High-dispersion weather-resistant polypropylene fiber master batch as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a high-dispersion weather-resistant polypropylene fiber master batch as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with thionyl chloride to prepare an acylating chlorination hindered phenol antioxidant; the preparation method comprises the following steps: reacting acyl chloride groups with 2-methylallylamine to prepare an alkenylated hindered phenol antioxidant; the preparation method comprises the following steps: carrying out hydrolytic condensation reaction on gamma-aminopropyl trimethoxy silane and vinyl trimethoxy silane under the catalysis of acid to prepare polyhedral oligomeric silsesquioxane; reacting polyhedral oligomeric silsesquioxane with the epoxy modified nano-zinc oxide through amino groups on molecules to prepare nano-zinc oxide grafted POSS (Polyhedral Oligomeric Silsesquioxane); the preparation method comprises the following steps: mixing an alkenylated hindered phenol antioxidant, nano zinc oxide grafted POSS (Polyhedral Oligomeric Silsesquioxane), 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl 2-methacrylate, polypropylene and an initiator, and melting, so as to obtain the high-dispersion weather-resistant polypropylene fiber master batch.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and specifically relates to a highly dispersed weather-resistant polypropylene fiber masterbatch and a preparation method and application thereof. Background Art

[0002] Polypropylene fiber, also known as polypropylene fiber, is made by melt spinning polypropylene resin. It has the advantages of light texture and strong warmth retention, and is widely used in the field of textile fabrics. However, polypropylene has poor weather resistance and is easily affected by ultraviolet radiation and oxidation, which causes aging and reduces mechanical properties. The existing technology generally improves the weather resistance of polypropylene by adding weather-resistant components.

[0003] Chinese patent CN113845735B discloses a heat-resistant aging polypropylene composite material, which improves the dispersibility in the polypropylene resin matrix by adding a hybrid filler with a large specific surface area, thereby improving the heat-resistant aging of the polypropylene product. However, the hybrid filler and the polypropylene still have a physical effect, and the dispersibility of the filler in the polypropylene needs to be improved; Chinese patent CN112694664B discloses a circular economy polypropylene composition, which improves the thermal oxidation resistance and anti-ultraviolet performance of polypropylene by adding an ultraviolet absorber, a light stabilizer and an antioxidant. However, the raw materials are also simply physically mixed, and there is also the problem of poor performance caused by poor dispersibility. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a highly dispersed weather-resistant polypropylene fiber masterbatch to solve the problem of performance degradation caused by poor dispersion between weather-resistant materials and polypropylene in the prior art.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch comprises the following steps: Step 1, preparing an olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein the olefinic hindered phenol antioxidant comprises the following steps to prepare: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, adding dichlorothionyl dropwise under nitrogen protection, reacting after the addition is complete, and rotary evaporating after the reaction to obtain an acyl chloride hindered phenol antioxidant; S12, dissolving the acyl chloride hindered phenol antioxidant in dichloromethane, adding 2-methylallylamine and pyridine, reacting, and rotary evaporating after the reaction is complete to purify , dried to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and concentrated hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, reacted, after the reaction is completed, filtered, purified, and dried to obtain POSS (cage-type silsesquioxane); S22, POSS is dissolved in toluene, epoxy-modified nano zinc oxide is added, reacted, after the reaction is completed, filtered, washed, and dried to obtain nano zinc oxide grafted POSS; Step 2: polypropylene, olefinic hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, and initiator are mixed, melt-extruded, cooled, and pelletized to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0006] Preferably, in the step 1: when preparing the olefinic hindered phenol antioxidant, in S11, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, dichloromethane and dichlorothionyl is 3.5:(400-600):(1.7-2.2), and the reaction conditions are stirring and reflux reaction at 45-55°C under nitrogen protection for 4-6 hours.

[0007] Preferably, in the step 1: when preparing the olefinic hindered phenol antioxidant, in S12, the mass ratio of the chlorinated hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine is 29.7: (500-700): (7.5-8.5): (3-5), and the reaction conditions are to react at room temperature for 4-6 hours.

