylamino)propyltrimethoxysilane hydrolysate. Mix titanium dioxide and the 3-(N-allylamino)propyltrimethoxysilane hydrolysate at a mass ratio of 1:8 until homogeneous. Stir and react at 65°C and 200 r / min for 3 hours. The solvent was removed by evaporation, and the mixture was vacuum dried at 60℃ for 10 h to obtain pre-modified titanium dioxide. The pre-modified titanium dioxide, 2-hydroxy-4-acryloyloxybenzophenone, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.2:10. The mixture was stirred at 200 r / min for 4 h at room temperature, centrifuged at 8000 rpm for 10 min, and the resulting precipitate was washed twice with anhydrous ethanol and vacuum dried at 40℃ for 10 h to obtain modified titanium dioxide.

[0038] (2) Polypropylene powder, 3-butenyl dichlorophosphate, benzophenone and acetone were mixed evenly in a mass ratio of 1:1.5:0.2:10. An ultraviolet lamp with a wavelength of 365nm and a light intensity of 45mW / cm2 was used as the light source. The ultraviolet light irradiation distance was 15cm and the irradiation time was 8min. The mixture was centrifuged at 8000rpm for 10min. The precipitate was washed three times each with anhydrous ethanol and deionized water and dried under vacuum at 40℃ for 10h to obtain pre-modified polypropylene. Pre-modified polypropylene, citronellol, triethylamine and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2:1:10. The mixture was stirred at 60℃ and 200r / min for 10h. N,N-dimethylformamide was removed by rotary evaporation. The mixture was washed twice with acetone and dried under vacuum at 40℃ for 10h to obtain modified polypropylene.

[0039] (3) Modified polypropylene, modified titanium dioxide and azobisisobutyronitrile are mixed evenly at a mass ratio of 1:0.05:0.002 and added to a twin-screw extruder for melt blending. The die head temperature is 190℃, zone 1 temperature is 200℃, zone 2 temperature is 210℃, zone 3 temperature is 220℃, zone 4 temperature is 210℃, zone 5 temperature is 220℃, and the screw speed is 100rpm. The material is then injection molded using a vertical injection molding machine with zone 1 temperature of 180℃, zone 2 temperature of 195℃, nozzle temperature of 175℃, and injection pressure of 5MPa to obtain an anti-aging resin material.

[0040] Example 2: A method for preparing an anti-aging resin material, comprising the following preparation steps:

[0041] (1) 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol were mixed evenly at a mass ratio of 1:2.5:9, and the pH was adjusted to 5 with glacial acetic acid. The mixture was hydrolyzed at room temperature for 3.5 h to obtain a 3-(N-allylamino)propyltrimethoxysilane hydrolysate. Titanium dioxide and the 3-(N-allylamino)propyltrimethoxysilane hydrolysate were mixed evenly at a mass ratio of 1:9 and stirred at 70 °C and 250 r / min for 4 h. The solvent was removed by rotary evaporation, and the mixture was dried under vacuum at 65°C for 11 h to obtain pre-modified titanium dioxide. The pre-modified titanium dioxide, 2-hydroxy-4-acryloyloxybenzophenone, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.3:11. The mixture was stirred at 250 r / min for 5 h at room temperature, centrifuged at 9000 rpm for 11 min, and the resulting precipitate was washed three times with anhydrous ethanol and dried under vacuum at 45°C for 11 h to obtain modified titanium dioxide.

[0042] (2) Polypropylene powder, 3-butenyl dichlorophosphate, benzophenone and acetone were mixed evenly in a mass ratio of 1:1.8:0.25:11. A UV lamp with a wavelength of 365nm and a light intensity of 45mW / cm2 was used as the light source. The UV light irradiation distance was 15cm and the irradiation time was 9min. The mixture was then centrifuged at 9000rpm for 11min. The precipitate was washed 4 times each with anhydrous ethanol and deionized water and dried under vacuum at 45℃ for 11h to obtain pre-modified polypropylene. Pre-modified polypropylene, citronellol, triethylamine and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:2.5:1.2:11. The mixture was stirred at 65℃ and 250r / min for 11h. N,N-dimethylformamide was removed by rotary evaporation. The mixture was washed 3 times with acetone and dried under vacuum at 45℃ for 11h to obtain modified polypropylene.

