Hydrophilic modified PVC film and preparation method thereof

Abstract

The invention discloses a hydrophilic modified PVC film and a preparation method thereof, and relates to the field of high polymer materials. When the hydrophilic modified PVC film is prepared, 2, 4-dihydroxybenzophenone and allyl succinic anhydride react to prepare a modified ultraviolet absorbent; the preparation method comprises the following steps: modifying a phase change microcapsule with allyltrimethoxysilane, and reacting with a modified ultraviolet absorbent, allylsuccinic anhydride and 8-chloro-1-octylene to obtain a modified microcapsule; reacting the iodine-terminated polyvinyl chloride with allyl polyethylene glycol and N, N-dimethylaminoethyl methacrylate to prepare hydrophilic polyvinyl chloride; the modified phase change microcapsules, triphenyl phosphate and a liquid calcium-zinc stabilizer are mixed and pressed to prepare the composite material. The hydrophilic modified PVC film prepared by the preparation method disclosed by the invention has excellent hydrophilic performance and good antibacterial and anti-ultraviolet aging performance.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, in particular to a hydrophilic modified PVC film and a preparation method thereof. Background Art

[0002] From its discovery to its application, plastics have become an important material that cannot be lacking in people's daily production and life as well as social and economic development. Polyvinyl chloride is one of the five general-purpose plastics. It has the advantages of excellent mechanical properties, low price, flame retardancy, wear resistance, electrical insulation, chemical corrosion resistance, and easier processing than other granular resins. It is widely used in industry, agriculture, construction, daily chemicals, packaging, toys, medical devices and other fields.

[0003] Polyvinyl chloride film is a polyvinyl chloride resin and functional processing aids such as plasticizers, stabilizers, lubricants, etc., which are made by calendering or blow molding. PVC film has excellent properties such as corrosion resistance and wear resistance, and the production cost of PVC is low, so PVC film is widely used in packaging, building materials, cables, packaging, medical hygiene and other fields. However, PVC film has poor hydrophilicity and is prone to aging when exposed to outdoor sunlight for a long time. The hydrophilic modified PVC film prepared by the present invention has excellent hydrophilicity, good antibacterial and anti-ultraviolet aging properties, and has good market prospects. Summary of the invention

[0004] The object of the present invention is to provide a hydrophilic modified PVC film and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A hydrophilic modified PVC film is prepared by reacting 2,4-dihydroxybenzophenone with allyl succinic anhydride to obtain a modified ultraviolet absorber; modifying a phase change microcapsule with allyl trimethoxysilane and then reacting the modified ultraviolet absorber, allyl succinic anhydride and 8-chloro-1-octene to obtain a modified phase change microcapsule; reacting iodine-terminated polyvinyl chloride with allyl polyethylene glycol and N,N-dimethylaminoethyl methacrylate to obtain a hydrophilic polyvinyl chloride; and mixing and pressing the modified phase change microcapsule with triphenyl phosphate and a liquid calcium zinc stabilizer to obtain a hydrophilic modified PVC film.

[0007] A method for preparing a hydrophilic modified PVC film comprises the following preparation steps:

[0008] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene are mixed in a mass ratio of 1: (0.5-0.7): (0.04-0.06): (20-30), and stirred at room temperature at 400-600 r / min for 1-2 hours to prepare a modified ultraviolet absorber;

[0009] (2) Mix phase change microcapsules, allyltrimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol in a mass ratio of 1: (0.3-0.5): (4-6): (13-17), stir at 250-350 r / min for 20-30 min at room temperature, add 0.2-0.4 times the mass of the phase change microcapsules modified ultraviolet absorber, 0.1-0.2 times the mass of the phase change microcapsules 8-chloro-1-octene, and 0.02-0.04 times the mass of the phase change microcapsules azobisisobutyronitrile, stir at 400-600 r / min for 1-2 h at 40-50° C., filter, wash the filter residue with anhydrous ethanol for 3-5 times, and vacuum dry at 45-55° C. for 4-6 h to obtain modified phase change microcapsules;

