阅读说明：本技术 一种高疏水抗菌聚氨酯膜的制备工艺 (Preparation process of high-hydrophobicity antibacterial polyurethane film ) 是由 王飞 于 2020-05-28 设计创作，主要内容包括：本发明公开了一种高疏水抗菌聚氨酯膜的制备工艺,称取如下重量份原料：100-120份丙酮,30-40份含氟烷基聚醚二元醇,1-2份单丁基氧化锡,20-40份二异氰酸酯,0.5-1.5份扩链剂,5-10份KH550,20-45份二甲基甲酰胺,3-5份抗菌剂；通过静电纺丝制备出的纤维膜在纺丝过程中纤维无规取向叠加,形成多级粗糙结构,使得纤维膜表面粗糙度进一步增加,其疏水角也增加,赋予该纤维膜优异的疏水性；解决了聚氨酯本身为一种软段和硬段相间的嵌段聚合物,其中硬段能够起到防水的作用,软段具有透湿作用,所以使用时具有透湿性能,导致膜包装的材料潮湿,影响使用的技术问题。(The invention discloses a preparation process of a high-hydrophobicity antibacterial polyurethane film, which comprises the following raw materials in parts by weight: 100-120 parts of acetone, 30-40 parts of fluorine-containing alkyl polyether glycol, 1-2 parts of monobutyl tin oxide, 20-40 parts of diisocyanate, 0.5-1.5 parts of chain extender, 5-10 parts of KH550, 20-45 parts of dimethylformamide and 3-5 parts of antibacterial agent; the fiber membrane prepared by electrostatic spinning is randomly oriented and superposed in the spinning process to form a multilevel rough structure, so that the surface roughness of the fiber membrane is further increased, the hydrophobic angle of the fiber membrane is also increased, and the fiber membrane is endowed with excellent hydrophobicity; the polyurethane self-body is a block polymer with soft segments and hard segments which are alternated, wherein the hard segments can play a waterproof role, and the soft segments have a moisture permeable effect, so that the polyurethane has moisture permeable performance in use, and the technical problem that the use of the polyurethane is affected due to the fact that the material of a film package is wet is solved.)

1. A preparation process of a high-hydrophobicity antibacterial polyurethane film is characterized by comprising the following steps:

firstly, weighing the following raw materials in parts by weight: 100-120 parts of acetone, 30-40 parts of fluorine-containing alkyl polyether glycol, 1-2 parts of monobutyl tin oxide, 20-40 parts of diisocyanate, 0.5-1.5 parts of chain extender, 5-10 parts of KH550, 20-45 parts of dimethylformamide and 3-5 parts of antibacterial agent;

secondly, uniformly mixing acetone and fluorine-containing alkyl polyether glycol, adding a mixed catalyst, magnetically stirring for 30min, heating in a water bath at 40-50 ℃, dropwise adding diisocyanate, controlling the dropwise adding time to be 3-5min, reacting for 1-5h at the temperature, adding a chain extender, stirring at a constant speed, reacting for 5h, adding KH550, heating to 60-65 ℃, and reacting for 4h to obtain fluorine-containing polyurethane;

and thirdly, adding the fluorine-containing polyurethane into dimethylformamide, heating in a water bath at 40-45 ℃, magnetically stirring at the rotating speed of 420-450r/min, reacting for 24 hours to obtain a mixed stock solution, adding an antibacterial agent, transferring the mixed stock solution into an injector for electrostatic spinning, controlling the injection speed to be 8mL/h, the spinning environment temperature to be 25-28 ℃ and the relative humidity to be 40-43% until a fiber membrane with the thickness of 35-40 mu m is prepared, and transferring the fiber membrane into a vacuum drying oven for drying for 10 hours to obtain the high-hydrophobic antibacterial polyurethane membrane.

2. The process for preparing a highly hydrophobic antibacterial polyurethane film as claimed in claim 1, wherein the chain extender is one or both of 1, 4-butanediol and 1, 6-hexanediol.

3. The process for preparing a highly hydrophobic antibacterial polyurethane film as claimed in claim 1, wherein the mixed catalyst is a mixture of dimethyltin, dibenzoyl peroxide and N, N-dimethylaniline in a weight ratio of 1: 0.1.

