CN111621141B - Slow-release chlorine dioxide-waterborne polyurethane antibacterial film and preparation method thereof - Google Patents

Slow-release chlorine dioxide-waterborne polyurethane antibacterial film and preparation method thereof Download PDF

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CN111621141B
CN111621141B CN202010532685.XA CN202010532685A CN111621141B CN 111621141 B CN111621141 B CN 111621141B CN 202010532685 A CN202010532685 A CN 202010532685A CN 111621141 B CN111621141 B CN 111621141B
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chlorine dioxide
waterborne polyurethane
slow
antibacterial film
release
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CN111621141A (en
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黄崇杏
赵辉
许承龙
黄兴强
黄丽婕
段青山
王健
赵媛
黄浩河
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Guangxi University
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Abstract

The invention discloses a slow-release chlorine dioxide-waterborne polyurethane antibacterial film and a preparation method thereof, belonging to the field of antibacterial materials, wherein the preparation method comprises two steps, the first step is the synthesis of a waterborne polyurethane dispersion liquid, and the synthesis raw materials of the dispersion liquid comprise a hard segment, a soft segment, 2-dimethylolpropionic acid, triethylamine, acetone and a catalyst dibutyltin dilaurate; secondly, preparing a chlorine dioxide-waterborne polyurethane antibacterial film, namely adding a stable chlorine dioxide aqueous solution into the dispersion liquid, and preparing the slow-release chlorine dioxide-waterborne polyurethane antibacterial film by a casting method; the carboxylic acid in the membrane is used as an acid activator for reacting with chlorine dioxide, chlorine dioxide gas can be produced, the membrane material has antibacterial performance, and the release of the chlorine dioxide gas is controlled by the release of the carboxylic acid in the membrane, so that a certain slow release effect is achieved.

Description

Slow-release chlorine dioxide-waterborne polyurethane antibacterial film and preparation method thereof
Technical Field
The invention relates to the field of antibacterial materials, in particular to a slow-release chlorine dioxide-waterborne polyurethane antibacterial film and a preparation method thereof.
Background
The antibacterial film is the most applied form in antibacterial packaging, and has better application prospect mainly because the antibacterial film has low preparation cost, wide application range and obvious antibacterial effect. The bacteriostasis effect of the antibacterial film is mainly determined by the added antibacterial agent, and different antibacterial agents have great influence on the bacteriostasis effect of the antibacterial film. As for the antibacterial agent, the antibacterial film may be classified into an organic antibacterial film, an inorganic antibacterial film and a natural antibacterial film, and the antibacterial effect of these antibacterial films depends on the kind and the addition amount of the antibacterial agent and the base material of the film.
The Waterborne Polyurethane (WPU) takes water as a solvent, is green, environment-friendly, pollution-free and free of toxic and side effects, and gradually replaces Polyurethane (PU) to become a more green and environment-friendly synthetic material. The waterborne polyurethane has good compatibility, mechanical property and film-forming property, and can be used as a film substrate.
Chlorine dioxide (ClO)2) The chlorine dioxide disinfectant has the advantages of high-efficiency sterilization effect, no pollution to the environment, no three-cause (carcinogenic, teratogenic and mutagenic) substances during use and the like, so the chlorine dioxide is classified as an A1 grade product in safe disinfection substances by the world health organization, and the chlorine dioxide is also widely applied to the fields of water treatment, air purification, medical treatment, food preservation and the like. In the life and production, the gaseous chlorine dioxide is easy to decompose under the action of light or heat, and the liquid chlorine dioxide is liquidCompared with the prior art, the solid chlorine dioxide has the advantages of strong stability, convenient storage and transportation and certain slow release effect. However, solid chlorine dioxide still has some defects, such as sudden release of chlorine dioxide in a slow release stage, difficulty in controlling the release rate, and the like, and the problems need to be solved urgently. The patent documents currently mentioning the control of the release rate of chlorine dioxide include the following technical solutions:
the catalytic invention discloses a preparation method of formaldehyde-removing chlorine dioxide sustained-release gel, which comprises the steps of mixing sodium gluconate, a gelling agent and a chlorine dioxide precursor to obtain a chlorine dioxide gel system; adding polyethylene glycol and an acidic reagent into the system to obtain an activated chlorine dioxide sustained-release gel system; and adding barium sulfate into the system to obtain a stable activated chlorine dioxide gel system.