[0010] (3) Mix iodomethane, hydroxypropyl cellulose, methyl cellulose and deionized water in a mass ratio of 1:

[0011] (0.075-0.079): (0.03-0.035): (100-120) were added to the reaction kettle and mixed. Under a nitrogen atmosphere, 35-45 times the mass of methyl iodide of vinyl chloride was added. The mixture was stirred at 600-800 r / min for 25-35 min at 33-37 ° C. A mixed solution of sodium persulfate and sodium bicarbonate with a mass of 0.5-0.6 times the mass of methyl iodide was added. The mixture was stirred for 8-12 h to obtain iodine-terminated polyvinyl chloride. The iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N, N-dimethylaminoethyl methacrylate, Tween-60, and cyclohexanone are added into a reaction kettle in a mass ratio of 1: (0.2-0.4): (1.5-2.5): (0.04-0.06): (10-15) and mixed evenly; stirred at 30-40°C and 600-800 r / min for 25-35 min under a nitrogen atmosphere; a mixed solution of sodium persulfate and sodium bicarbonate in an amount of 2-3 times the mass of iodine-terminated polyvinyl chloride is added; stirred for 8-12 h to obtain hydrophilic polyvinyl chloride;

[0012] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1: (0.2-0.4): (0.06-0.08): (0.08-0.1), mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0013] As an optimization, the phase change microcapsules in step (2) are phase change microcapsules with silica composite methyl methacrylate-acrylic acid as wall material and paraffin as core material, which were purchased from Xi'an Qiyue Biotechnology Co., Ltd.

[0014] As an optimization, the preparation method of the mixed solution of sodium persulfate and sodium bicarbonate in step (3) is: sodium persulfate, sodium bicarbonate, and deionized water are mixed in a mass ratio of 1: (0.26-0.27): (3-3.4).

[0015] As an optimization, the allyl polyethylene glycol in step (3) is APEG-700 allyl polyvinyl chloride, which was purchased from Hai'an Petrochemical Plant in Jiangsu Province.

[0016] As an optimization, the liquid calcium zinc stabilizer in step (4) is an industrial grade liquid calcium zinc stabilizer purchased from Jinan Xiangfeng Weiye Chemical Co., Ltd.

[0017] As an optimization, the temperature of the double rolls of the double roll rubber mixer in step (4) is 160° C., and the mixing time is 6 to 8 minutes.

[0018] As an optimization, the film pressing method of the flat vulcanizer in step (4) is: preheating to a temperature of 170°C, hot pressing at a pressure of 1.5 MPa for 6 minutes, cooling to 80°C and then maintaining the pressure for cold pressing for 30 minutes, and naturally cooling to room temperature before taking out.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] When preparing the hydrophilic modified PVC film, the present invention comprises the following steps: reacting 2,4-dihydroxybenzophenone with allyl succinic anhydride to obtain a modified ultraviolet absorber; modifying a phase-change microcapsule with allyl trimethoxysilane and then reacting the modified ultraviolet absorber, allyl succinic anhydride and 8-chloro-1-octene to obtain a modified phase-change microcapsule; reacting iodine-terminated polyvinyl chloride with methyl iodide and vinyl chloride to obtain iodine-terminated polyvinyl chloride; reacting iodine-terminated polyvinyl chloride with allyl polyethylene glycol and N,N-dimethylaminoethyl methacrylate to obtain hydrophilic polyvinyl chloride; and mixing and pressing the modified phase-change microcapsule with triphenyl phosphate and a liquid calcium zinc stabilizer to obtain a hydrophilic modified PVC film.

