CN110804179A - High-molecular ionic liquid with good film forming property and long-term antibacterial activity and application thereof - Google Patents
High-molecular ionic liquid with good film forming property and long-term antibacterial activity and application thereof Download PDFInfo
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Abstract
The invention discloses a high molecular ionic liquid with good film forming property and long-term bacteriostatic activity and application thereof. Guanidine salt and hexamethylene diamine are taken and are subjected to polymerization reaction through the control of a staged heating-cooling process to obtain the guanidine salt and the hexamethylene diamineProducts and compositions comprising PF6‑、BF4‑、(CF3SO2)2N‑、CF3SO3Ion exchange of the interior, to obtain. The ionic liquid antibacterial agent developed by the invention has low glass transition temperature, and the application range of guanidine salt disinfectants is expanded. Furthermore, the polymer ionic liquid antibacterial agent can be compounded with the polyvinyl alcohol enhancement liquid to form a compound film-forming enhancement liquid with good film-forming property and long-term bacteriostasis, and the compound film-forming enhancement liquid is prepared on the film material base layer through a dip-coating method to form a composite layer, so that the mechanical property (polyvinyl alcohol) and the antibacterial property (ionic liquid) of the film material can be improved, and the film material has very outstanding practical effect and application prospect.
Description
Technical Field
The invention relates to an ionic liquid, in particular to a bacteriostatic high-molecular ionic liquid prepared on the basis of guanidine salt.
Background
The chemical disinfectant is a chemical drug which can kill or inhibit microorganisms. The disinfectant is mainly used for disinfecting skin, mucous membrane, wound, environment and some articles, and has the functions of preventing and controlling infection. Most of the existing chemical disinfectants are chlorine-containing disinfectants, such as 84 disinfectants and hypochlorite; peroxide disinfectants such as hydrogen peroxide, chlorine dioxide, peracetic acid; alcohol disinfectants, such as ethanol (ethyl alcohol); iodine-containing disinfectants such as iodine tincture and iodophor; aldehyde disinfectants such as formaldehyde (formalin), glutaraldehyde, and the like. The disinfectants have been widely used in the production and life of human for many years, make great contribution to the health of people, but have more or less toxic and side effects. Guanidine disinfectants are a class of disinfection disinfectants widely used in recent years, have low toxicity, no stimulation, low effective concentration, moderate price and capability of inhibiting bacteria for a long time without toxic and side effects and sterilizing at high temperature, and are widely applied to medicine disinfection and disinfection of food and other daily necessities.
Polyhexamethylene guanidine (PHGC) is a novel broad-spectrum disinfectant developed in recent years, Mathias K. Oule 1 and the like have good inhibition effects on staphylococcus, salmonella, escherichia and the like through experimental determination of PHGC, and the antibacterial concentration is determined to be 0.001-0.1%, the action time is 5-10 min, and the bactericidal ability is very good. The influence of various factors on the sterilization capacity of the strain is researched through experiments, and the strain proves that PHGC has the characteristics of weak corrosion to some metals, low toxicity, no stimulation and allergy to skin, broad-spectrum sterilization effect, high stability and the like. The antibacterial performance of the prepared samples is evaluated by a Minimum Inhibitory Concentration (MIC) method, the MIC of all the samples is not more than 0.2 per mill, and the test proves that PHGC has good antibacterial performance. The Wangbimei and the like perform on-site simulation disinfection experiments on the PHGC-containing Taicheng brand disinfectant, and prove that the disinfectant has good sterilization effect.
PHGC is a disinfectant with good antibacterial effect, but the solid property of PHGC limits the application range of the disinfectant, and a liquid-phase PHGC preparation or a compound preparation needs to be developed urgently at present, so that the application range of the guanidine salt disinfectant is expanded.