The Shanghai ocean university invents a preparation method of chlorine dioxide slow-release preservative gel, the chlorine dioxide slow-release preservative gel comprises a gel layer A and a gel layer B, the raw materials for preparing the gel layer A comprise chitosan, sodium hydroxide aqueous solution and sodium chlorite, and the raw materials for preparing the gel layer B comprise chitosan, acetic acid aqueous solution, acidic substances and glutaraldehyde aqueous solution; when the adhesive is applied, the gel layer A and the gel layer B are attached.
The Qingdao agricultural university invents a micro-controlled release high-efficiency gas fresh-keeping material, which comprises sodium chlorite, citric acid, ferrous chloride, ferrous sulfate, ammonium ferrous sulfate, silica gel, gelatin, polyacrylamide, sodium alginate, beta-cyclodextrin and deionized water, and the fresh-keeping material with 1-4 layers of chlorine dioxide sandwich layers can be prepared according to the preparation process.
The Ningbo university invents a long-acting slow-release chlorine dioxide preservative, which consists of tablets and powder, wherein the tablets mainly consist of a silica gel adsorbent, sodium chlorite, a microporous network structure forming agent, an ion field forming agent and water; the powder is mainly composed of weak acid activator, silica gel adsorbent, water and adhesive, and then the tablet and powder are put into a breathable non-woven fabric packaging bag. The application method comprises slightly squeezing the packaging bag, and placing in humid environment.
However, in the preparation of chlorine dioxide antibacterial materials, researchers often add sodium chlorite powder and organic acid directly. Sodium chlorite is a precursor for generating chlorine dioxide, is directly mixed in a material, is unstable and is easy to decompose under the conditions of illumination, high temperature and high humidity, and the yield and the acting time of the chlorine dioxide are limited to a certain extent.
Disclosure of Invention
The invention aims to provide a slow-release chlorine dioxide-waterborne polyurethane antibacterial film and a preparation method thereof, which are used for solving the problems in the prior art, so that the antibacterial film can achieve the controlled release effect on chlorine dioxide, prolong the slow release time and achieve the long-acting antibacterial and fresh-keeping effect.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a slow-release chlorine dioxide-waterborne polyurethane antibacterial film, which comprises the steps of adding a stable chlorine dioxide aqueous solution into a waterborne polyurethane dispersion, stirring and mixing uniformly, putting into a mould, and air-drying at room temperature to form a film, thus obtaining the slow-release chlorine dioxide-waterborne polyurethane antibacterial film;
the preparation method of the aqueous polyurethane dispersion comprises the following steps:
adding a soft segment and 2, 2-hydroxymethyl propionic acid under a protective atmosphere, adding acetone under a stirring condition, carrying out first heating, stirring, dropwise adding a catalyst, adding a hard segment and acetone, carrying out condensation reflux, adding triethylamine and acetone, and carrying out second heating;
stopping heating, cooling, dripping distilled water, and reacting to obtain the aqueous polyurethane dispersion.
Further, in each raw material, the total molar ratio of isonitrile acid radicals to hydroxyl groups is 1.4:1, and the molar weight ratio of triethylamine to 2, 2-dimethylolpropionic acid is 1: 1.
Further, when the acetone is added for the first time, the stirring speed of the stirring condition is 150-250r/min, the adding amount of the acetone is 10-200% of the soft segment molar weight, and the amount of the acetone added each time is the same.
Further, the temperature of the first heating is 40-50 ℃, and the stirring time after heating is 20-30 min.
Further, before the catalyst is added dropwise, the solution system is required to be colorless and transparent.
Further, the heating time of the second heating is 1 h.
Further, the dropping process of the distilled water is carried out in a stirring state, and the cooling is carried out to be below 10 ℃;
before the distilled water is dripped, the stirring speed is 900-1100r/min, the dripping speed is 2-3 s/min, and when the solution system shows the phenomenon of thickening and thinning, the stirring speed is adjusted to 400-600 r/min.