[0008] Preferably, in the step 1: when preparing nano zinc oxide grafted POSS, in S21, the mass ratio of deionized water, methanol, concentrated hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is (5-8): (160-180): (6-8): 12.5: 1.5, and the reaction conditions are stirring the reaction at 40-50° C. under nitrogen protection for 35-45 hours.

[0009] Preferably, the concentrated hydrochloric acid is 37 wt % hydrochloric acid (the mass percentage of hydrogen chloride in the hydrogen chloride aqueous solution is 37%).

[0010] Preferably, in the step 1: when preparing nano zinc oxide grafted POSS, in S22, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide is 66.4: (800-1200): (60.9-64.4), and the reaction conditions are sealed at 55-65°C for 8-12h.

[0011] Preferably, the epoxy-modified nano zinc oxide is prepared by the following steps: adding γ-glycidyloxypropyltrimethoxysilane to an ethanol aqueous solution, adding nano zinc oxide after ultrasonication, reacting, filtering, washing, and drying after the reaction to obtain epoxy-modified nano zinc oxide; wherein the mass ratio of γ-glycidyloxypropyltrimethoxysilane, ethanol aqueous solution, and nano zinc oxide is (8-12): (300-500): 8.1, and the reaction conditions are reacting at a temperature of 50-70°C for 4-6h.

[0012] Preferably, the ethanol aqueous solution is 90 wt % ethanol aqueous solution.

[0013] Preferably, in the step 2, the mass ratio of polypropylene, olefinic hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, and initiator is 100:(1-2):(1-2):(1-3):(0.1-0.4), and the melting temperature is 180-200°C.

[0014] Preferably, the initiator includes at least one of dicumyl peroxide and di-tert-butyl peroxide.

[0015] The present invention also discloses a highly dispersed weather-resistant polypropylene fiber masterbatch prepared by the method for preparing the highly dispersed weather-resistant polypropylene fiber masterbatch as described above.

[0016] An application of the above-mentioned highly dispersed weather-resistant polypropylene fiber masterbatch on weather-resistant polypropylene fiber.

[0017] Compared with the prior art, the present invention has the following beneficial effects: in the present invention, a weather-resistant component antioxidant and an ultraviolet absorber are used to compound to improve the weather resistance of polypropylene, and the heat-oxidative aging resistance and light-aging resistance of polypropylene can be improved; the antioxidant in the present invention is 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, which, as a hindered phenol antioxidant, can effectively capture peroxide free radicals during the polymer aging process, thereby terminating the oxidation process; the carboxyl group is converted into an acyl chloride group by reacting with thionyl chloride; and the acyl chloride group is reacted with 2-methylallylamine undergoes an acylation reaction to introduce an alkenyl group into the hindered phenol antioxidant molecule; the ultraviolet absorber in the present invention comprises an inorganic ultraviolet absorber and an organic ultraviolet absorber, wherein the inorganic ultraviolet absorber is nano zinc oxide, and the nano zinc oxide is epoxy-modified, and then the epoxy group reacts with the amino group on the POSS (cage silsesquioxane) molecule formed by hydrolysis and condensation reaction of γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane as raw materials to graft the nano zinc oxide onto the POSS molecule; the alkenyl group is introduced into the hindered phenol antioxidant molecule; the ultraviolet absorber in the present invention comprises an inorganic ultraviolet absorber and an organic ultraviolet absorber, wherein the inorganic ultraviolet absorber is nano zinc oxide, and the nano zinc oxide is epoxy-modified, and then the epoxy group reacts with the amino group on the POSS (cage silsesquioxane) molecule formed by hydrolysis and condensation reaction of γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane as raw materials to graft the nano zinc oxide onto the POSS molecule; Phenol antioxidant, nano zinc oxide grafted POSS, and organic ultraviolet absorber 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate are used as grafting monomers, and polypropylene is grafted and modified under the action of an initiator to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch; when the highly dispersed weather-resistant polypropylene fiber masterbatch is mixed with a polypropylene resin to prepare polypropylene materials such as polypropylene fibers, the high dispersion of the weather-resistant component can be achieved through the entanglement between polypropylene molecular chains, thereby achieving high weather resistance of the polypropylene; in the present invention, the nano zinc oxide not only acts as an ultraviolet absorber, but also can be used as an inorganic filler to improve the mechanical properties of the polypropylene; the inorganic core composed of a rigid Si-O alternately connected silicon oxygen skeleton in the POSS molecule can inhibit the chain movement of the polymer molecule and give the polymer material good thermal stability and mechanical properties; the synergistic effect of the nano zinc oxide and the POSS can further achieve the weather resistance of the polypropylene; in addition, the nano zinc oxide and the POSS can also improve the wear resistance of the polypropylene, thereby overcoming the problem of poor wear resistance of the polypropylene. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The present invention is a process flow chart for preparing highly dispersed weather-resistant polypropylene fiber masterbatch; Figure 2 It is a bar graph showing the measurement results of the tensile strength retention rate after light aging and the tensile strength retention rate after thermal oxidative aging of the highly dispersed weather-resistant polypropylene fiber masterbatch prepared in Examples 1-6 of the present invention and Comparative Examples 1-2 in the weather resistance test; Figure 3 This is a bar graph showing the wear rate measurement results of the highly dispersed weather-resistant polypropylene fiber masterbatch prepared in Examples 1-6 of the present invention and Comparative Examples 1-2 in the wear resistance test. DETAILED DESCRIPTION

