CN111574679A - Degradable TiO2Polylactic acid grafted polyurethane antibacterial material and preparation method thereof - Google Patents

Degradable TiO2Polylactic acid grafted polyurethane antibacterial material and preparation method thereof Download PDF

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CN111574679A
CN111574679A CN202010516162.6A CN202010516162A CN111574679A CN 111574679 A CN111574679 A CN 111574679A CN 202010516162 A CN202010516162 A CN 202010516162A CN 111574679 A CN111574679 A CN 111574679A
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polylactic acid
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张中明
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    • C08G18/40—High-molecular-weight compounds
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    • C08G2230/00—Compositions for preparing biodegradable polymers

Abstract

The invention relates to the technical field of antibacterial materials, and discloses degradable TiO2The polylactic acid grafted polyurethane antibacterial material comprises the following formula raw materials and components: polylactic acid grafted nano TiO2Polyester polyol, isocyanate, 1, 4-butanediol and stannous octoate. The degradable TiO is2Polylactic acid grafted polyurethane antibacterial material, Mn-N codoped nano TiO2The crystal lattice of N substituted O has good photoresponse and photochemical activity under visible light, oxygen vacancy generated by the crystal lattice defect can be used as a trap for capturing photoproduction electrons to promote the separation of the photoproduction electrons and holes, and polylactic acid grafted nano TiO of hydroxyl at the chain end2In-situ polymerization of the modified material and isocyanate to obtain grafted nanometer TiO with branched chain containing polylactic acid2The polyurethane improves Mn-N co-doped nano TiO2The compatibility with polyurethane endows the polyurethane with excellent photocatalytic antibacterial activity and good biodegradation performance.

Description

Degradable TiO2Polylactic acid grafted polyurethane antibacterial material and preparation method thereof
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to degradable TiO2Polylactic acid grafted polyurethane antibacterial material and a preparation method thereof.
Background
The antibacterial material is usually compounded by mechanically blending an antibacterial agent and an organic polymer material, and has the function of killing pathogenic microorganisms or inhibiting the growth of pathogenic microorganisms, such as antibacterial textiles, antibacterial plastics, antibacterial packaging films and the like, wherein the antibacterial agent mainly comprises inorganic antibacterial agents such as zinc oxide, nano titanium dioxide, nano silver and the like, and organic antibacterial agents such as imidazoles, thiazoles, quaternary ammonium salts and the like.
Polyurethane is a polyurethane polymer which is mainly obtained by polymerizing isocyanate monomers and polyol monomers, and mainly comprises polyurethane foam plastics, polyurethane elastomers, polyurethane fiber plastics, polyurethane coatings, adhesives, sealants and the like, but the traditional polyurethane material does not have antibacterial performance, and the nano titanium dioxide and other antibacterial agents are simply compounded with the polyurethane by a mechanical blending method, so that the dispersibility of the nano titanium dioxide and the polyurethane is poor, and the nano titanium dioxide and the polyurethane are easy to agglomerate and block.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides degradable TiO2The polylactic acid grafted polyurethane antibacterial material and the preparation method thereof solve the problem that nano titanium dioxide is easy to form agglomeration in polyurethane and solve the problem that photo-generated electrons and holes of titanium dioxide are easy to compound.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: degradable TiO2-poly-milkThe acid-grafted polyurethane antibacterial material comprises the following raw materials and components: polylactic acid grafted nano TiO2The adhesive comprises polyester polyol, isocyanate, 1, 4-butanediol and stannous octoate according to the mass ratio of 10-25:100:50-70:6-10: 0.5-1.
Preferably, the isocyanate is any one of L-lysine diisocyanate, isophorone diisocyanate, and 4,4' -methylenebis (phenyl isocyanate).
Preferably, the degradable TiO2The preparation method of the polylactic acid grafted polyurethane antibacterial material comprises the following steps:
(1) adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dropwise adding glacial acetic acid, adjusting the pH value of the solution to 1-2, carrying out aging reaction for 1-3h, slowly dropwise adding aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant temperature reactor, stirring at a constant speed of 30-40 ℃ until gel is formed, fully drying the gel product, placing the dried gel product into a muffle furnace, heating at a rate of 2-5 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in sodium hydroxide solution with the mass fraction of 1-5%, stirring at a constant speed for 48-96h at 20-30 ℃, filtering the solution, washing with distilled water until the solution is neutral and dried, placing the solid product in tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as a catalyst after stirring uniformly, heating to 150 ℃ in a nitrogen atmosphere, stirring at a constant speed for reaction for 6-10h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol and drying fully to prepare the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 70-80 ℃ for reaction for 2-4h, adding 1, 4-butanediol as a micromolecular chain extender, stirring at a constant speed for reaction for 2-3h, pouring the solution into a mould, naturally casting into a curing film, and preparing the degradable TiO2Polylactic acid grafted polyurethane antibacterial material.