Disclosure of Invention
The invention aims to provide a high-molecular ionic liquid with good film forming property and long-term bacteriostatic activity, a preparation method and application thereof, and a multifunctional compound preparation containing the ionic liquid and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
A high-molecular ionic liquid with excellent filming nature and long-term antibacterial activity is prepared from guanidine salt and hexanediamine through stepwise heating-cooling for polymerizing reaction to obtain product, PF6-、BF4-、(CF3SO2)2N-、CF3SO3Ion exchange in the ion exchange solution to prepare the polymer ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.
According to the preparation method of the high-molecular ionic liquid, hexamethylenediamine and guanidinium are heated and stirred under the protection of nitrogen, after the hexamethylenediamine and the guanidinium are heated to 80-120 ℃, the temperature is kept at 5-15 ℃ per liter for 10-20min until the temperature is raised to 160-200 ℃, the reaction is continued for 3-9h, and the polymerization reaction is completed; and naturally cooling the polymer to 100-140 ℃, adding acid into the polymer, and reacting for 2-6 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.
As a preferable technical scheme of the invention, the molar ratio of the hexamethylene diamine to the guanidine salt to the acid is 1 (0.8-1.2) to 0.8-1.2.
As a preferred embodiment of the present invention, the guanidine salt is selected from: guanidine hydrochloride, 6-guanidinohexanoic acid hydrochloride, hexamethylenebiguanide hydrochloride, hexamethylenebioctaguanidine, 4-hydroxyisoquinolin, 1- (5-nitrofurfurylidene) aminoguanidine hydrochloride, N-ethylguanidine hydrochloride, nitrosoguanidine, 3-chlorophenylguanidine, dodecylguanidine monohydrochloride, diethylguanidine sulfate, triaminoguanidine hydrochloride, metaiodophenylguanidine sulfate, hexamethyleneguanidine hydrochloride sulfaguanidine, hexamethyleneguanidine phosphate, aminoguanidine bicarbonate, biguanide nitrate, chloroguanidine, methylguanidine, hydrogenphosphate, N- (3, 4-dichlorophenyl) guanidine, polyaminopropylbiguanide, hexamethylene1, 6-dicyandiamide, monoguanidine phosphate, cimetidine, dodecylguanidine acetate, and triguanidine phosphate.
As a preferred embodiment of the present invention, the acid is selected from: tetrafluoroboric acid, hexafluorophosphoric acid, fluorosulfonic acid, sulfuric acid, nitric acid, trifluoroacetic acid, oxalic acid, succinic acid, adipic acid, KMD acid, methanesulfonic acid, p-toluenesulfonic acid, citric acid, aspartic acid, acetic acid, propionic acid, chloric acid.
As a preferred technical scheme, 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride are added into a dry 250mL three-necked bottle, nitrogen is introduced, the mixture is heated and stirred under the protection of nitrogen, after the mixture is heated to 100 ℃, the temperature of 10 ℃ per liter is kept for 15min until the temperature is raised to 180 ℃, the reaction is continued for 6h, and the polymerization reaction is completed; and naturally cooling the polymer to 120 ℃, adding 1mol of tetrafluoroboric acid into the polymer, and reacting for 4 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.
The polymer ionic liquid is used as a film forming agent and/or a bacteriostatic agent, or is compounded with other auxiliary agents to be used as the film forming agent and/or the bacteriostatic agent.
A compound film-forming enhancing liquid with good film-forming property and long-term bacteriostasis is prepared by compounding the macromolecular ionic liquid and a polyvinyl alcohol enhancing liquid.
As a preferable technical scheme of the invention, the volume ratio of the high molecular ionic liquid to the polyvinyl alcohol reinforced liquid is 1 (5-20).
As a preferred technical scheme of the invention, the preparation method of the polyvinyl alcohol enhanced liquid comprises the following steps: adding polyvinyl alcohol and water into a reaction container, adjusting the temperature to 80-100 ℃, magnetically stirring for 1.5-2.5h, adding a plasticizer, and continuously stirring for 5-10 min to obtain a uniform and transparent polyvinyl alcohol reinforcing solution.