[0019] Example 1 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein, the olefinic hindered phenol antioxidant comprises the following steps to prepare: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, dichloromethane and dichlorothionyl is 3.5:400:1.7, the adding time of dichlorothionyl is 30min, after the adding is completed, stirring and refluxing for 6h at 45°C and 100r / min under nitrogen protection, after the reaction is completed, removing the solvent dichloromethane and unreacted dichlorothionyl by rotary evaporation at 50°C. Sulfone, to obtain an acyl chloride hindered phenol antioxidant; S12, after dissolving the acyl chloride hindered phenol antioxidant in dichloromethane, add 2-methylallylamine and pyridine, the mass ratio of acyl chloride hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine is 29.7:500:7.5:3, react at room temperature for 4 hours, after the reaction is completed, remove the solvent dichloromethane by rotary evaporation at 30°C, wash the reaction product with deionized water, and place it in a 50°C drying oven for 24 hours to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after mixing deionized water, methanol and 37wt% hydrochloric acid, add γ-aminopropyltrimethoxysilane and vinyl The mass ratio of trimethoxysilane, deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 5:160:6:12.5:1.5. The mixture is stirred at 300r / min under nitrogen protection at 40°C for 45h. After the reaction, the mixture is filtered and the filter cake is washed with ethanol and recrystallized with dichloromethane. The crystals are dried in a vacuum drying oven at 60°C for 24h to obtain POSS. S22. POSS is dissolved in toluene and epoxy-modified nano zinc oxide is added. The mass ratio of POSS, toluene and epoxy-modified nano zinc oxide is 66.4:800:60.9. The mixture is sealed and reacted at 55°C for 12h. After the reaction, the mixture was filtered, washed with ethanol, and dried in a vacuum oven at 60°C for 24 hours to obtain nano zinc oxide grafted POSS; wherein the epoxy-modified nano zinc oxide was prepared by the following steps: γ-glycidyloxypropyltrimethoxysilane was added to a 90wt% ethanol aqueous solution, and ultrasonically hydrolyzed at a frequency of 50kHz for 30 minutes, and then nano zinc oxide was added, wherein the mass ratio of γ-glycidyloxypropyltrimethoxysilane, 90wt% ethanol aqueous solution, and nano zinc oxide was 10:400:8.1, and the mixture was reacted at 60°C for 5 hours. After the reaction, the mixture was filtered, washed with ethanol, and dried in a vacuum oven at 60°C for 24 hours to obtain epoxy-modified nano zinc oxide; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide is 100:1:1:1:0.1, and melt extrude at a melting temperature of 180°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0020] Example 2 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, prepare olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein, the olefinic hindered phenol antioxidant comprises the following steps to prepare: S11, dissolve 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, add dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, dichloromethane and dichlorothionyl is 3.5:600:2.2, the addition time of dichlorothionyl is 60min, after the addition is completed, under nitrogen protection, at a temperature of 55°C and a speed of 200r / min, the mixture is stirred for 2 hours. The mixture was stirred and refluxed at 50 ℃ for 4 hours. After the reaction was completed, the solvent dichloromethane and unreacted dichlorothionyl were removed by rotary evaporation at 50 ℃ to obtain an acyl chloride hindered phenol antioxidant; S12, after the acyl chloride hindered phenol antioxidant was dissolved in dichloromethane, 2-methylallylamine and pyridine were added. The mass ratio of the acyl chloride hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine was 29.7:700:8.5:5. The mixture was reacted at room temperature for 6 hours. After the reaction was completed, the solvent dichloromethane was removed by rotary evaporation at 30 ℃. The reaction product was washed with deionized water and dried in a drying oven at 50 ℃. Dry for 24 hours to obtain an olefinic hindered phenol antioxidant; wherein, the nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and 37wt% hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, the mass ratio of deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 8:180:8:12.5:1.5, under nitrogen protection, at a temperature of 50°C and a speed of 500r / min, the reaction is stirred for 35 hours, and after the reaction is completed, the reaction is filtered, After the filter cake is washed with ethanol, it is recrystallized with dichloromethane, and the crystals are placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain POSS; S22, POSS is dissolved in toluene, epoxy-modified nano zinc oxide is added, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide is 66.4:1200:64.4, and the reaction is sealed at 65°C for 8 hours. After the reaction is completed, it is filtered, washed with ethanol, and placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain nano zinc oxide grafted POSS; wherein the preparation method of the epoxy-modified nano zinc oxide is the same as that of Example 1; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, diisopropylbenzene peroxide and di-tert-butyl peroxide; the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, diisopropylbenzene peroxide and di-tert-butyl peroxide is 100:2:2:3:0.2:0.2; melt extrude at a melting temperature of 200°C; cool and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0021] Example 3 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein, the olefinic hindered phenol antioxidant comprises the following steps to prepare: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, dichloromethane and dichlorothionyl is 3.5:440:1.8, the adding time of dichlorothionyl is 45min, after the adding is completed, under nitrogen protection, at a temperature of 50°C and a speed of 150r / min The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the solvent dichloromethane and unreacted dichlorothionyl were removed by rotary evaporation at 50°C to obtain an acyl