4. The process for preparing a highly hydrophobic antibacterial polyurethane film according to claim 1, wherein the antibacterial agent is prepared by the following method: adding diatomite into a three-neck flask, adding deionized water, stirring uniformly, adding 1% sodium dodecyl benzene sulfonate solution, heating in water bath at 40-50 ℃, stirring at constant speed for 15-20min, adding 3% silver ammonia solution, heating to 55-60 ℃, adjusting pH until the pH is 8-9, then placing under ultraviolet irradiation for reaction for 3-5h, centrifuging, washing and drying to obtain the antibacterial agent.

5. The process for preparing a highly hydrophobic antibacterial polyurethane film as claimed in claim 4, wherein the weight ratio of the modified bentonite, 1% sodium dodecylbenzenesulfonate solution, deionized water and 3% silver ammonia solution is controlled to be 1: 10: 20: 2-5.

Technical Field

The invention belongs to the technical field of polyurethane film preparation, and particularly relates to a preparation process of a high-hydrophobicity antibacterial polyurethane film.

Background

Polyurethane is a block polymer composed of alternating soft and hard segment structures, wherein the soft segment is in a high elastic state at room temperature and can generate large tensile deformation, and the hard segment provides nodes for the elongation and deformation of the soft segment. The unique chemical structure of polyurethane makes it have high elasticity, high strength, wear resistance, heat resistance, chemical resistance and other characteristics, so that it is widely used in medical health, special clothing, industrial fields such as airplane parts, safety bulletproof glass and the like.

Polyurethane films have many excellent properties, but their texture is generally soft, and they have the disadvantages of poor hydrophobicity, poor antimicrobial properties, etc., which in some applications can lead to problems such as poor appearance, reduced protective properties, and shortened service life. Although the hardness can be affected by changing the degree of crosslinking, the overall performance of the polyurethane film is greatly affected in the process, and the surface is modified only by modifying the surface, and the other properties of the polyurethane film are not greatly affected, so that the application range of the polyurethane is not favorably expanded.

The invention of China patent CN104693777A is an anti-scratch polyurethane film and its preparation method, the anti-scratch polyurethane film is mainly prepared by surface modification of polyurethane film, the surface modifier of the polyurethane film is aqueous solution of fluorine-containing silicon glycol and photoinitiator, aldehyde group reacts with unreacted groups on the surface of the polyurethane film under proper conditions, the chains containing fluorine and silicon are firmly fixed on the surface, the hardness of the surface of the polyurethane film is increased, the surface tension is reduced to reduce friction, thus playing the role of anti-scratch and being beneficial to expanding the application range of the polyurethane film.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a preparation process of a high-hydrophobicity antibacterial polyurethane film.

The technical problems to be solved by the invention are as follows:

(1) the polyurethane is a segmented polymer with alternating soft segments and hard segments, wherein the hard segments can play a role in water resistance, and the soft segments have a moisture permeable function, so that the polyurethane has moisture permeability when in use, and the material of the film package is wet, so that the use is influenced;

(2) the action force between the silver ions as the bactericide and the carrier is weak, so that the system is unstable.

The purpose of the invention can be realized by the following technical scheme:

a preparation process of a high-hydrophobicity antibacterial polyurethane film comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 100-120 parts of acetone, 30-40 parts of fluorine-containing alkyl polyether glycol, 1-2 parts of monobutyl tin oxide, 20-40 parts of diisocyanate, 0.5-1.5 parts of chain extender, 5-10 parts of KH550, 20-45 parts of dimethylformamide and 3-5 parts of antibacterial agent;

secondly, uniformly mixing acetone and fluorine-containing alkyl polyether glycol, adding a mixed catalyst, magnetically stirring for 30min, heating in a water bath at 40-50 ℃, dropwise adding diisocyanate, controlling the dropwise adding time to be 3-5min, reacting for 1-5h at the temperature, adding a chain extender, uniformly stirring and reacting for 5h, adding KH550, heating to 60-65 ℃, and reacting for 4h to obtain fluorine-containing polyurethane;

and thirdly, adding the fluorine-containing polyurethane into dimethylformamide, heating in a water bath at 40-45 ℃, magnetically stirring at the rotating speed of 420-450r/min, reacting for 24 hours to obtain a mixed stock solution, adding an antibacterial agent, transferring into an injector for electrostatic spinning, controlling the injection speed to be 8mL/h, the spinning environment temperature to be 25-28 ℃ and the relative humidity to be 40-43% until a fiber membrane with the thickness of 35-40 mu m is prepared, and transferring into a vacuum drying oven for drying for 10 hours to obtain the high-hydrophobicity antibacterial polyurethane membrane.