[0021] Firstly, the phase change microcapsules were modified with allyltrimethoxysilane and had double bonds. After the reaction of 2,4-dihydroxybenzophenone with allyl succinic anhydride, the double bonds were polymerized with 8-chloro-1-octene through free radicals to the surface of the silane-modified phase change microcapsules to obtain modified phase change microcapsules. 2,4-dihydroxybenzophenone can store and release heat energy through the opening and closing of hydrogen bonds, thereby improving the photothermal conversion ability of the hydrophilic modified PVC film. At the same time, the carboxyl group produced by the reaction of 2,4-dihydroxybenzophenone with allyl succinic anhydride can improve the hydrophilic properties of the PVC film.

[0022] Secondly, polyethylene glycol was introduced into the modified polyvinyl chloride prepared by the reaction of iodine-terminated polyvinyl chloride and allyl polyethylene glycol and N,N-dimethylaminoethyl methacrylate, which effectively improved the hydrophilicity of the PVC film; tertiary amines were introduced through the copolymerization of N,N-dimethylaminoethyl methacrylate, and the modified phase change microcapsules were grafted onto the modified polyvinyl chloride through the reaction of quaternary ammonium salts to generate quaternary ammonium salts, thereby improving the antibacterial and hydrophilic properties of the PVC film. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Example 1

[0025] A hydrophilic modified PVC film comprises the following preparation steps:

[0026] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene were mixed in a mass ratio of 1:0.5:0.04:20, and stirred at 400 r / min for 1 h at room temperature to prepare a modified ultraviolet absorber;

[0027] (2) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.3:4:13, stirred at 250 r / min for 20 min at room temperature, added with 0.2 times the mass of the phase change microcapsules, 0.1 times the mass of the phase change microcapsules, 8-chloro-1-octene, and 0.02 times the mass of the phase change microcapsules, stirred at 400 r / min for 1 h at 40°C, filtered, washed the filter residue with anhydrous ethanol for 3 times, and dried in vacuum at 45°C for 4 h to obtain modified phase change microcapsules;

[0028] (3) Add iodine methyl chloride, hydroxypropyl cellulose, methyl cellulose and deionized water in a mass ratio of 1:0.075:0.03:100 to a reactor and mix well. Add vinyl chloride in an amount of 35 to 45 times the mass of iodine methyl chloride under a nitrogen atmosphere, stir at 600 r / min at 33°C for 25 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount of 0.5 times the mass of iodine methyl chloride, and continue stirring for 8 h to obtain iodine-terminated polyvinyl chloride. Add iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N,N-dimethylaminoethyl methacrylate, Tween-60 and cyclohexanone in a mass ratio of 1:0.2:1.5:0.04:10 to a reactor and mix well. Under a nitrogen atmosphere, stir at 600 r / min at 30°C for 25 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount of 2 times the mass of iodine-terminated polyvinyl chloride, and continue stirring for 8 h to obtain hydrophilic polyvinyl chloride.

[0029] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.2:0.06:0.08, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0030] Example 2

[0031] A hydrophilic modified PVC film comprises the following preparation steps:

[0032] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene were mixed in a mass ratio of 1:0.6:0.05:25, and stirred at 500 r / min for 1.5 h at room temperature to prepare a modified ultraviolet absorber;

[0033] (2) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.4:5:15, stirred at 300 r / min for 25 min at room temperature, and 0.3 times the mass of the phase change microcapsules were added with a modified ultraviolet absorber, 0.15 times the mass of the phase change microcapsules, and 0.03 times the mass of the phase change microcapsules. The mixture was stirred at 500 r / min for 1.5 h at 45 ° C., filtered, and the filter residue was washed with anhydrous ethanol for 4 times, and vacuum dried at 50 ° C. for 5 h to obtain modified phase change microcapsules;

[0034] (3) Add iodine methyl chloride, hydroxypropyl cellulose, methyl cellulose and deionized water in a mass ratio of 1:0.077:0.032:110 to a reactor and mix well. Add vinyl chloride in an amount 40 times the mass of iodine methyl chloride under a nitrogen atmosphere, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount 0.55 times the mass of iodine methyl chloride, and continue stirring for 10 h to obtain iodine-terminated polyvinyl chloride. Add iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N,N-dimethylaminoethyl methacrylate, Tween-60 and cyclohexanone in a mass ratio of 1:0.3:2:0.05:12 to a reactor and mix well. Under a nitrogen atmosphere, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount 2.5 times the mass of iodine-terminated polyvinyl chloride, and continue stirring for 10 h to obtain hydrophilic polyvinyl chloride.