chloride hindered phenol antioxidant. S12. The acyl chloride hindered phenol antioxidant was dissolved in dichloromethane, and 2-methylallylamine and pyridine were added. The mass ratio of the acyl chloride hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine was 29.7:540:7.7:3.4. The mixture was reacted at room temperature for 5 hours. After the reaction was completed, the solvent dichloromethane was removed by rotary evaporation at 30°C. The reaction product was washed with deionized water and dried in a drying oven at 50°C. 24h, to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS comprises the following steps to prepare: S21, after deionized water, methanol and 37wt% hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, the mass ratio of deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 5.5:165:6.4:12.5:1.5, under nitrogen protection, at a temperature of 45°C, at a speed of 400r / min, stirring the reaction for 40h, after the reaction is completed, extract Filter, wash the filter cake with ethanol, recrystallize with dichloromethane, and dry the crystals in a vacuum oven at 60°C for 24 hours to obtain POSS; S22, dissolve POSS in toluene, add epoxy-modified nano zinc oxide, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide is 66.4:850:61.6, and react at 60°C for 10 hours. After the reaction is completed, filter, wash with ethanol, and dry in a vacuum oven at 60°C for 24 hours to obtain nano zinc oxide grafted POSS; wherein the preparation method of the epoxy-modified nano zinc oxide is the same as that of Example 1; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and di-tert-butyl peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and di-tert-butyl peroxide is 100:1.2:1.2:1.4:0.15, melt extrude at a melting temperature of 190°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0022] Example 4 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein, the olefinic hindered phenol antioxidant is prepared by the following steps: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, dichloromethane and dichlorothionyl is 3.5:480:1.9, the adding time of dichlorothionyl is 45min, after the adding is completed, under nitrogen protection, at a temperature of 50°C and a speed of 150r / min The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the solvent dichloromethane and unreacted dichlorothionyl were removed by rotary evaporation at 50°C to obtain an acyl chloride hindered phenol antioxidant; S12, after the acyl chloride hindered phenol antioxidant was dissolved in dichloromethane, 2-methylallylamine and pyridine were added. The mass ratio of the acyl chloride hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine was 29.7:580:7.9:3.8. The mixture was reacted at room temperature for 5 hours. After the reaction was completed, the solvent dichloromethane was removed by rotary evaporation at 30°C. The reaction product was washed with deionized water and dried in a drying oven at 50°C. Dry for 24 hours to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and 37wt% hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, the mass ratio of deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 6:170:6.8:12.5:1.5, under nitrogen protection, at a temperature of 45°C, at a speed of 400r / min, stirring and reacting for 40 hours, after the reaction is completed, filter , the filter cake was washed with ethanol, and then recrystallized with dichloromethane. The crystals were placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain POSS; S22, POSS was dissolved in toluene, epoxy-modified nano zinc oxide was added, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide was 66.4:900:62.3, and the reaction was sealed at 60°C for 10 hours. After the reaction was completed, it was filtered, washed with ethanol, and placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain nano zinc oxide grafted POSS; wherein the preparation method of the epoxy-modified nano zinc oxide is the same as that of Example 1; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide is 100:1.4:1.4:1.8:0.2, and melt extrude at a melting temperature of 190°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0023] Example 5 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; The olefinic hindered phenol antioxidant is prepared by the following steps: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, dichloromethane and dichlorothionyl is 3.5:520:2, the adding time of dichlorothionyl is 45min, after the adding is completed, stirring and refluxing for reaction for 5h at 50°C and 150r / min under nitrogen protection, after the reaction is completed, heating at 50°C The solvent dichloromethane and unreacted dichlorothionyl are removed by rotary evaporation to obtain an acylated hindered phenol antioxidant; S12, after dissolving the acylated hindered phenol antioxidant in dichloromethane, 2-methylallylamine and pyridine are added, the mass ratio of the acylated hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine is 29.7:620:8.1:4.2, and the reaction is carried out at room temperature for 5 hours. After the reaction is completed, the solvent dichloromethane is removed by rotary evaporation at 30°C, the reaction product is washed with deionized water, and then placed in a drying oven at 50°C for 24 hours to obtain an olefinic hindered phenol antioxidant. agent; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and 37wt% hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, the mass ratio of deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 7:170:7.2:12.5:1.5, under nitrogen protection, at a temperature of 45°C, at a speed of 400r / min, stirring and reacting for 40h, after the reaction is completed, suction filtration is performed, and the filter cake is washed with ethanol After washing, recrystallization is performed with dichloromethane, and the crystals are placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain POSS; S22, POSS is dissolved in toluene, epoxy-modified nano zinc oxide is added, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide is 66.4:1000:63, and the reaction is sealed at 60°C for 10 hours. After the reaction is completed, it is filtered, washed