阅读说明：本技术 一种纳米TiO2改性聚乙烯的复合抗菌薄膜及其制法 (Nano TiO (titanium dioxide)2Modified polyethylene composite antibacterial film and preparation method thereof ) 是由 王国成 于 2020-06-05 设计创作，主要内容包括：本发明涉及抗菌材料技术领域,且公开了一种纳米TiO<Sub>2</Sub>改性聚乙烯的复合抗菌薄膜,包括以下配方原料及组分：聚乙烯、聚乙烯醇、苯乙烯、催化剂、分散剂、改性TiO<Sub>2</Sub>-壳聚糖微球。该一种纳米TiO<Sub>2</Sub>改性聚乙烯的复合抗菌薄膜,TiO<Sub>2</Sub>纳米管具有巨大的比表面积,暴露出大量的光反应活性位点,并且Ni掺杂取代了部分Ti的晶格,使TiO<Sub>2</Sub>的光吸收边发生红移,降低了TiO<Sub>2</Sub>的禁带宽度,使TiO<Sub>2</Sub>在可见光区域内也具有良好的光化学活性,壳聚糖吸附Ni掺杂TiO<Sub>2</Sub>纳米管,顺丁烯二酸酐接枝壳聚糖微球,通过自由基聚合反应,使TiO<Sub>2</Sub>纳米管通过化学键与聚苯乙烯交联,改善了TiO<Sub>2</Sub>纳米管与聚乙烯复合材料的分散性和相容性,赋予了聚乙烯薄膜材料优异的光化学抗菌性能。(The invention relates to the technical field of antibacterial materials, and discloses nano TiO 2 Composite resistance of modified polyethyleneThe bacterial membrane comprises the following formula raw materials and components: polyethylene, polyvinyl alcohol, styrene, catalyst, dispersant and modified TiO 2 -chitosan microspheres. The nanometer TiO 2 Composite antibacterial film of modified polyethylene, TiO 2 The nanotube has great specific surface area, large amount of photoreaction active sites are exposed, and Ni is doped to replace partial crystal lattice of Ti, so that TiO 2 The light absorption edge of the film is red-shifted, and TiO is reduced 2 Forbidden band width of (A) to make TiO 2 Has good photochemical activity in a visible light region, and the chitosan adsorbs Ni-doped TiO 2 Nano tube, maleic anhydride grafted chitosan microsphere, free radical polymerization reaction to make TiO 2 The nanotube is crosslinked with polystyrene via chemical bond to improve TiO 2 The dispersibility and compatibility of the nanotube and the polyethylene composite material endow the polyethylene film material with excellent photochemical antibacterial performance.)

1. Nano TiO (titanium dioxide)₂The modified polyethylene composite antibacterial film comprises the following formula raw materials and components in parts by weight, and is characterized in that: 70-86 parts of polyethylene, 4-8 parts of polyvinyl alcohol, 5-10 parts of styrene, 0.5-1 part of catalyst, 1.5-3 parts of dispersing agent and 3-8 parts of modified TiO₂-chitosan microspheres.

2. The nano TiO of claim 1₂The composite antibacterial film of modified polyethylene is characterized in that: the dispersant is sodium dodecyl benzene sulfonate.

3. The nano TiO of claim 1₂The composite antibacterial film of modified polyethylene is characterized in that: the catalyst is dibenzoyl peroxide.

4. The nano TiO of claim 1₂The composite antibacterial film of modified polyethylene is characterized in that: the modified Ag-TiO₂The preparation method of the composite material comprises the following steps:

(1) adding tetrabutyl titanate into ethanol solvent, stirring, preparing 10-15% nitric acid solution, adding Ni (NO)₃)₂Pouring the solution into an ethanol solution of tetrabutyl titanate after uniform stirring, heating the solution to 40-60 ℃, uniformly stirring for 1-2h, standing and aging for 5-10h to form gel, drying the gel solid to remove the solvent, grinding into fine powder, placing the fine powder into a sodium hydroxide solution with the mass fraction of 70-80%, heating to 40-50 ℃, uniformly stirring for 20-25h, transferring the solution into a reaction kettle, heating to 120-₂A nanotube;

(2) adding chitosan into 1-5 wt% acetic acid solution, performing ultrasonic dispersion treatment at 30-60 deg.C for 20-40min, and adding Ni-doped TiO₂Performing ultrasonic dispersion treatment on the nanotube for 10-30min, adding epichlorohydrin, heating to 45-75 ℃, reacting for 3-6h, dropwise adding a sodium hydroxide solution into the solution, stirring at constant speed until a large amount of precipitates are produced, removing the solvent from the solution, washing a solid product, and drying to obtain TiO₂Loading chitosan microspheres;

(3) adding TiO into N, N-dimethyl formamide solvent₂Loading chitosan microspheres, maleic anhydride, a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, heating the solution to 100 ℃ and 120 ℃, reacting for 18-25h, adding distilled water into the solution until a large amount of precipitate is formed, removing the solvent from the solution, washing a solid product and drying to prepare the modified TiO grafted by the maleic anhydride₂-chitosan microspheres.