In the second step, acetone is used as an organic solvent, fluorine-containing alkyl polyether diol and diisocyanate are used for preparing fluorine-containing polyurethane, fluorine groups are introduced into the polyurethane in the preparation process of the fluorine-containing polyurethane, and the fluorine groups can be combined with excellent mechanical properties of the polyurethane and can further enhance the hydrophobicity of the polyurethane; in the third step, the fluorine-containing polyurethane and the polyurethane are mixed, a fiber membrane is prepared through electrostatic spinning, the polyurethane is a segmented polymer with a soft segment and a hard segment which are alternated, the hard segment can play a waterproof role, and the fibers of the fiber membrane prepared through electrostatic spinning are randomly oriented and superposed in the spinning process to form a multistage rough structure, so that the surface roughness of the fiber membrane is further increased, the hydrophobic angle of the fiber membrane is also increased, and the fiber membrane is endowed with excellent hydrophobicity.

Further, the chain extender is one or two of 1, 4-butanediol and 1, 6-hexanediol.

Further, the mixed catalyst is formed by mixing dimethyl tin, dibenzoyl peroxide and N, N-dimethylaniline according to the weight ratio of 1: 0.1.

Further, the antibacterial agent is prepared by the following method: adding diatomite into a three-neck flask, adding deionized water, stirring uniformly, adding a sodium dodecyl benzene sulfonate solution with the mass fraction of 1%, heating in water bath at 40-50 ℃, stirring at a constant speed for 15-20min, adding a silver ammonia solution with the mass fraction of 3%, heating to 55-60 ℃, adjusting the pH until the pH is 8-9, then placing under ultraviolet irradiation for reaction for 3-5h, centrifuging, washing and drying to obtain the antibacterial agent.

The antibacterial agent is prepared through the silver ammonia solution and the diatomite, silver ions enter the diatomite, the diatomite has a large specific surface area and a large pore volume, and further has excellent adsorption performance, the silver ions are adsorbed between diatomite layers and in micropores, the silver ions are firmly fixed by clamping force between the diatomite layers, the stability of a system is guaranteed, the technical problems that the acting force of the silver ions between the antibacterial agent and a carrier is weak, and the system is unstable are solved, and the antibacterial agent can endow the polyurethane film with excellent antibacterial performance.

Furthermore, the weight ratio of the modified bentonite, 1 percent sodium dodecyl benzene sulfonate solution, deionized water and 3 percent silver ammonia solution is controlled to be 1: 10: 20: 2-5.

The invention has the beneficial effects that:

according to the preparation process of the high-hydrophobicity antibacterial polyurethane film, acetone is used as an organic solvent in the second step in the preparation process, fluorine-containing alkyl polyether diol and diisocyanate are used for preparing fluorine-containing polyurethane, fluorine groups are introduced into the polyurethane in the preparation process of the fluorine-containing polyurethane, and the fluorine groups can be combined with excellent mechanical properties of the polyurethane and can further enhance the hydrophobicity of the polyurethane; in the third step, fluorine-containing polyurethane and polyurethane are mixed, a fiber membrane is prepared by electrostatic spinning, the polyurethane is a segmented polymer with a soft segment and a hard segment which are alternated, wherein the hard segment can play a waterproof role, and the fibers of the fiber membrane prepared by electrostatic spinning are randomly oriented and superposed in the spinning process to form a multistage rough structure, so that the surface roughness of the fiber membrane is further increased, the hydrophobic angle of the fiber membrane is also increased, and the fiber membrane is endowed with excellent hydrophobicity; the polyurethane self-body is a block polymer with soft segments and hard segments which are alternated, wherein the hard segments can play a waterproof role, and the soft segments have a moisture permeable effect, so that the polyurethane has moisture permeable performance in use, and the technical problem that the use of the polyurethane is affected due to the fact that the material of a film package is wet is solved.

The invention also discloses an antibacterial agent, which is prepared from the silver ammonia solution and the diatomite, silver ions enter the diatomite, the diatomite has larger specific surface area and pore volume and further has excellent adsorption performance, the silver ions are adsorbed between layers of the diatomite and in micropores, the silver ions are firmly fixed by the clamping force between the layers of the diatomite, the stability of a system is ensured, the technical problems that the acting force between the silver ions as a bactericide and a carrier is weaker and the system is unstable are solved, and the antibacterial agent can endow the polyurethane film with excellent antibacterial performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.