with ethanol, and placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain nano zinc oxide grafted POSS; wherein the preparation method of the epoxy-modified nano zinc oxide is the same as that of Example 1; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide is 100:1.6:1.6:2.2:0.3, melt extrude at a melting temperature of 190°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0024] Example 6 This embodiment discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein, the olefinic hindered phenol antioxidant comprises the following steps to prepare: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, dichloromethane and dichlorothionyl is 3.5:560:2.1, the adding time of dichlorothionyl is 45min, after the adding is completed, under nitrogen protection, at a temperature of 50°C and a speed of 150r / min The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the solvent dichloromethane and unreacted dichlorothionyl were removed by rotary evaporation at 50°C to obtain an acyl chloride hindered phenol antioxidant. S12. The acyl chloride hindered phenol antioxidant was dissolved in dichloromethane, and 2-methylallylamine and pyridine were added. The mass ratio of the acyl chloride hindered phenol antioxidant, dichloromethane, 2-methylallylamine and pyridine was 29.7:660:8.3:4.6. The mixture was reacted at room temperature for 5 hours. After the reaction was completed, the solvent dichloromethane was removed by rotary evaporation at 30°C. The reaction product was washed with deionized water and dried in a drying oven at 50°C for 2 hours. 4h, to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and 37wt% hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, the mass ratio of deionized water, methanol, 37wt% hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is 7.5:175:7.6:12.5:1.5, under nitrogen protection, at a temperature of 45°C, at a speed of 400r / min, stirring the reaction for 40h, after the reaction is completed, filter , the filter cake was washed with ethanol, and then recrystallized with dichloromethane. The crystals were placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain POSS; S22, POSS was dissolved in toluene, epoxy-modified nano zinc oxide was added, the mass ratio of POSS, toluene, and epoxy-modified nano zinc oxide was 66.4:1100:63.7, and the reaction was sealed at 60°C for 10 hours. After the reaction was completed, it was filtered, washed with ethanol, and placed in a vacuum drying oven at 60°C and dried for 24 hours to obtain nano zinc oxide grafted POSS; wherein the preparation method of the epoxy-modified nano zinc oxide is the same as that of Example 1; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, and diisopropylbenzene peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, and diisopropylbenzene peroxide is 100:1.8:1.8:2.6:0.35, and melt extrude at a melting temperature of 190°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0025] Comparative Example 1 This comparative example discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Step 1, preparing olefinic hindered phenol antioxidant and olefinic modified nano zinc oxide; wherein the olefinic hindered phenol antioxidant is prepared by the following steps: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, dichloromethane and dichlorothionyl is 3.5:400:1.7, and the amount of dichlorothionyl is added dropwise. The addition time is 30 minutes. After the dropwise addition is completed, the reaction is stirred and refluxed at 100r / min for 6 hours at 45°C under nitrogen protection. After the reaction is completed, the solvent dichloromethane and unreacted dichlorothionyl are removed by rotary evaporation at 50°C to obtain an acyl chloride hindered phenol antioxidant; S12, after dissolving the acyl chloride hindered phenol antioxidant in dichloromethane, 2-methylallylamine and pyridine are added, the acyl chloride hindered phenol antioxidant, dichloromethane, The mass ratio of 2-methylallylamine and pyridine is 29.7:500:6:3, and the reaction is carried out at room temperature for 4 hours. After the reaction is completed, the solvent dichloromethane is removed by rotary evaporation at a temperature of 30°C, and the reaction product is washed with deionized water and placed in a 50°C drying oven for 24 hours to obtain an olefinic hindered phenol antioxidant; wherein, the olefin-modified nano zinc oxide is prepared by the following steps: γ-methacryloxypropyltrimethoxysilane (KH570) is added to a 90wt% ethanol aqueous solution, ultrasonically hydrolyzed at a frequency of 50kHz for 30 minutes, and then nano zinc oxide is added. The mass ratio of γ-glycidyloxypropyltrimethoxysilane, 90wt% ethanol aqueous solution, and nano zinc oxide is 10:400:8.1, and the reaction is carried out at a temperature of 60°C for 5 hours. After the reaction is completed, the mixture is filtered, washed with ethanol, and then placed in a 60°C vacuum drying oven for 24 hours to obtain olefin-modified nano zinc oxide; Step 2: Mix polypropylene, alkenyl hindered phenol antioxidant, alkenyl modified nano zinc oxide, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide, wherein the mass ratio of polypropylene, alkenyl hindered phenol antioxidant, alkenyl modified nano zinc oxide, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate and diisopropylbenzene peroxide is 100.5:1:0.5:1:0.1, melt extrude, the melting temperature is 180°C, cool, and pelletize to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0026] Comparative Example 2 This comparative example discloses a method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, comprising the following steps: Polypropylene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, nano zinc oxide, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl 2-methacrylate and dicumyl peroxide are mixed, and the mass ratio of polypropylene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, nano zinc oxide, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl 2-methacrylate and dicumyl peroxide is 100.6:0.9:0.5:1:0.1. The mixture is melt-extruded at a melting temperature of 180°C, cooled, and pelletized to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