[0043] (3) Modified polypropylene, modified titanium dioxide and azobisisobutyronitrile are mixed evenly in a mass ratio of 1:0.06:0.003 and added to a twin-screw extruder for melt blending. The die head temperature is 190℃, zone 1 temperature is 200℃, zone 2 temperature is 210℃, zone 3 temperature is 220℃, zone 4 temperature is 210℃, zone 5 temperature is 220℃, and the screw speed is 100rpm. The material is then injection molded using a vertical injection molding machine with zone 1 temperature of 180℃, zone 2 temperature of 195℃, nozzle temperature of 175℃, and injection pressure of 5MPa to obtain an anti-aging resin material.

[0044] Example 3: A method for preparing an anti-aging resin material, comprising the following preparation steps:

[0045] (1) 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol were mixed evenly at a mass ratio of 1:3:10. The pH was adjusted to 5 with glacial acetic acid, and hydrolyzed at room temperature for 4 h to obtain 3-(N-allylamino)propyltrimethoxysilane hydrolysate. Titanium dioxide and 3-(N-allylamino)propyltrimethoxysilane hydrolysate were mixed evenly at a mass ratio of 1:10, and stirred at 75℃ and 300 r / min for 5 h. The solvent was removed by evaporation, and the mixture was dried under vacuum at 70°C for 12 h to obtain pre-modified titanium dioxide. The pre-modified titanium dioxide, 2-hydroxy-4-acryloyloxybenzophenone, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.4:12. The mixture was stirred at 300 r / min for 6 h at room temperature, centrifuged at 10000 rpm for 12 min, and the resulting precipitate was washed four times with anhydrous ethanol and dried under vacuum at 50°C for 12 h to obtain modified titanium dioxide.

[0046] (2) Polypropylene powder, 3-butenyl dichlorophosphate, benzophenone and acetone were mixed evenly in a mass ratio of 1:2:0.3:12. A UV lamp with a wavelength of 365nm and a light intensity of 45mW / cm2 was used as the light source. The UV light irradiation distance was 15cm and the irradiation time was 10min. The mixture was then centrifuged at 10000rpm for 12min. The precipitate was washed 5 times each with anhydrous ethanol and deionized water and dried under vacuum at 50℃ for 12h to obtain pre-modified polypropylene. Pre-modified polypropylene, citronellol, triethylamine and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:3:1.5:12. The mixture was stirred at 70℃ and 300r / min for 12h. N,N-dimethylformamide was removed by rotary evaporation. The mixture was washed 4 times with acetone and dried under vacuum at 50℃ for 12h to obtain modified polypropylene.

[0047] (3) Modified polypropylene, modified titanium dioxide and azobisisobutyronitrile are mixed evenly at a mass ratio of 1:0.07:0.004 and added to a twin-screw extruder for melt blending. The die head temperature is 190℃, zone 1 temperature is 200℃, zone 2 temperature is 210℃, zone 3 temperature is 220℃, zone 4 temperature is 210℃, zone 5 temperature is 220℃, and the screw speed is 100rpm. The material is injection molded using a vertical injection molding machine with zone 1 temperature of 180℃, zone 2 temperature of 195℃, nozzle temperature of 175℃, and injection pressure of 5MPa to obtain an anti-aging resin material.

[0048] Comparative Example 1

[0049] The difference between the preparation method of the anti-aging resin material in Comparative Example 1 and Example 2 lies in step (1). Step (1) is modified as follows: 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol are mixed evenly at a mass ratio of 1:2.5:9, the pH is adjusted to 5 with glacial acetic acid, and hydrolyzed at room temperature for 3.5 h to obtain a 3-(N-allylamino)propyltrimethoxysilane hydrolysate; titanium dioxide and the 3-(N-allylamino)propyltrimethoxysilane hydrolysate are mixed evenly at a mass ratio of 1:9, stirred at 70°C and 250 r / min for 4 h, the solvent is removed by rotary evaporation, and the mixture is vacuum dried at 65°C for 11 h to obtain modified titanium dioxide. The remaining steps are the same as in Example 2.