Further, the adding amount of the stable chlorine dioxide water solution is 6-30% of the volume of the aqueous polyurethane dispersion liquid.
Further, the catalyst was dibutyltin dilaurate, and the amount added was 0.25 ml.
Further, the hard segment is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the soft segment is one or more of polytetrahydrofuran with molecular weight of 1000-3000, polytrimethylene ether glycol, polycaprolactone glycol and polycarbonate glycol.
The invention also provides the slow-release chlorine dioxide-waterborne polyurethane antibacterial film prepared by the preparation method of the slow-release chlorine dioxide-waterborne polyurethane antibacterial film.
The invention discloses the following technical effects:
1) the base material of the antibacterial film is selected from waterborne polyurethane, and the antibacterial film has the advantages of no toxicity, no pollution to the environment, easy processing and the like, has good compatibility and excellent mechanical property and film forming property, and can be used as a food packaging material.
2) Under the preparation process condition of the invention, the prepared slow-release chlorine dioxide/waterborne polyurethane antibacterial film has the tensile strength of 10.0-11.8MPa, the elongation at break of about 450-530 percent, and the water vapor transmission of the film is 120 g/(m-224h) oxygen transmission rate of the membrane3.3-6.2cm3·m-2·24h-1The antibacterial rate of the antibacterial film can reach more than 98%.
3) For the first time, carboxylic acid in the waterborne polyurethane film is taken as an activating agent, and ClO is utilized on the premise of not adding other acidic reagents2And the chlorine dioxide gas is reacted with acid under the excitation of moisture at a constant speed, so that the slow release effect is improved, and the sudden release phenomenon which is easy to occur in the release process of the chlorine dioxide gas is effectively improved.
Drawings
FIG. 1 is a plan view of a sustained-release chlorine dioxide-aqueous polyurethane antibacterial film prepared in example 1;
FIG. 2 is a sectional view of the slow-release chlorine dioxide-aqueous polyurethane antibacterial film prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
Example 1
1) Synthesis of aqueous polyurethane dispersion:
adding 62.9109g of polytetrahydrofuran and 2.4842g of 2, 2-dimethylolpropionic acid into a 500ml round-bottom four-neck flask which is provided with a digital display stirrer, a temperature control device and Ar protective gas; regulating the rotation speed of the stirrer to 200r/min, and adding 125ml of acetone while stirring; the interface is wound by a polytetrafluoroethylene raw material tape after the coiled condenser tube is connected to ensure the sealing property.
Controlling the heating temperature to be 40-50 ℃ by a temperature control device, heating and stirring for 20min, when the solution in the four-neck flask is colorless and transparent, dropwise adding 0.25ml of catalyst (dibutyltin dilaurate) after 5min, dropwise adding 15.54g of isophorone diisocyanate and equivalent acetone after 5 min; when the temperature in the four-mouth flask reaches about 70 ℃, condensation reflux begins to appear in the condensation tube, and 1.8724g of triethylamine and equivalent acetone are added after 4 hours of condensation reflux; stopping heating after triethylamine is added for one hour, taking down the condenser pipe when the temperature in the four-neck flask is reduced to below 10 ℃, connecting the condenser pipe to a constant-pressure funnel filled with 160ml of distilled water, and dropwise adding at the speed of 6ml/min (the rotating speed of a stirrer is adjusted to 1000r/min before dropwise adding), wherein the solution in the flask can be thickened and thinned in the dropwise adding process, and the rotating speed of the stirrer is adjusted to 500r/min at the moment, so that the solution is prevented from splashing to the inner wall of the flask; and after the distilled water in the constant-pressure funnel is dripped, reacting for 30min to obtain the aqueous polyurethane dispersion, and pouring the aqueous polyurethane dispersion into a silk-mouth bottle for sealing and storing.