[0035] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.3:0.07:0.09, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0036] Example 3

[0037] A hydrophilic modified PVC film comprises the following preparation steps:

[0038] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene were mixed in a mass ratio of 1:0.7:0.06:30, and stirred at 600 r / min for 2 h at room temperature to prepare a modified ultraviolet absorber;

[0039] (2) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.5:6:17, stirred at 350 r / min for 30 min at room temperature, and 0.4 times the mass of the phase change microcapsules were added with a modified ultraviolet absorber, 0.2 times the mass of the phase change microcapsules, and 0.04 times the mass of the phase change microcapsules. The mixture was stirred at 600 r / min at 50°C for 2 h, filtered, and the residue was washed with anhydrous ethanol for 5 times, and vacuum dried at 55°C for 6 h to obtain modified phase change microcapsules;

[0040] (3) Add iodine, hydroxypropyl cellulose, methyl cellulose, and deionized water in a mass ratio of 1:0.079:0.035:120 to a reactor and mix well. Under a nitrogen atmosphere, add vinyl chloride 45 times the mass of iodine, stir at 800 r / min at 37°C for 35 minutes, add a mixed solution of sodium persulfate and sodium bicarbonate 0.6 times the mass of iodine, and continue to stir for 12 hours to obtain iodine-terminated polyvinyl chloride; add iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N,N-dimethylaminoethyl methacrylate, Tween-60, and cyclohexanone in a mass ratio of 1:0.4:2.5:0.06:15 to a reactor and mix well. Under a nitrogen atmosphere, stir at 40°C and 800 r / min for 35 minutes, add a mixed solution of sodium persulfate and sodium bicarbonate 3 times the mass of iodine-terminated polyvinyl chloride, and continue to stir for 12 hours to obtain hydrophilic polyvinyl chloride;

[0041] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.4:0.08:0.1, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0042] Comparative Example 1

[0043] A hydrophilic modified PVC film comprises the following preparation steps:

[0044] (1) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.4:5:15, stirred at 300 r / min for 25 min at room temperature, 8-chloro-1-octene (0.15 times the mass of the phase change microcapsules) and azobisisobutyronitrile (0.03 times the mass of the phase change microcapsules) were added, stirred at 500 r / min for 1.5 h at 45° C., filtered, and the residue was washed with anhydrous ethanol for 4 times, and vacuum dried at 50° C. for 5 h to obtain modified phase change microcapsules;

[0045] (2) Add iodine methyl chloride, hydroxypropyl cellulose, methyl cellulose and deionized water in a mass ratio of 1:0.077:0.032:110 to a reactor and mix well. Add vinyl chloride in an amount 40 times the mass of iodine methyl chloride under a nitrogen atmosphere, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount 0.55 times the mass of iodine methyl chloride, and continue stirring for 10 h to obtain iodine-terminated polyvinyl chloride. Add iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N,N-dimethylaminoethyl methacrylate, Tween-60 and cyclohexanone in a mass ratio of 1:0.3:2:0.05:12 to a reactor and mix well. Under a nitrogen atmosphere, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate in an amount 2.5 times the mass of iodine-terminated polyvinyl chloride, and continue stirring for 10 h to obtain hydrophilic polyvinyl chloride.