[0050] Comparative Example 2

[0051] The difference between the preparation method of the anti-aging resin material in Comparative Example 2 and Example 2 lies in the absence of step (1). Step (3) is modified as follows: Modified polypropylene, titanium dioxide, and azobisisobutyronitrile are mixed evenly at a mass ratio of 1:0.06:0.003, and then melt-blended in a twin-screw extruder. The die head temperature is 190°C, zone 1 temperature is 200°C, zone 2 temperature is 210°C, zone 3 temperature is 220°C, zone 4 temperature is 210°C, zone 5 temperature is 220°C, and the screw speed is 100 rpm. Injection molding is performed using a vertical injection molding machine with zone 1 temperature of 180°C, zone 2 temperature of 195°C, nozzle temperature of 175°C, and injection pressure of 5 MPa to obtain the anti-aging resin material. The remaining steps are the same as in Example 2.

[0052] Comparative Example 3

[0053] The preparation method of the anti-aging resin material in Comparative Example 3 differs from that in Example 2 in that step (1) is omitted, and step (3) is modified as follows: Modified polypropylene is added to a twin-screw extruder for melt blending, with the die head temperature at 190°C, zone 1 temperature at 200°C, zone 2 temperature at 210°C, zone 3 temperature at 220°C, zone 4 temperature at 210°C, zone 5 temperature at 220°C, and screw speed at 100 rpm; injection molding is performed using a vertical injection molding machine with zone 1 temperature at 180°C, zone 2 temperature at 195°C, nozzle temperature at 175°C, and injection pressure at 5 MPa to obtain the anti-aging resin material. The remaining steps are the same as in Example 2.

[0054] Comparative Example 4

[0055] The difference between the preparation method of the anti-aging resin material in Comparative Example 4 and Example 2 lies in step (2). Step (2) is modified as follows: Polypropylene powder, 3-butenyl dichlorophosphate, benzophenone, and acetone are mixed evenly in a mass ratio of 1:1.8:0.25:11. An ultraviolet lamp with a wavelength of 365 nm and a light intensity of 45 mW / cm2 is used as the light source. The ultraviolet light irradiation distance is 15 cm, and the irradiation time is 9 min. The mixture is then centrifuged at 9000 rpm for 11 min. The resulting precipitate is washed four times each with anhydrous ethanol and deionized water, and then vacuum dried at 45 °C for 11 h to obtain modified polypropylene. The remaining steps are the same as in Example 2.

[0056] Comparative Example 5

[0057] The preparation method of the anti-aging resin material in Comparative Example 5 differs from that in Example 2 in that step (2) is omitted, and step (3) is modified as follows: Polypropylene, modified titanium dioxide, and azobisisobutyronitrile are mixed evenly at a mass ratio of 1:0.06:0.003, and then melt-blended in a twin-screw extruder. The die head temperature is 190°C, zone 1 temperature is 200°C, zone 2 temperature is 210°C, zone 3 temperature is 220°C, zone 4 temperature is 210°C, zone 5 temperature is 220°C, and the screw speed is 100 rpm. Injection molding is performed using a vertical injection molding machine with zone 1 temperature of 180°C, zone 2 temperature of 195°C, nozzle temperature of 175°C, and injection pressure of 5 MPa to obtain the anti-aging resin material. The remaining steps are the same as in Example 2.

[0058] Test Example 1

[0059] Mechanical properties and anti-aging properties testing:

[0060] The specific testing method is as follows:

[0061] Mechanical property testing method: The anti-aging resin materials prepared in each example and comparative example were used to prepare the same specimens according to GB / T1040.2-2006 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics". The tensile strength M of the specimens was tested using an Instron electronic universal testing machine at a test temperature of 25°C and a tensile speed of 50 mm / min.