[0027] In the above embodiments and comparative examples: 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 20170-32-5; 2-methylallylamine was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 2878-14-0; γ-aminopropyltrimethoxysilane was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 13822-56-5; vinyltrimethoxysilane was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No. 2768-02-7; γ-glycidyloxypropyltrimethoxy Silane was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 2530-83-8; 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate was purchased from BASF (Shanghai) Biopharmaceutical Technology Co., Ltd., CAS No.: 96478-09-0; Nano zinc oxide was purchased from Shanghai Yaotian New Materials Technology Co., Ltd., item No.: YT-Oy-02-1, average particle size: 20 nm; Polypropylene is a polypropylene homopolymer purchased from Shanghai Jiejun Plastic Technology Co., Ltd., brand: pt231, specific gravity: 0.901 g / cm 3 , melt flow rate (230℃ / 2.16kg): 26g / 10min.

[0028] Test Case The highly dispersed weather-resistant polypropylene fiber masterbatches prepared in Examples 1-6 and Comparative Examples 1-2 were respectively mixed with polypropylene resin in a mass ratio of 50%:50%, and samples to be tested were prepared by an injection molding machine, wherein the polypropylene resin was the same as the polypropylene resin in Examples 1-6 and Comparative Examples 1-2; (1) Weathering performance test: With reference to standard ISO527-1-2012, the tensile strength of each newly prepared sample to be tested, the tensile strength of each sample to be tested after 1000 hours of ultraviolet irradiation at UVA340nm, and the tensile strength of the sample to be tested after 1000 hours of thermal oxidative aging at 140°C were measured. The tensile speed was 10mm / min, and the tensile strength retention rate after light aging and the tensile strength retention rate after thermal oxidative aging were calculated. The measurement results are shown in Table 1:

[0029] As shown in Table 1, the highly dispersed weather-resistant polypropylene fiber masterbatch prepared by the present invention can effectively improve the weather resistance of polypropylene, thereby improving the light aging resistance and heat-oxidative aging resistance of polypropylene. After the antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the inorganic ultraviolet absorber are modified to introduce alkenyl groups, the organic ultraviolet absorber 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate containing alkenyl groups is used as a grafting monomer to graft-modify polypropylene, thereby achieving high dispersion of the weather-resistant component in the polypropylene resin, thereby making the polypropylene have excellent weather resistance. Compared with Example 1, in Comparative Example 1, POSS was not introduced, and the mechanical properties and thermal stability of polypropylene decreased, that is, the tensile strength of the newly prepared sample to be tested and the tensile strength retention rate after thermal oxidative aging were both reduced; in Comparative Example 2, POSS was not introduced, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and nano zinc oxide were not grafted into the polypropylene molecules, and the dispersibility decreased. Compared with Comparative Example 1, the tensile strength of the newly prepared sample to be tested and the tensile strength retention rate after thermal oxidative aging were further reduced, and the tensile strength retention rate after light aging was also reduced.

[0030] (2) Wear resistance test: The wear rate of the sample to be tested was measured according to the reference standard GB / T3960-2016 (test conditions: 200N force, 2h). The test results are shown in Table 2:

[0031] As can be seen from Table 2, the highly dispersed weather-resistant polypropylene fiber masterbatch prepared by the present invention can also effectively improve the wear resistance of polypropylene materials. Nano zinc oxide can improve the weather resistance and mechanical properties of polypropylene while also improving the wear resistance of polypropylene; not only can POSS molecules connect nano zinc oxide and polypropylene, improve the dispersibility of nano zinc oxide in polypropylene, improve the thermal stability and mechanical properties of polymer materials, but also improve the wear resistance of polypropylene. Compared with Example 1, in Comparative Example 1, POSS was not introduced, and the wear resistance of polypropylene was reduced; in Comparative Example 2, POSS was not introduced, and nano zinc oxide was not grafted into polypropylene molecules, the dispersibility decreased, and compared with Comparative Example 1, the wear resistance of polypropylene was further reduced.