As a preferred technical scheme of the invention, the dosage of each material in the polyvinyl alcohol reinforcing liquid is as follows: 3-10 parts by weight of polyvinyl alcohol, 3-20 parts by weight of plasticizer and 70-94 parts by weight of water; wherein, the polymerization degree of the polyvinyl alcohol is 1750 +/-50; the plasticizer is selected from one or a combination of more of glycerol, ethylene glycol and ethanolamine.
The compound film-forming reinforcing liquid is used as a composite layer of a film material, and the mechanical property and the antibacterial property of the film material are improved.
The application method of the compound film-forming enhancing liquid comprises the steps of immersing a cellulose film prepared in advance into the compound film-forming enhancing liquid, stirring to enable the surface of the film to be uniformly covered with a layer of the compound film-forming enhancing liquid, taking out the film and vertically placing the film, enabling redundant liquid to flow down along the surface of the film, supporting the film tightly by using a support, preventing the film from being tightened and wrinkled due to surface shrinkage in the drying process, and drying for 2-4 hours to obtain the natural degradable cellulose-reinforced composite film with a long-term antibacterial effect.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the invention develops a guanidine salt high-molecular ionic liquid antibacterial agent with thermal stability, which is in a white transparent viscous liquid state at normal temperature, the solution of the antibacterial agent can achieve the antibacterial effect on escherichia coli within the concentration range of 5-50 ppm, and meanwhile, the antibacterial agent is non-volatile and non-combustible, can inhibit bacteria for a long time, and has the characteristics of low toxicity, good thermal stability, low glass transition temperature, simple and convenient production and the like, and the application range of a guanidine salt disinfectant is expanded due to the fact that the antibacterial agent is in a liquid state at normal temperature.
The high-molecular ionic liquid antibacterial agent can be compounded with polyvinyl alcohol reinforcing liquid to form compound film-forming reinforcing liquid with good film-forming property and long-term antibacterial activity, and the compound film-forming reinforcing liquid is prepared on a film material base layer through a dip-coating method to form a composite layer, so that the mechanical property (polyvinyl alcohol) and the antibacterial property (ionic liquid) of the film material can be improved, and the high-molecular ionic liquid antibacterial agent is particularly suitable for a cellulose natural film layer (the tensile strength after reinforcement is 7.75-46.25 Mpa, the elongation at break is 226.67-695.83%, and has the long-term antibacterial activity of the ionic liquid), and has very outstanding practical effect and application prospect.
Drawings
FIG. 1 is a photograph of a bacteriostasis test, wherein the effective concentration of the left picture is 30ppm, and the effective concentration of the right picture is 50ppm, which have good bacteriostasis effects.
FIG. 2 is a photograph of a film forming test sample.
FIG. 3 shows the distribution of bacteria around the bacteriostatic membrane.
Figure 4 shows no bacterial growth under the bacteriostatic membrane.
Detailed Description
The following examples illustrate the invention in detail. The raw materials and various devices used in the invention are conventional commercially available products, and can be directly obtained by market purchase.
Example 1 preparation of Ionic liquid
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and naturally cooling the polymer to 120 ℃, adding 1mol of hexafluorophosphoric acid into the polymer, reacting for 3h, and obtaining the antibacterial macromolecular ionic liquid product after the reaction is finished.
Example 2 preparation of Ionic liquid (II)
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and naturally cooling the polymer to 120 ℃, adding 1mol of fluorosulfonic acid into the polymer, and reacting for 5 hours to obtain the antibacterial high-molecular ionic liquid product.
Example 3 preparation of Ionic liquid (III)
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and (3) performing suspended evaporation to remove the solvent, performing suction filtration to obtain a polymerization product, heating to 120 ℃, adding 1mol of tetrafluoroboric acid into the polymer, reacting for 4 hours, and finishing the reaction to obtain the antibacterial macromolecular ionic liquid product.