[0062] Anti-aging performance test method: The anti-aging resin materials prepared in each example and comparative example were used to prepare identical specimens according to GB / T1040.2-2006 "Determination of tensile properties of plastics - Part 2: Test conditions for molding and extruded plastics". These specimens were then placed in a UV aging test chamber for UV aging experiments, with the temperature set at 60℃ and the UV radiation power at 50W / m². 2 The wavelength was 340 nm, the distance between the sample and the light source was 20 cm, and the aging time was 120 h. The tensile strength N of the sample was tested again. The performance degradation rate was calculated as (MN) / M×100%.

[0063] The results are shown in Table 1.

[0064] Table 1

[0065]

[0066] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 1 reveals that the anti-aging resin material prepared by this invention possesses excellent mechanical and anti-aging properties.

[0067] By comparison, the tensile strength of Examples 1-3 is greater than that of Comparative Examples 2 and 2-5, indicating that the double bonds on the modified titanium dioxide and the double bonds on the modified polypropylene react under the action of the initiator to form a cross-linked network structure, thereby improving the mechanical properties of the anti-aging resin material.

[0068] By comparison, the tensile strength of Examples 1-3 is greater than that of Comparative Example 3, indicating that titanium dioxide, as a nanoparticle, has good mechanical properties. When mixed with polypropylene, it further improves the mechanical properties of the anti-aging resin material.

[0069] By comparison, the performance degradation rate of Examples 1-3 was less than that of Comparative Examples 1-2, indicating that the reaction of titanium dioxide with 3-(N-allylamino)propyltrimethoxysilane improves the dispersibility of titanium dioxide in polypropylene and introduces secondary amine groups onto titanium dioxide. The secondary amine undergoes a Michael addition reaction with the double bond on 2-hydroxy-4-acryloyloxybenzophenone, introducing benzophenone-type ultraviolet absorbing groups onto titanium dioxide. The absorbed ultraviolet light is released in the form of heat energy, thereby improving the anti-aging performance of the anti-aging resin material.

[0070] By comparison, the performance degradation rate of Examples 1-3 was less than that of Comparative Example 3, indicating that titanium dioxide, as a nano-ultraviolet shielding agent, can stimulate the generation of conduction band electrons when the irradiation wavelength is less than 387.5 nm, and at the same time generate corresponding holes. Under this excited state, the electrons generated by light can recombine with the holes. In this process, light energy can be converted into heat energy or other forms of energy, thereby further improving the anti-aging performance of the material.

[0071] By comparison, the performance degradation rate of Examples 1-3 was less than that of Comparative Examples 4-5, indicating that the phosphoryl chloride group on the pre-modified polypropylene can react with the hydroxyl group on the ethanol. Introducing coumarin groups on polypropylene can absorb ultraviolet light of 280-400nm, thereby improving the anti-aging performance of the anti-aging resin material.

[0072] Test Example 2

[0073] Flame retardant performance test:

[0074] Limiting oxygen index test: The anti-aging resin materials obtained from each example and comparative example were used to prepare samples of the same size according to GB / T2406.2-2009 "Determination of burning behavior by oxygen index method for plastics - Part 2: Room temperature test", and the limiting oxygen index of the samples was tested using a limiting oxygen index meter.

[0075] Vertical burning test: The anti-aging resin materials obtained from each example and comparative example were made into 80mm×10mm×3.2mm specimens. The vertical burning test was carried out on the samples using a vertical burning tester in accordance with GB / T2408-2021 "Determination of the flammability of plastics - Horizontal and Vertical Methods".

[0076] The results are shown in Table 2.

[0077] Table 2

[0078]

[0079] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-5 in Table 2 shows that the anti-aging resin material prepared by the present invention has good flame retardant properties.

[0080] By comparing the limiting oxygen index and UL 94 rating of Examples 1-3 with those of Comparative Examples 2-3, it is demonstrated that the silicon element on the modified titanium dioxide and the phosphorus element on the modified polypropylene work together to retard flame, further improving the flame retardant performance of the anti-aging resin material.