5. The nano TiO of claim 4₂The composite antibacterial film of modified polyethylene is characterized in that: said tetrabutyl titanate and Ni (NO)₃)₂The mass ratio of (A) to (B) is 94-99: 1.

6. The nano TiO of claim 4₂The composite antibacterial film of modified polyethylene is characterized in that: the chitosan and Ni are doped with TiO₂The mass ratio of the nanotube to the epichlorohydrin is 2-5:1: 1.5-2.5.

7. The nano TiO of claim 4₂The composite antibacterial film of modified polyethylene is characterized in that: the TiO is₂The mass ratio of the loaded chitosan microspheres to the maleic anhydride to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1:2-4:3.5-4.5: 0.1-0.3.

8. The nano TiO of claim 1₂The composite antibacterial film of modified polyethylene is characterized in that: what is needed isThe nano TiO₂The preparation method of the composite antibacterial film of the modified polyethylene comprises the following steps:

(1) adding 5-10 parts of styrene, 0.5-1 part of catalyst dibenzoyl peroxide, 1.5-3 parts of dispersant sodium dodecyl benzene sulfonate and 3-8 parts of modified TiO into a mixed solvent of distilled water and ethanol with the volume ratio of 3-4:1₂-chitosan microspheres, heating the solution to 50-80 ℃, reacting for 3-6h, removing the solvent from the solution, washing the solid product and drying to prepare the TiO₂Modified polystyrene grafted with chitosan;

(2) placing the modified polystyrene, 70-86 parts of polyethylene and 4-8 parts of polyvinyl alcohol into an internal mixer, blending for 2-4h at the temperature of 180 plus materials and 210 ℃, and performing blow molding on the blended material through a film blowing machine at the temperature of 160 plus materials and 190 ℃ to prepare the nano TiO₂Modified polyethylene composite antibacterial film.

Technical Field

The invention relates to the technical field of antibacterial materials, in particular to nano TiO₂A composite antibacterial film of modified polyethylene and its production are disclosed.

Background

The antibacterial material is a novel functional material with the capability of inhibiting or killing microorganisms, usually, antibacterial agents or antibacterial substances are added to endow the material with certain capability of inhibiting or killing surface bacteria, such as antibacterial plastics, antibacterial films, antibacterial fibers, antibacterial coatings and the like, the antibacterial material has extremely wide application prospect in the fields of medical treatment, household articles, food packaging and the like, the antibacterial agents mainly comprise inorganic antibacterial agents, such as zinc oxide, titanium dioxide, ammonium dihydrogen phosphate and the like, organic antibacterial agents, such as acylaniline compounds, thiazole compounds, quaternary ammonium salt compounds and the like, wherein the titanium dioxide is a good photocatalytic antibacterial material, can generate photoproduction electrons and holes under ultraviolet radiation, the photoproduction electrons and the holes can react with oxygen and water to produce superoxide radical and hydroxyl radical with extremely high activity, and can perform oxidation-reduction reaction with biological enzyme activity biological macromolecules in microorganisms such as bacteria, fungi and the like, destroying the normal metabolic process of the microorganism, thereby inhibiting the growth and reproduction of the microorganism.

Polyethylene is a thermoplastic resin, has strong low-temperature resistance, stable chemical properties, excellent acid and alkali resistance, excellent electrochemical properties such as electric insulation and the like, is a widely used high polymer material, has wide application in the fields of food packaging, medical treatment and the like, but the unmodified polyethylene material has almost no antibacterial property, and the common polyethylene material cannot meet the requirements of people on life and production.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides nano TiO₂The composite antibacterial polyethylene film and its preparation process solve the problem of poor antibacterial performance of polyethylene material and the problem of poor antibacterial performance of polyethylene materialTiO is₂The photochemical activity in the visible light range is low.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: nano TiO (titanium dioxide)₂The modified polyethylene composite antibacterial film comprises the following formula raw materials in parts by weight: 70-86 parts of polyethylene, 4-8 parts of polyvinyl alcohol, 5-10 parts of styrene, 0.5-1 part of catalyst, 1.5-3 parts of dispersing agent and 3-8 parts of modified TiO₂-chitosan microspheres.

Preferably, the dispersant is sodium dodecyl benzene sulfonate.

Preferably, the catalyst is dibenzoyl peroxide.