Example 4 preparation of Ionic liquid (IV)
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and (3) performing suspended evaporation to remove the solvent, performing suction filtration to obtain a polymerization product, heating to 120 ℃, adding 1mol of trifluoroacetic acid into the polymer, reacting for 6 hours, and finishing the reaction to obtain the antibacterial high-molecular ionic liquid product.
Example 5 preparation of Ionic liquid (V)
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 90 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and (3) performing suspended evaporation to remove the solvent, performing suction filtration to obtain a polymerization product, heating to 120 ℃, adding 1mol of thiocyanic acid into the polymer, reacting for 6 hours, and obtaining the antibacterial high-molecular ionic liquid after the reaction is finished.
Example 6 preparation of Ionic liquid (VI)
Adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing argon, heating and stirring under the protection of argon, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is raised to 170 ℃, continuing to react for 6h, and finishing the polymerization reaction; and (3) performing suspended evaporation to remove the solvent, performing suction filtration to obtain a polymerization product, heating to 120 ℃, adding 1mol of trifluoromethanesulfonic acid into the polymer, reacting for 6h, and finishing the reaction to obtain the antibacterial high-molecular ionic liquid product.
Example 7 melting Point measurement of Ionic liquid
The ionic liquids prepared in the above examples were measured for melting point, which ranged from 6.2 ℃ to 7.1 ℃ with an average of 6.7 ℃.
Example 8 antimicrobial Performance testing of Ionic liquids
And (3) testing the short-term bacteriostatic effect of the ionic liquid: the Escherichia coli bacterial suspension is placed in a constant-temperature incubator at 37 ℃ and 170r/min for half an hour. Diluting the bacterial suspension with normal saline to 10 of the original concentration in a sterile table-3.5Shaking up with a vortex mixer, injecting ionic liquid with corresponding concentration, shaking up again, standing for 30s, placing 100 μ l on the prepared Escherichia coli culture medium, wiping the coating rod with alcohol, burning with alcohol lamp for 5s, cooling to room temperature, and rotating clockwise to uniformly coat the bacterial suspension on the culture medium. The coated culture medium is placed in a constant-temperature incubator at 37 ℃, cultured for 24h, and subjected to a viable count method, blank experiments and control experiments are simultaneously carried out, each sample is parallelly measured for five times, the bacteriostasis rate is obtained, and the results are shown in the table below.
From the bacteriostatic results in the table above, the bacteriostatic polymeric ionic liquid has a bacteriostatic effect on escherichia coli, and when the concentration of the polymeric ionic liquid is 10ppm to 50ppm, the bacteriostatic rate increases with the increase of the concentration of the polymeric ionic liquid; when the concentration of the polymer ionic liquid is increased to 100ppm or more, the antibacterial rate of the polymer ionic liquid to escherichia coli reaches 100%.
And (3) testing the long-term bacteriostatic effect of the ionic liquid: the Escherichia coli bacterial suspension is placed in a constant-temperature incubator at 37 ℃ and 170r/min for half an hour. Diluting the bacterial suspension with normal saline to 10 of the original concentration in a sterile table-3.5By mixing it with a vortex mixerShaking, injecting treated ionic liquid with corresponding concentration, shaking again, standing for 30s, placing 100 μ l on prepared Escherichia coli culture medium, wiping coating rod with alcohol, burning with alcohol lamp for 5s, cooling to room temperature, and rotating clockwise to uniformly coat the bacterial suspension on culture medium containing enough nutrients. And (3) placing the coated culture medium in a constant-temperature incubator, carrying out constant-temperature culture at 37 ℃ for 6 months, carrying out a viable count method, simultaneously carrying out blank experiments and control experiments, carrying out parallel determination on each sample for five times, obtaining the bacteriostasis rate, and obtaining the result shown in the following table.
From the bacteriostatic results in the table above, after 6 months of accelerated experiments, when the concentration of the polymer ionic liquid is 10ppm to 50ppm, the bacteriostatic rate of the bacteriostatic polymer ionic liquid increases with the increase of the concentration of the polymer ionic liquid, but the bacteriostatic rate of the polymer ionic liquid with the same concentration decreases, and when the concentration reaches 100ppm or more, the bacteriostatic rate of the bacteriostatic polymer ionic liquid on escherichia coli is still 100%.