Preferably, the mass ratio of tetrabutyl titanate, urea and manganese chloride is 100:5-15:0.8-1.5
Preferably, the Mn-N co-doped nano TiO2The mass ratio of the DL-lactic acid to the stannous octoate is 20-35:100: 0.5-1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the degradable TiO is2The polylactic acid grafted polyurethane antibacterial material is prepared by taking urea as a nitrogen source and manganese chloride as a manganese source through a sol-gel method to obtain Mn-N co-doped nano TiO2Lattice of N substituted O in TiO2New impurity energy level is generated in the crystal lattice, an O-Ti-N bond is formed between a conduction band and a valence band, and the Mn-N co-doping of the nano TiO is promoted2The light absorption edge of the nano TiO material is red-shifted, so that the visible light absorption range of the nano TiO material is widened, and the Mn-N co-doped nano TiO material is enabled to be2The Mn-N co-doped nano TiO material has good photoresponse and photochemical activity under visible light, Mn replaces the crystal lattice of Ti to form a large number of crystal lattice defects, the generated oxygen vacancies can be used as capture traps of photo-generated electrons to promote the separation of the photo-generated electrons and holes, the recombination and recombination of carriers are reduced, and the Mn-N co-doped nano TiO material is obviously enhanced2Photocatalytic chemistry and photocatalytic antimicrobial properties.
The degradable TiO is2The-polylactic acid grafted polyurethane antibacterial material is etched by sodium hydroxide strong base, so that Mn-N co-doped nano TiO is greatly improved2The surface hydroxyl concentration ensures that the carboxyl of the DL-lactic acid is co-doped with Mn-N nano TiO under the action of a catalyst2The surface of the polylactic acid grafted nanometer TiO with a large amount of hydroxyl is polymerized in situ to generate chain end hydroxyl2Then the polylactic acid is grafted with nano TiO2In-situ polymerization of the modified material and isocyanate to obtain grafted nanometer TiO with branched chain containing polylactic acid2The polyurethane improves Mn-N co-doped nano TiO through chemical covalent bond modification of in-situ polymerization2Compatibility with polyurethane, avoiding agglomeration in polyurethane material and endowing polyurethane with excellent lightThe catalytic antibacterial activity and the excellent biodegradability of polylactic acid molecules are introduced into the branched chains of the molecular chains of the polyurethane, so that the molecular chains of the polyurethane can be damaged when the polylactic acid is biodegraded, a good biodegradation effect is achieved, and pollution and damage to the environment caused by random discarding of polyurethane materials are avoided.
Drawings
FIG. 1 shows Mn-N codoped nano TiO2SEM image of Scanning Electron Microscope (SEM);
FIG. 2 is a degradable TiO2Fourier infrared spectrum FT-IR spectrum of the polylactic acid grafted polyurethane antibacterial material.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: degradable TiO2The polylactic acid grafted polyurethane antibacterial material comprises the following raw materials and components: polylactic acid grafted nano TiO2The adhesive comprises polyester polyol, isocyanate, 1, 4-butanediol and stannous octoate in a mass ratio of 10-25:100:50-70:6-10:0.5-1, wherein the isocyanate is any one of L-lysine diisocyanate, isophorone diisocyanate and 4,4' -methylene bis (phenyl isocyanate).
Degradable TiO2The preparation method of the polylactic acid grafted polyurethane antibacterial material comprises the following steps:
(1) adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dropwise adding glacial acetic acid, adjusting the pH value of the solution to 1-2, carrying out aging reaction for 1-3h, slowly dropwise adding an aqueous solution of urea and an aqueous solution of manganese chloride while stirring, placing the mixture into a constant temperature reactor, stirring at a constant speed of 30-40 ℃ until the mixture is gelatinous, fully drying the gelatinous product, placing the product into a muffle furnace at a heating rate of 2-5 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing into 1-5 wt% sodium hydroxide solution, stirring at 20-30 deg.C for 48-96 hr, filtering, washing with distilled water until it is neutral, and dryingPutting the solid product into tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as catalyst after stirring uniformly, wherein Mn-N codoped nano TiO2Heating DL-lactic acid and stannous octoate to 150-2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 70-80 ℃ for reaction for 2-4h, adding 1, 4-butanediol as a micromolecular chain extender, stirring at a constant speed for reaction for 2-3h, pouring the solution into a mould, naturally casting into a curing film, and preparing the degradable TiO2Polylactic acid grafted polyurethane antibacterial material.