[0046] (3) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.3:0.07:0.09, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0047] Comparative Example 2

[0048] A hydrophilic modified PVC film comprises the following preparation steps:

[0049] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene were mixed in a mass ratio of 1:0.6:0.05:25, and stirred at 500 r / min for 1.5 h at room temperature to prepare a modified ultraviolet absorber;

[0050] (2) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.4:5:15, stirred at 300 r / min for 25 min at room temperature, and 0.3 times the mass of the phase change microcapsules were added with a modified ultraviolet absorber, 0.15 times the mass of the phase change microcapsules, and 0.03 times the mass of the phase change microcapsules. The mixture was stirred at 500 r / min for 1.5 h at 45 ° C., filtered, and the filter residue was washed with anhydrous ethanol for 4 times, and vacuum dried at 50 ° C. for 5 h to obtain modified phase change microcapsules;

[0051] (3) Add iodine methyl chloride, hydroxypropyl cellulose, methyl cellulose, and deionized water in a mass ratio of 1:0.077:0.032:110 to a reactor and mix well. Under a nitrogen atmosphere, add vinyl chloride 40 times the mass of iodine methyl chloride, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate 0.55 times the mass of iodine methyl chloride, and continue stirring for 10 hours to obtain iodine-terminated polyvinyl chloride; add iodine-terminated polyvinyl chloride, allyl polyethylene glycol, Tween-60, and cyclohexanone in a mass ratio of 1:0.3:0.05:12 to a reactor and mix well. Under a nitrogen atmosphere, stir at 35°C and 700 r / min for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate 2.5 times the mass of iodine-terminated polyvinyl chloride, and continue stirring for 10 hours to obtain hydrophilic polyvinyl chloride;

[0052] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.3:0.07:0.09, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0053] Comparative Example 3

[0054] A hydrophilic modified PVC film comprises the following preparation steps:

[0055] (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene were mixed in a mass ratio of 1:0.6:0.05:25, and stirred at 500 r / min for 1.5 h at room temperature to prepare a modified ultraviolet absorber;

[0056] (2) Phase change microcapsules, allyl trimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol were mixed in a mass ratio of 1:0.4:5:15, stirred at 300 r / min for 25 min at room temperature, and 0.3 times the mass of the phase change microcapsules were added with a modified ultraviolet absorber, 0.15 times the mass of the phase change microcapsules, and 0.03 times the mass of the phase change microcapsules. The mixture was stirred at 500 r / min for 1.5 h at 45 ° C., filtered, and the filter residue was washed with anhydrous ethanol for 4 times, and vacuum dried at 50 ° C. for 5 h to obtain modified phase change microcapsules;

[0057] (3) Add iodine, hydroxypropyl cellulose, methyl cellulose, and deionized water in a mass ratio of 1:0.077:0.032:110 into a reactor and mix well. Under a nitrogen atmosphere, add vinyl chloride 40 times the mass of iodine, stir at 700 r / min at 35°C for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate 0.55 times the mass of iodine, and continue to stir for 10 hours to obtain iodine-terminated polyvinyl chloride; add iodine-terminated polyvinyl chloride, N, N-dimethylaminoethyl methacrylate, Tween-60, and cyclohexanone in a mass ratio of 1:2:0.05:12 into a reactor and mix well. Under a nitrogen atmosphere, stir at 35°C and 700 r / min for 30 min, add a mixed solution of sodium persulfate and sodium bicarbonate 2.5 times the mass of iodine-terminated polyvinyl chloride, and continue to stir for 10 hours to obtain hydrophilic polyvinyl chloride;

[0058] (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1:0.3:0.07:0.09, mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

[0059] Test Example 1

[0060] Anti-ultraviolet aging test:

[0061] Test method: Take a hydrophilic modified PVC film with a size of 10cm×2cm, place it under a 30w ultraviolet lamp at a distance of 5cm, and observe the discoloration of the material after irradiation for one week. The results are shown in Table 1.

[0062] Table 1

[0063]

[0064]

[0065] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the hydrophilic modified PVC film prepared by the present invention has good anti-ultraviolet aging performance.