[0032] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch, characterized in that: The following steps are involved: Step 1, preparing an olefinic hindered phenol antioxidant and nano zinc oxide grafted POSS; wherein the olefinic hindered phenol antioxidant comprises the following steps of preparing: S11, dissolving 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in dichloromethane, adding dichlorothionyl under nitrogen protection, reacting after the addition is complete, and rotary evaporating after the reaction to obtain an acyl chloride hindered phenol antioxidant; S12, dissolving the acyl chloride hindered phenol antioxidant in dichloromethane, adding 2-methylallylamine and pyridine, reacting, and after the reaction is complete, Rotary evaporation, purification, and drying are performed to obtain an olefinic hindered phenol antioxidant; wherein, nano zinc oxide grafted POSS is prepared by the following steps: S21, after deionized water, methanol and concentrated hydrochloric acid are mixed, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane are added, reacted, after the reaction is completed, suction filtration, purification, and drying are performed to obtain POSS; S22, POSS is dissolved in toluene, epoxy-modified nano zinc oxide is added, reacted, after the reaction is completed, filtered, washed, and dried to obtain nano zinc oxide grafted POSS; Step 2: polypropylene, olefinic hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methacrylate, and initiator are mixed, melt-extruded, cooled, and pelletized to obtain a highly dispersed weather-resistant polypropylene fiber masterbatch.

2. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 1, characterized in that: In the step 1, when preparing the olefinic hindered phenol antioxidant, in S11, the mass ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, dichloromethane and dichlorothionyl is 3.5:(400-600):(1.7-2.2), and the reaction conditions are stirring and reflux reaction at 45-55° C. under nitrogen protection for 4-6 hours.

3. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 1, characterized in that: In the step 1, when preparing the olefinic hindered phenol antioxidant, in S12, the mass ratio of the chlorinated hindered phenol antioxidant, dichloromethane, 2-methylallylamine, and pyridine is 29.7: (500-700): (7.5-8.5): (3-5), and the reaction conditions are to react at room temperature for 4-6 hours.

4. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 1, characterized in that: In the step 1: when preparing nano zinc oxide grafted POSS, in S21, the mass ratio of deionized water, methanol, concentrated hydrochloric acid, γ-aminopropyltrimethoxysilane and vinyltrimethoxysilane is (5-8): (160-180): (6-8): 12.5: 1.5, and the reaction conditions are stirring the reaction at 40-50° C. for 35-45 hours under nitrogen protection.

5. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 1, characterized in that: In the step 1, when preparing nano zinc oxide grafted POSS, in S22, the mass ratio of toluene and epoxy modified nano zinc oxide is 66.4: (800-1200): (60.9-64.4), and the reaction conditions are sealed at 55-65° C. for 8-12 hours.

6. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 5, characterized in that: The epoxy-modified nano zinc oxide is prepared by the following steps: adding γ-glycidyloxypropyltrimethoxysilane to an ethanol aqueous solution, after ultrasonication, adding nano zinc oxide, reacting, filtering, washing, and drying after the reaction is completed to obtain the epoxy-modified nano zinc oxide; wherein the mass ratio of γ-glycidyloxypropyltrimethoxysilane, the ethanol aqueous solution, and the nano zinc oxide is (8-12): (300-500): 8.1, and the reaction conditions are reacting at a temperature of 50-70° C. for 4-6 hours.

7. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 1, characterized in that: In the step 2, the mass ratio of polypropylene, olefinic hindered phenol antioxidant, nano zinc oxide grafted POSS, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl 2-methylacrylate, and initiator is 100:(1-2):(1-2):(1-3):(0.1-0.4), and the melting temperature is 180-200°C.

8. The method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch according to claim 7, characterized in that: The initiator includes at least one of dicumyl peroxide and di-tert-butyl peroxide.

9. A highly dispersed weather-resistant polypropylene fiber masterbatch prepared by the method for preparing a highly dispersed weather-resistant polypropylene fiber masterbatch as described in any one of claims 1 to 8.

10. Use of the highly dispersed weather-resistant polypropylene fiber masterbatch as claimed in claim 9 on weather-resistant polypropylene fiber.

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