Preferably, the modified Ag-TiO₂The preparation method of the composite material comprises the following steps:

(1) adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, preparing a nitric acid solution with the mass fraction of 10-15%, and adding Ni (NO)₃)₂Pouring the solution into an ethanol solution of tetrabutyl titanate after uniform stirring, placing a reaction bottle in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 1-2h, standing and aging for 5-10h to form gel, drying the gel solid to remove the solvent, grinding into fine powder, placing the fine powder in a sodium hydroxide solution with the mass fraction of 70-80%, placing the reaction bottle in the constant-temperature water bath kettle, heating to 40-50 ℃, uniformly stirring for 20-25h, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a drying oven, heating to 120-, then annealing at 480-540 ℃ for 1-2h to prepare Ni-doped TiO₂A nanotube.

(2) Adding 1-5 wt% acetic acid solution and chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 30-60 deg.C for 20-40min, and adding Ni-doped TiO₂Performing ultrasonic dispersion treatment on the nanotube for 10-30min, and adding chloropropylene oxide into the reaction flaskPlacing alkane in a constant temperature water bath kettle, heating to 45-75 ℃, stirring at constant speed for reaction for 3-6h, dropwise adding sodium hydroxide solution into a reaction bottle, stirring at constant speed until a large amount of precipitate is produced, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water, and fully drying to obtain TiO₂And (3) loading chitosan microspheres.

(3) Adding N, N-dimethylformamide solvent and TiO into a reaction bottle₂Loading chitosan microspheres, stirring uniformly, adding maleic anhydride, a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, placing a reaction bottle in an oil bath pot, heating to 100-120 ℃, reacting for 18-25h, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is formed, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the modified TiO grafted with the maleic anhydride₂-chitosan microspheres.

Preferably, said tetrabutyl titanate and Ni (NO)₃)₂The mass ratio of (A) to (B) is 94-99: 1.

Preferably, the chitosan and Ni are doped with TiO₂The mass ratio of the nanotube to the epichlorohydrin is 2-5:1: 1.5-2.5.

Preferably, the TiO is₂The mass ratio of the loaded chitosan microspheres to the maleic anhydride to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1:2-4:3.5-4.5: 0.1-0.3.

Preferably, the nano TiO₂The preparation method of the composite antibacterial film of the modified polyethylene comprises the following steps:

(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3-4:1, and adding 5-10 parts of styrene, 0.5-1 part of catalyst dibenzoyl peroxide, 1.5-3 parts of dispersant sodium dodecyl benzene sulfonate and 3-8 parts of modified TiO₂Placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-80 ℃, stirring at a constant speed for reaction for 3-6h, vacuum drying the solution to remove the solvent, washing the solid product with ethanol, and fully drying to obtain TiO₂Modified polystyrene grafted by chitosan is loaded.

(2) Placing the modified polystyrene, 70-86 parts of polyethylene and 4-8 parts of polyvinyl alcohol into an internal mixer, blending for 2-4h at the temperature of 180 plus materials and 210 ℃, and performing blow molding on the blended material through a film blowing machine at the temperature of 160 plus materials and 190 ℃ to prepare the nano TiO₂Modified polyethylene composite antibacterial film.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the nanometer TiO₂The Ni-doped TiO is prepared by a sol-gel method by using a composite antibacterial film of modified polyethylene₂Nanotubes, TiO compared to ordinary titanium dioxide₂The nano tube has huge specific surface area, exposes a large number of photoreaction active sites, fully contacts with light radiation, and improves TiO₂The nanotube has high light energy utilization rate, and Ni is doped to replace partial Ti lattice₂A new energy level is generated on the valence band of TiO₂The light absorption edge of the film is red-shifted, and TiO is reduced₂The forbidden band width of TiO is widened₂Ultraviolet-visible absorption band of (A), making TiO₂The modified polyvinyl film has good photochemical activity in an ultraviolet region and a visible light region, and the responsiveness to solar energy is enhanced, so that more photo-generated electrons and holes are generated, the modified polyvinyl film is favorable for reacting with oxygen and water to generate more superoxide radicals and hydroxyl radicals, and the antibacterial activity of the polyethylene film material is greatly enhanced.

The nanometer TiO₂Modified polyethylene composite antibacterial film, and Ni-doped TiO adsorbed by chitosan₂Nanotube to form TiO₂Loading chitosan microsphere, grafting maleic anhydride to chitosan microsphere through ring-opening esterification reaction of maleic anhydride and hydroxyl in chitosan, and in-situ polymerizing to make olefinic bond in styrene and maleic anhydride undergo free radical polymerization reaction so as to implement cross-linking polymerization and implement TiO₂The nanotube is crosslinked with polystyrene through chemical bond, and the modified polystyrene is then blended with polyvinyl alcohol and polyethylene for blow molding to prepare the modified polyethylene film materialGreatly improves TiO under the action of polystyrene₂The dispersity and compatibility of the nanotube and polyethylene avoid TiO₂The mechanical property of the polyethylene film material is influenced by the uneven dispersion of the nano-tubes, and the TiO doped with Ni₂The nano-tube endows the polyethylene film material with excellent photochemical antibacterial property.