[0066] By comparison, none of Examples 1 to 3 turns yellow obviously, but Comparative Example 1 turns yellow, indicating that the carbonyl group and the hydroxyl group on the 2,4-dihydroxybenzophenone molecule form an internal hydrogen bond to form a chelate ring with a stable conjugated structure. After absorbing ultraviolet rays, thermal vibration of the molecule occurs, the internal hydrogen bond is destroyed, the chelate ring is opened, and the ultraviolet light energy is converted into heat energy and released, which is absorbed by the phase change microcapsule and slowly released, thereby effectively improving the anti-ultraviolet aging performance of the hydrophilic modified PVC film.

[0067] Test Example 2

[0068] Antibacterial performance: The hydrophilic modified PVC films obtained in each embodiment and comparative example were crushed, passed through a 100-mesh sieve, and the same mass was taken to test the antibacterial rate of the materials against Staphylococcus aureus according to the Quine test method. The results are shown in Table 2.

[0069] Table 2

[0070] Antibacterial rate Antibacterial rate Example 1 98.8％ Comparative Example 1 98.7％ Example 2 99.1％ Comparative Example 2 66.3％ Example 3 98.9％ Comparative Example 3 98.9％

[0071] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the hydrophilic modified PVC film prepared by the present invention has good antibacterial properties.

[0072] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that N, N-dimethylaminoethyl methacrylate participates in the copolymerization to introduce tertiary amine, which reacts with the modified phase change microcapsules to form quaternary ammonium salts. Cationic quaternary ammonium salts have high antibacterial properties and can improve the antibacterial properties of PVC film.

[0073] Test Example 3

[0074] Hydrophilic performance test:

[0075] Contact angle test: Take a hydrophilic modified PVC film with a size of 100 mm × 100 mm and use an OAC20 optical contact angle meter to test the static contact angle of water. The results are shown in Table 3.

[0076] Table 3

[0077] Static contact angle Static contact angle Example 1 56.1 Comparative Example 1 57.7 Example 2 55.7 Comparative Example 2 58.2 Example 3 55.8 Comparative Example 3 72.5

[0078] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the hydrophilic modified PVC film prepared by the present invention has good hydrophilic properties.

[0079] By comparison, the static contact angles of Examples 1 to 3 are smaller than that of Comparative Example 1, indicating that the reaction of 2,4-dihydroxybenzophenone with allyl succinic anhydride introduces hydrophilic carboxyl groups, which can improve the hydrophilicity of the PVC film; the static contact angles of Examples 1 to 3 are smaller than that of Comparative Example 2, indicating that tertiary amines are introduced by copolymerization of N,N-dimethylaminoethyl methacrylate, which reacts with the modified phase-change microcapsules to form quaternary ammonium salts, and the quaternary ammonium salts have good hydrophilicity, thereby improving the hydrophilicity of the PVC film; the static contact angles of Examples 1 to 3 are smaller than that of Comparative Example 3, indicating that allyl polyethylene glycol and polyvinyl chloride block copolymerization successfully introduces polyethylene glycol segments with good hydrophilicity, effectively improving the hydrophilicity of the hydrophilic modified PVC film.

[0080] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A hydrophilic modified PVC film, characterized in that: The hydrophilic modified PVC film is prepared by reacting 2,4-dihydroxybenzophenone with allyl succinic anhydride to obtain a modified ultraviolet absorber; modifying a phase change microcapsule with allyl trimethoxysilane and then reacting the modified ultraviolet absorber, allyl succinic anhydride and 8-chloro-1-octene to obtain a modified phase change microcapsule; reacting iodine-terminated polyvinyl chloride with allyl polyethylene glycol and N,N-dimethylaminoethyl methacrylate to obtain a hydrophilic polyvinyl chloride; and mixing and pressing the modified phase change microcapsule with triphenyl phosphate and a liquid calcium zinc stabilizer to obtain a hydrophilic modified PVC film.