EXAMPLE 9 preparation of polyvinyl alcohol enhancing solution
The preparation method of the polyvinyl alcohol enhancing liquid comprises the following steps: adding polyvinyl alcohol and water into a reaction vessel, adjusting the temperature to 90 ℃, magnetically stirring for 2h, adding a plasticizer, and continuously stirring for 8min to obtain a uniform and transparent polyvinyl alcohol reinforcing solution. Wherein the dosage of each material is as follows: 7 parts of polyvinyl alcohol, 10 parts of plasticizer glycerol and 83 parts of water; wherein, the polymerization degree of the polyvinyl alcohol is 1750 +/-50.
Example 10 preparation of a Compound film-Forming enhancing solution
The compound film-forming enhancing liquid is formed by compounding a high-molecular ionic liquid and a polyvinyl alcohol enhancing liquid, and has good film-forming property and long-term antibacterial activity. Wherein the volume ratio of the polymer ionic liquid to the polyvinyl alcohol reinforced liquid is 1: 15.
Example 11 preparation of cellulose-reinforced composite Membrane that is naturally degradable and has Long-term bacteriostatic Effect
The compound film-forming enhancing liquid prepared by the embodiment is prepared on the film material base layer by a dip-coating method to form a composite layer, can improve the mechanical property (polyvinyl alcohol) and the antibacterial property (ionic liquid) of the film material, is particularly suitable for a cellulose natural film layer, and has very outstanding practical effect and application prospect. The preparation method comprises the following steps: and (2) immersing a cellulose membrane prepared in advance into the compound film-forming enhancing liquid, stirring to uniformly cover a layer of the compound film-forming enhancing liquid on the surface of the membrane, taking out the membrane and vertically placing the membrane, allowing redundant liquid to flow down along the surface of the membrane, tightly supporting the membrane by using a support, preventing the membrane from being tightened and wrinkled due to surface shrinkage in the drying process, and drying for 2-4 hours to obtain the natural degradable cellulose-reinforced composite membrane with a long-term antibacterial effect.
Example 12 mechanical index of cellulose-reinforced composite film
The cellulose reinforced composite film prepared in example 11 was measured for tensile strength: 7.75-46.25 MPa; elongation at break: 226.67% -695.83%; the composite membrane is shown to have obviously enhanced mechanical property indexes.
The above description is only presented as an enabling solution for the present invention and should not be taken as a sole limitation on the solution itself.
Claims (13)
1. A high molecular ionic liquid with good film forming property and long-term bacteriostasis is characterized in that: firstly, guanidine salt and hexamethylene diamine are taken and are subjected to polymerization reaction through the control of a staged heating-cooling process, and the obtained product and PF6-、BF4-、(CF3SO2)2N-、CF3SO3Ion exchange in the ion exchange solution to prepare the polymer ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.
2. A method for preparing the polymeric ionic liquid of claim 1, wherein: heating and stirring hexamethylene diamine and guanidine salt under the protection of nitrogen, keeping the temperature of 5-15 ℃ per liter for 10-20min after heating to 80-120 ℃, continuing to react for 3-9h until the temperature is raised to 160-200 ℃, and finishing the polymerization reaction; the polymer is naturally cooled to 140 ℃ below zero, acid is added into the polymer, and the polymer is reacted for 2 to 6 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term bacteriostasis.
3. The method for producing a polymeric ionic liquid according to claim 2, wherein: the molar ratio of the hexamethylene diamine to the guanidine salt to the acid is 1 (0.8-1.2) to 0.8-1.2.