Example 1
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dripping glacial acetic acid, adjusting the pH value of the solution to 2, carrying out aging reaction for 1h, slowly dripping aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant-temperature reactor, stirring at a constant speed of 30 ℃ until gel is formed, fully drying the gel product, placing the gel product into a muffle furnace, heating at a rate of 2 ℃/min, and carrying out heat preservation and calcination for 2h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in sodium hydroxide solution with mass fraction of 1%, stirring at constant speed at 20 deg.C for 48h, filtering the solution, washing with distilled water until neutral and drying, placing the solid product in tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as catalyst after stirring, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 150 deg.c in nitrogen atmosphere at the mass ratio of 20:100:0.5, stirring at constant speed for 6 hr, cooling the solution to room temperature, centrifuging to eliminate solventWashing the solid product with ethanol and fully drying to prepare the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding L-lysine diisocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 70 ℃ for reaction for 2 hours, and then adding 1, 4-butanediol serving as a micromolecular chain extender, wherein polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 10:100:50:6:0.5, the mixture is stirred at a constant speed for reaction for 2 hours, the solution is poured into a mould for natural casting to form a curing film, and the degradable TiO is prepared2Polylactic acid grafted polyurethane antibacterial material 1.
Example 2
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dripping glacial acetic acid, adjusting the pH value of the solution to 2, carrying out aging reaction for 1h, slowly dripping aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant temperature reactor, stirring at a constant speed of 30 ℃ until gel is formed, fully drying the gel product, placing the gel product into a muffle furnace, heating at a heating rate of 5 ℃/min, and carrying out heat preservation and calcination for 3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in a sodium hydroxide solution with the mass fraction of 2%, stirring at a constant speed for 60h at 30 ℃, filtering the solution, washing with distilled water until the solution is neutral and dried, placing the solid product in a tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as a catalyst after stirring uniformly, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 170 ℃ in a nitrogen atmosphere, uniformly stirring and reacting for 10 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol, and fully drying to prepare the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid for graftingNano TiO 22And polyester polyol, adding isophorone diisocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 75 ℃ for reaction for 2 hours, and then adding 1, 4-butanediol serving as a micromolecular chain extender, wherein polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 15:100:58:7:0.6, the mixture is stirred at a constant speed for reaction for 3 hours, the solution is poured into a mould for natural casting to form a curing film, and the degradable TiO is prepared2Polylactic acid grafted polyurethane antibacterial material 2.
Example 3
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dripping glacial acetic acid, adjusting the pH value of the solution to 1, carrying out aging reaction for 2 hours, slowly dripping aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant-temperature reactor, stirring at constant speed at 35 ℃ until gel is formed, fully drying the gel product, placing the gel product into a muffle furnace, heating at the rate of 4 ℃/min, and carrying out heat preservation and calcination for 2.5 hours to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in a sodium hydroxide solution with the mass fraction of 2%, stirring at a constant speed for 72h at 25 ℃, filtering the solution, washing with distilled water until the solution is neutral and dried, placing the solid product in a tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as a catalyst after stirring uniformly, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 160 ℃ in a nitrogen atmosphere, uniformly stirring for reacting for 8 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol, and fully drying to obtain the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding 4,4' -methylene bis (phenyl isocyanate) and a catalyst stannous octoate after ultrasonic dispersion is uniform, stirring at a constant speed at 75 ℃ for reaction for 3 hours, and adding 1, 4-butanediol serving as a small molecule to expandChain agent, in which polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 20:100:65:9:0.9, the mixture is stirred at a constant speed for reaction for 2.5 hours, the solution is poured into a mould for natural casting to form a curing film, and the degradable TiO is prepared2Polylactic acid grafted polyurethane antibacterial material 3.
Example 4
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dripping glacial acetic acid, adjusting the pH value of the solution to 1, carrying out aging reaction for 3h, slowly dripping aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant-temperature reactor, stirring at a constant speed of 40 ℃ until gel is formed, fully drying the gel product, placing the gel product into a muffle furnace, heating at a heating rate of 5 ℃/min, and carrying out heat preservation and calcination for 3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing the solution in a sodium hydroxide solution with the mass fraction of 5%, uniformly stirring the solution at 30 ℃ for 96 hours, filtering the solution, washing the solution by using distilled water until the solution is neutral and dried, placing a solid product in a tetrahydrofuran solvent, adding DL-lactic acid after uniformly dispersing the solid product by using ultrasonic waves, adding stannous octoate serving as a catalyst after uniformly stirring the solid product, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 170 ℃ in a nitrogen atmosphere, uniformly stirring for reaction for 10 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol, and fully drying to prepare the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 80 ℃ for reaction for 4 hours, and then adding 1, 4-butanediol serving as a micromolecular chain extender, wherein polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 25:100:70:6-10:1, the mixture is stirred at a constant speed for reaction for 3 hours, and the solution is poured into a mould to be naturally cast into a cured filmPreparation of degradable TiO2Polylactic acid grafted polyurethane antibacterial material 4.