2. A method for preparing a hydrophilic modified PVC film, characterized in that: The method comprises the following preparation steps: (1) 2,4-dihydroxybenzophenone, allyl succinic anhydride, p-toluenesulfonic acid, and toluene are mixed in a mass ratio of 1: (0.5-0.7): (0.04-0.06): (20-30), and stirred at room temperature at 400-600 r / min for 1-2 hours to prepare a modified ultraviolet absorber; (2) Mix phase change microcapsules, allyltrimethoxysilane, 10% hydrochloric acid solution, and anhydrous ethanol in a mass ratio of 1: (0.3-0.5): (4-6): (13-17), stir at 250-350 r / min for 20-30 min at room temperature, add 0.2-0.4 times the mass of the phase change microcapsules modified ultraviolet absorber, 0.1-0.2 times the mass of the phase change microcapsules 8-chloro-1-octene, and 0.02-0.04 times the mass of the phase change microcapsules azobisisobutyronitrile, stir at 400-600 r / min for 1-2 h at 40-50° C., filter, wash the filter residue with anhydrous ethanol for 3-5 times, and vacuum dry at 45-55° C. for 4-6 h to obtain modified phase change microcapsules; (3) Mix iodomethane, hydroxypropyl cellulose, methyl cellulose and deionized water in a mass ratio of 1: (0.075-0.079): (0.03-0.035): (100-120) were added to the reaction kettle and mixed. Under a nitrogen atmosphere, 35-45 times the mass of methyl iodide of vinyl chloride was added. The mixture was stirred at 600-800 r / min for 25-35 min at 33-37 ° C. A mixed solution of sodium persulfate and sodium bicarbonate with a mass of 0.5-0.6 times the mass of methyl iodide was added. The mixture was stirred for 8-12 h to obtain iodine-terminated polyvinyl chloride. The iodine-terminated polyvinyl chloride, allyl polyethylene glycol, N, N-dimethylaminoethyl methacrylate, Tween-60, and cyclohexanone are added into a reaction kettle in a mass ratio of 1: (0.2-0.4): (1.5-2.5): (0.04-0.06): (10-15) and mixed evenly; stirred at 30-40°C and 600-800 r / min for 25-35 min under a nitrogen atmosphere; a mixed solution of sodium persulfate and sodium bicarbonate in an amount of 2-3 times the mass of iodine-terminated polyvinyl chloride is added; stirred for 8-12 h to obtain hydrophilic polyvinyl chloride; (4) The hydrophilic polyvinyl chloride, modified phase change microcapsules, triphenyl phosphate, and liquid calcium zinc stabilizer are mixed in a mass ratio of 1: (0.2-0.4): (0.06-0.08): (0.08-0.1), mixed on a double-roll rubber mixer, and then pressed into shape using a flat vulcanizer to obtain a hydrophilic modified PVC film.

3. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The phase change microcapsules in step (2) are phase change microcapsules with silica composite methyl methacrylate-acrylic acid as wall material and paraffin as core material.

4. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The preparation method of the mixed solution of sodium persulfate and sodium bicarbonate in step (3) is as follows: sodium persulfate, sodium bicarbonate and deionized water are mixed in a mass ratio of 1: (0.26-0.27): (3-3.4).

5. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The allyl polyethylene glycol in step (3) is APEG-700 type allyl polyvinyl chloride.

6. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The liquid calcium zinc stabilizer in step (4) is an industrial grade liquid calcium zinc stabilizer.

7. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The temperature of the double rollers of the double roller rubber mixer in step (4) is 160° C., and the mixing time is 6 to 8 minutes.

8. The method for preparing a hydrophilic modified PVC film according to claim 2, characterized in that: The film forming method of the flat vulcanizing machine in step (4) is: preheating to a temperature of 170°C, hot pressing at a pressure of 1.5 MPa for 6 minutes, cooling to 80°C and then maintaining the pressure for cold pressing for 30 minutes, and naturally cooling to room temperature before taking out.

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