The nanometer TiO₂The composite antibacterial film of the modified polyethylene, the maleic anhydride grafted chitosan microspheres and the styrene are subjected to free radical chemical polymerization reaction to generate the modified polystyrene, so that the chitosan, the polyethylene and the polyvinyl alcohol successfully form a composite material, the chitosan and the polyvinyl alcohol have excellent biodegradability, the biodegradability of the polyethylene composite film-coated material can be greatly improved, and the pollution and damage of the polyethylene to the environment are effectively reduced.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: nano TiO (titanium dioxide)₂The modified polyethylene composite antibacterial film comprises the following formula raw materials in parts by weight: 70-86 parts of polyethylene, 4-8 parts of polyvinyl alcohol, 5-10 parts of styrene, 0.5-1 part of catalyst, 1.5-3 parts of dispersing agent and 3-8 parts of modified TiO₂Chitosan microspheres, dispersant sodium dodecylbenzene sulfonate, catalyst dibenzoyl peroxide.

Modified Ag-TiO₂The preparation method of the composite material comprises the following steps:

(1) adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, preparing a nitric acid solution with the mass fraction of 10-15%, and adding Ni (NO)₃)₂In which tetrabutyl titanate and Ni (NO)₃)₂The mass ratio of the substances is 94-99:1, the solution is poured into an ethanol solution of tetrabutyl titanate after being uniformly stirred, a reaction bottle is placed in a constant-temperature water bath kettle, the temperature is increased to 40-60 ℃, the uniform stirring is carried out for 1-2h, then the standing and aging are carried out for 5-10h to form gel, the gel solid is dried to remove the solvent and is ground into fine powder, the fine powder is placed in a sodium hydroxide solution with the mass fraction of 70-80%, the reaction bottle is placed in a constant-temperature water bath kettle, the heating is carried out to 40-50 ℃, and the uniform stirring is carried outStirring at a high speed for 20-25h, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, heating to 140 ℃ for reaction for 20-30h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in a resistance furnace at a temperature rise rate of 5-10 ℃/min, carrying out heat preservation treatment for 1-2h at 480 ℃ and 540 ℃, and then carrying out annealing treatment for 1-2h at 480 ℃ and 540 ℃ to prepare the Ni-doped TiO₂A nanotube.

(2) Adding 1-5 wt% acetic acid solution and chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 30-60 deg.C for 20-40min, and adding Ni-doped TiO₂The nanotube is subjected to ultrasonic dispersion treatment for 10-30min, and epichlorohydrin is added into a reaction bottle, wherein the chitosan and the Ni are doped with TiO₂The mass ratio of the nanotube to the epichlorohydrin is 2-5:1:1.5-2.5, the mixture is placed in a constant temperature water bath kettle, the mixture is heated to 45-75 ℃, the mixture is stirred at a constant speed for reaction for 3-6h, a sodium hydroxide solution is dripped into a reaction bottle, the mixture is stirred at a constant speed until a large amount of precipitates are produced, the solution is dried in vacuum to remove the solvent, a solid product is washed by distilled water and is fully dried to prepare TiO₂And (3) loading chitosan microspheres.

(3) Adding N, N-dimethylformamide solvent and TiO into a reaction bottle₂Loading chitosan microspheres, stirring uniformly, adding maleic anhydride, a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine in a mass ratio of 1:2-4:3.5-4.5:0.1-0.3, placing a reaction bottle in an oil bath, heating to 100-₂-chitosan microspheres.

Nano TiO 2₂The preparation method of the composite antibacterial film of the modified polyethylene comprises the following steps:

(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3-4:1, and adding 5-10 parts of styrene, 0.5-1 part of catalyst dibenzoyl peroxide and 1.5-3 parts of dispersant dodecyl benzene sulfonic acidSodium and 3-8 parts of modified TiO₂Placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-80 ℃, stirring at a constant speed for reaction for 3-6h, vacuum drying the solution to remove the solvent, washing the solid product with ethanol, and fully drying to obtain TiO₂Modified polystyrene grafted by chitosan is loaded.

(2) Placing the modified polystyrene, 70-86 parts of polyethylene and 4-8 parts of polyvinyl alcohol into an internal mixer, blending for 2-4h at the temperature of 180 plus materials and 210 ℃, and performing blow molding on the blended material through a film blowing machine at the temperature of 160 plus materials and 190 ℃ to prepare the nano TiO₂Modified polyethylene composite antibacterial film.