Comparative example 1
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle, stirring uniformly, slowly dripping glacial acetic acid, adjusting the pH value of the solution to 2, carrying out aging reaction for 3h, slowly dripping aqueous solution of urea and aqueous solution of manganese chloride while stirring, placing the mixture into a constant-temperature reactor, stirring at a constant speed of 40 ℃ until gel is formed, fully drying the gel product, placing the gel product into a muffle furnace, heating at a heating rate of 3 ℃/min, and carrying out heat preservation and calcination for 3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in sodium hydroxide solution with mass fraction of 4%, stirring at constant speed for 96h at 20 ℃, filtering the solution, washing with distilled water until neutral and drying, placing the solid product in tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as catalyst after stirring uniformly, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 170 ℃ in a nitrogen atmosphere, uniformly stirring and reacting for 6 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol, and fully drying to obtain the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 80 ℃ for reaction for 4 hours, and then adding 1, 4-butanediol serving as a micromolecular chain extender, wherein polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 6:100:25:4:0.2, the mixture is stirred at a constant speed for reaction for 3 hours, the solution is poured into a mould for natural casting to form a curing film, and the degradable TiO is prepared2Polylactic acid grafted polyurethane antibacterial material 1.
Comparative example 2
(1) Adding ethanol solvent and tetrabutyl titanate into a reaction bottle,uniformly stirring, slowly dropwise adding glacial acetic acid, adjusting the pH value of the solution to 2, carrying out aging reaction for 1h, slowly dropwise adding a urea aqueous solution and a manganese chloride aqueous solution while stirring, wherein the mass ratio of tetrabutyl titanate, urea and manganese chloride is 100:40:2, placing the mixture in a constant-temperature reactor, uniformly stirring at 40 ℃ until a gel is formed, fully drying the gel product, placing the dried gel product in a muffle furnace, heating at the rate of 2 ℃/min, and carrying out heat preservation and calcination for 3h to obtain the Mn-N co-doped nano TiO2。
(2) Mn-N codoped nano TiO2Placing in 5% sodium hydroxide solution, stirring at 20 deg.C for 60h, filtering the solution, washing with distilled water until neutral and drying, placing the solid product in tetrahydrofuran solvent, adding DL-lactic acid after ultrasonic dispersion, adding stannous octoate as catalyst after stirring, wherein Mn-N codoped nano TiO is2Heating DL-lactic acid and stannous octoate to 170 ℃ in a nitrogen atmosphere, uniformly stirring and reacting for 10 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with ethanol, and fully drying to prepare the polylactic acid grafted nano TiO2。
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and polylactic acid to graft nano TiO2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, stirring at a constant speed at 70 ℃ for reaction for 2 hours, and then adding 1, 4-butanediol serving as a micromolecular chain extender, wherein polylactic acid is grafted with nano TiO2The mass ratio of the polyester polyol to the isocyanate to the 1, 4-butanediol to the stannous octoate is 28:100:75:12:1.2, the mixture is stirred at a constant speed for reaction for 3 hours, the solution is poured into a mould for natural casting to form a curing film, and the degradable TiO is prepared2Polylactic acid grafted polyurethane antibacterial material 2.
Degradable TiO in the examples and the comparative examples are respectively2Cutting the polylactic acid grafted polyurethane antibacterial material into small pieces, placing the small pieces in a culture dish, adding normal saline, activated escherichia coli suspension liquid and agar culture medium, and adding no degradable TiO2The polylactic acid grafted polyurethane antibacterial material is used as a blank control group and is uniformly vibratedThen placing the culture plate in a constant temperature and humidity incubator, culturing for 48h at 37 ℃, counting the number of colonies in a culture dish by using a 3W xenon lamp as a light source, and calculating the bacteriostasis rate, wherein the test standard is GB/T37247-.