[0081] By comparing the limiting oxygen index and UL 94 rating of Examples 1-3 with Comparative Example 5, it is demonstrated that polypropylene powder and 3-butenyl dichlorophosphate undergo a UV grafting reaction under the action of a photoinitiator, introducing phosphoryl chloride groups onto the polypropylene. During combustion, phosphorus can capture free radicals and block the combustion reaction, thereby improving the flame retardant properties of the anti-aging resin material.

[0082] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An anti-aging resin material, characterized in that, The anti-aging resin material is prepared by melt blending modified polypropylene with modified titanium dioxide and azobisisobutyronitrile and then injection molding. The modified polypropylene is prepared by reacting pre-modified polypropylene with Murraya paniculata alcohol. The pre-modified polypropylene is prepared by reacting polypropylene powder with 3-butenyl dichlorophosphate; The modified titanium dioxide is prepared by reacting pre-modified titanium dioxide with 2-hydroxy-4-acryloyloxybenzophenone; The pre-modified titanium dioxide is prepared by reacting titanium dioxide with 3-(N-allylamino)propyltrimethoxysilane.

2. A method for preparing an anti-aging resin material, characterized in that, The preparation steps include the following: (1) Pre-modified titanium dioxide, 2-hydroxy-4-acryloyloxybenzophenone and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(1.2~1.4):(10~12), stirred and reacted at room temperature for 4~6 hours, centrifuged, washed and dried to obtain modified titanium dioxide; (2) Premodified polypropylene, citronella alcohol, triethylamine and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(2~3):(1~1.5):(10~12), stirred and reacted at 60~70℃ for 10~12h, and then evaporated by rotary evaporation, washed and dried to obtain modified polypropylene; (3) Modified polypropylene, modified titanium dioxide and azobisisobutyronitrile are mixed evenly in a mass ratio of 1:(0.05~0.07):(0.002~0.004), added to a twin-screw extruder for melt blending, and injection molded using a vertical injection molding machine to obtain an anti-aging resin material.

3. The method for preparing an anti-aging resin material according to claim 2, characterized in that, The preparation steps of the pre-modified titanium dioxide in step (1) are as follows: titanium dioxide and 3-(N-allylamino)propyltrimethoxysilane hydrolysate are mixed evenly at a mass ratio of 1: (8~10), stirred and reacted at 65~75℃ for 3~5h, and then rotary evaporated and dried to obtain pre-modified titanium dioxide.

4. The method for preparing an anti-aging resin material according to claim 2, characterized in that, The preparation steps of the pre-modified polypropylene in step (2) are as follows: polypropylene powder, 3-butenyl dichlorophosphate, benzophenone and acetone are mixed evenly in a mass ratio of 1:(1.5~2):(0.2~0.3):(10~12), irradiated with ultraviolet light for 8~10 min, centrifuged, washed and dried to obtain pre-modified polypropylene.

5. The method for preparing an anti-aging resin material according to claim 2, characterized in that, The melt blending process parameters in step (3) are: die head temperature 190℃, zone 1 temperature 200℃, zone 2 temperature 210℃, zone 3 temperature 220℃, zone 4 temperature 210℃, zone 5 temperature 220℃, and screw speed 100rpm.

6. The method for preparing an anti-aging resin material according to claim 2, characterized in that, The injection molding process parameters in step (3) are: zone 1 temperature 180℃, zone 2 temperature 195℃, nozzle temperature 175℃, and injection pressure 5MPa.

7. The method for preparing an anti-aging resin material according to claim 3, characterized in that, The preparation steps of the 3-(N-allylamino)propyltrimethoxysilane hydrolysate are as follows: 3-(N-allylamino)propyltrimethoxysilane, deionized water, and anhydrous ethanol are mixed evenly in a mass ratio of 1:(2~3):(8~10), the pH is adjusted to 5 with glacial acetic acid, and hydrolyzed at room temperature for 3~4 hours to obtain the 3-(N-allylamino)propyltrimethoxysilane hydrolysate.

8. The method for preparing an anti-aging resin material according to claim 3, characterized in that, The titanium dioxide is rutile titanium dioxide with a particle size of 40 nm.

9. The method for preparing an anti-aging resin material according to claim 4, characterized in that, The polypropylene powder is of type M800E.

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