4. The method for producing a polymeric ionic liquid according to claim 2, wherein: the guanidine salt is selected from: guanidine hydrochloride, 6-guanidinohexanoic acid hydrochloride, hexamethylenebiguanide hydrochloride, hexamethylenebioctaguanidine, 4-hydroxyisoquinolin, 1- (5-nitrofurfurylidene) aminoguanidine hydrochloride, N-ethylguanidine hydrochloride, nitrosoguanidine, 3-chlorophenylguanidine, dodecylguanidine monohydrochloride, diethylguanidine sulfate, triaminoguanidine hydrochloride, metaiodophenylguanidine sulfate, hexamethyleneguanidine hydrochloride sulfaguanidine, hexamethyleneguanidine phosphate, aminoguanidine bicarbonate, biguanide nitrate, chloroguanidine, methylguanidine, hydrogenphosphate, N- (3, 4-dichlorophenyl) guanidine, polyaminopropylbiguanide, hexamethylene1, 6-dicyandiamide, monoguanidine phosphate, cimetidine, dodecylguanidine acetate, and triguanidine phosphate.
5. The method for producing a polymeric ionic liquid according to claim 2, wherein: the acid is selected from: tetrafluoroboric acid, hexafluorophosphoric acid, fluorosulfonic acid, sulfuric acid, nitric acid, trifluoroacetic acid, oxalic acid, succinic acid, adipic acid, KMD acid, methanesulfonic acid, p-toluenesulfonic acid, citric acid, aspartic acid, acetic acid, propionic acid, chloric acid.
6. The method for producing a polymeric ionic liquid according to claim 2, wherein: adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and naturally cooling the polymer to 120 ℃, adding 1mol of tetrafluoroboric acid into the polymer, and reacting for 4 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.
7. The use of the polymeric ionic liquid of claim 1 as a film-forming agent and/or a bacteriostatic agent, or as a film-forming agent and/or a bacteriostatic agent after being compounded with other auxiliary agents.
8. A compound film-forming enhancing liquid with good film-forming property and long-term bacteriostasis is characterized in that: the compound film-forming enhancing liquid is prepared by compounding the macromolecular ionic liquid and the polyvinyl alcohol enhancing liquid in claim 1.
9. The compound film-forming enhancing liquid with good film-forming property and long-term bacteriostasis of claim 8, which is characterized in that: the volume ratio of the high molecular ionic liquid to the polyvinyl alcohol reinforced liquid is 1 (5-20).
10. The compound film-forming enhancing liquid with good film-forming property and long-term bacteriostasis of claim 8, which is characterized in that: the preparation method of the polyvinyl alcohol enhancing liquid comprises the following steps: adding polyvinyl alcohol and water into a reaction vessel, adjusting the temperature to 80-100 ℃, magnetically stirring for 1.5-2.5h, adding a plasticizer, and continuously stirring for 5-10 min to obtain a uniform and transparent polyvinyl alcohol enhancement solution.
11. The compound film-forming enhancing liquid with good film-forming property and long-term bacteriostasis of claim 10, which is characterized in that: the dosage of each material in the polyvinyl alcohol enhancing liquid is as follows: 3-10 parts of polyvinyl alcohol, 3-20 parts of plasticizer and 70-94 parts of water; wherein, the polymerization degree of the polyvinyl alcohol is 1750 +/-50; the plasticizer is selected from one or a combination of more of glycerol, ethylene glycol and ethanolamine.
12. The use of the compound film-forming enhancing fluid of claim 8 as a composite layer of a film material to improve the mechanical properties and antibacterial properties of the film material.
13. Use according to claim 12, characterized in that: and (2) immersing a cellulose membrane prepared in advance into the compound film-forming enhancing liquid, stirring to uniformly cover a layer of the compound film-forming enhancing liquid on the surface of the membrane, taking out the membrane and vertically placing the membrane, allowing redundant liquid to flow down along the surface of the membrane, tightly supporting the membrane by using a support, preventing the membrane from being tightened and wrinkled due to surface shrinkage in the drying process, and drying for 2-4 hours to obtain the natural degradable cellulose-reinforced composite membrane with a long-term antibacterial effect.
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