Figure BDA0002530171220000091
Figure BDA0002530171220000101
In summary, the degradable TiO2The polylactic acid grafted polyurethane antibacterial material is prepared by taking urea as a nitrogen source and manganese chloride as a manganese source through a sol-gel method to obtain Mn-N co-doped nano TiO2Lattice of N substituted O in TiO2New impurity energy level is generated in the crystal lattice, an O-Ti-N bond is formed between a conduction band and a valence band, and the Mn-N co-doping of the nano TiO is promoted2The light absorption edge of the nano TiO material is red-shifted, so that the visible light absorption range of the nano TiO material is widened, and the Mn-N co-doped nano TiO material is enabled to be2The Mn-N co-doped nano TiO material has good photoresponse and photochemical activity under visible light, Mn replaces the crystal lattice of Ti to form a large number of crystal lattice defects, the generated oxygen vacancies can be used as capture traps of photo-generated electrons to promote the separation of the photo-generated electrons and holes, the recombination and recombination of carriers are reduced, and the Mn-N co-doped nano TiO material is obviously enhanced2Photocatalytic chemistry and photocatalytic antimicrobial properties.
The Mn-N co-doped nano TiO is greatly improved by the strong alkali etching of sodium hydroxide2The surface hydroxyl concentration ensures that the carboxyl of the DL-lactic acid is co-doped with Mn-N nano TiO under the action of a catalyst2The surface of the polylactic acid grafted nanometer TiO with a large amount of hydroxyl is polymerized in situ to generate chain end hydroxyl2Then the polylactic acid is grafted with nano TiO2In-situ polymerization of the modified material and isocyanate to obtain grafted nanometer TiO with branched chain containing polylactic acid2The polyurethane improves Mn-N co-doped nano TiO through chemical covalent bond modification of in-situ polymerization2The compatibility with polyurethane avoids the phenomenon of agglomeration in polyurethane materials and endows the polyurethane with excellent performanceDifferent photocatalytic antibacterial activity and excellent biodegradability of polylactic acid molecules are introduced into branched chains of molecular chains of polyurethane, and when the polylactic acid is subjected to biodegradation, the molecular chains of the polyurethane can be damaged, a good biodegradation effect is achieved, and pollution and damage to the environment caused by random discarding of polyurethane materials are avoided.

Claims (5)

1. Degradable TiO2The polylactic acid grafted polyurethane antibacterial material comprises the following raw materials and components, and is characterized in that: polylactic acid grafted nano TiO2The adhesive comprises polyester polyol, isocyanate, 1, 4-butanediol and stannous octoate according to the mass ratio of 10-25:100:50-70:6-10: 0.5-1.
2. The degradable TiO of claim 12-polylactic acid grafted polyurethane antibacterial material characterized in that: the isocyanate is any one of L-lysine diisocyanate, isophorone diisocyanate and 4,4' -methylene bis (phenyl isocyanate).
3. The degradable TiO of claim 12-polylactic acid grafted polyurethane antibacterial material characterized in that: the degradable TiO2The preparation method of the polylactic acid grafted polyurethane antibacterial material comprises the following steps:
(1) adding tetrabutyl titanate into an ethanol solvent, slowly dropwise adding glacial acetic acid to adjust the pH value of the solution to 1-2, carrying out aging reaction for 1-3h, slowly dropwise adding an aqueous solution of urea and an aqueous solution of manganese chloride while stirring, stirring at 30-40 ℃ until a gel is formed, fully drying the gel product, placing the gel product in a muffle furnace, heating at the rate of 2-5 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain the Mn-N co-doped nano TiO2；
(2) Mn-N codoped nano TiO2Placing in sodium hydroxide solution with mass fraction of 1-5%, stirring at constant speed for 48-96h at 20-30 ℃, filtering, washing and drying, placing the solid product in tetrahydrofuran solvent, adding DL-lactic acid and catalyst stannous octoate after ultrasonic dispersion, heating to 150-170 ℃ in nitrogen atmosphere for reactionCooling, centrifugally separating, washing and drying for 6-10h to prepare the polylactic acid grafted nano TiO2；
(3) Adding toluene solvent and polylactic acid grafted nano TiO in nitrogen atmosphere2And polyester polyol, adding isocyanate and a catalyst stannous octoate after uniform ultrasonic dispersion, reacting for 2-4h at 70-80 ℃, adding 1, 4-butanediol as a micromolecular chain extender, reacting for 2-3h, pouring the solution into a mould, naturally casting into a curing film, and preparing the degradable TiO2Polylactic acid grafted polyurethane antibacterial material.
4. A degradable TiO according to claim 32-polylactic acid grafted polyurethane antibacterial material characterized in that: the mass ratio of tetrabutyl titanate, urea and manganese chloride is 100:5-15: 0.8-1.5.
5. A degradable TiO according to claim 32-polylactic acid grafted polyurethane antibacterial material characterized in that: the Mn-N co-doped nano TiO2The mass ratio of the DL-lactic acid to the stannous octoate is 20-35:100: 0.5-1.
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