2) Preparing a chlorine dioxide-waterborne polyurethane antibacterial film:
measuring 30ml of the aqueous polyurethane dispersion prepared in the step 1) by using a measuring cylinder, adding 2ml of stable chlorine dioxide aqueous solution, stirring and mixing the two solutions uniformly, pouring the mixture into a horizontally placed square polytetrafluoroethylene mold, and naturally air-drying the mixture for 24 hours at room temperature to form a film, so as to obtain the slow-release chlorine dioxide-aqueous polyurethane antibacterial film, wherein the plan view of the film is shown in figure 1, and the cross section of the film is shown in figure 2.
The antibacterial film prepared in the embodiment 1 has the tensile strength of 10.5MPa, the elongation at break of 460 percent and the water vapor transmission capacity of 112 g/(m)224h) oxygen transmission rate of the membrane was 4.6cm3·m-2·24h-1The antibacterial rate of the antibacterial film can reach more than 98%.
Example 2
1) Synthesis of aqueous polyurethane dispersion:
adding 48.2248g of polytetrahydrofuran and 3.4826g of 2, 2-dimethylolpropionic acid into a 500ml round-bottom four-neck flask which is provided with a digital display stirrer, a temperature control device and Ar protective gas; regulating the rotation speed of the stirrer to 200r/min, and adding 100ml of acetone while stirring; the interface is wound by a polytetrafluoroethylene raw material tape after the coiled condenser tube is connected to ensure the sealing property.
Controlling the heating temperature to be 40-50 ℃ by a temperature control device, heating and stirring for 20min, when the solution in the four-neck flask is colorless and transparent, dropwise adding 0.25ml of catalyst (dibutyltin dilaurate) after 5min, dropwise adding 15.54g of isophorone diisocyanate and equivalent acetone after 5 min; when the temperature in the four-neck flask reaches about 70 ℃, condensation reflux begins to appear in the condensation pipe, and 2.6250g of triethylamine and equivalent acetone are added after 4 hours of condensation reflux; stopping heating after triethylamine is added for one hour, taking down the condenser pipe when the temperature in the four-neck flask is reduced to below 10 ℃, connecting the condenser pipe to a constant-pressure funnel filled with 140ml of distilled water, and dropwise adding at the speed of 6ml/min (the rotating speed of a stirrer is adjusted to 900r/min before dropwise adding), wherein the solution in the flask can be thickened and thinned in the dropwise adding process, and the rotating speed of the stirrer is adjusted to 450r/min at the moment, so that the solution is prevented from splashing to the inner wall of the flask; and (3) reacting for 30min after the distilled water in the constant-pressure funnel is dripped, thus obtaining the aqueous polyurethane dispersion, and pouring the aqueous polyurethane dispersion into a silk-mouth bottle for sealed storage.
2) Preparing a chlorine dioxide-waterborne polyurethane antibacterial film:
measuring 50ml of the waterborne polyurethane dispersion prepared in the step 1) by using a measuring cylinder, adding 5ml of stable chlorine dioxide aqueous solution, stirring and mixing the two solutions uniformly, pouring the mixture into a horizontally placed square polytetrafluoroethylene mold, and naturally drying the mixture for 24 hours at room temperature to form a film, thereby obtaining the slow-release chlorine dioxide-waterborne polyurethane antibacterial film.
The antibacterial film prepared in the embodiment 2 has the tensile strength of 11.0MPa, the elongation at break of 480 percent and the water vapor transmission capacity of 110 g/(m)224h) oxygen transmission rate of the membrane was 3.6cm3·m-2·24h-1The antibacterial rate of the antibacterial film can reach more than 99%.
Example 3
1) Synthesis of aqueous polyurethane dispersion:
adding 37.2014g of polytetrahydrofuran and 4.2062g of 2, 2-dimethylolpropionic acid into a 500ml round-bottom four-neck flask which is provided with a digital display stirrer, a temperature control device and Ar protective gas; the rotation speed of the stirrer is adjusted to 250r/min, and 75ml of acetone is added during stirring; the interface is wound by a polytetrafluoroethylene raw material tape after the coiled condenser tube is connected to ensure the sealing property.
Controlling the heating temperature to be 40-50 ℃ by a temperature control device, heating and stirring for 25min, when the solution in the four-neck flask is colorless and transparent, dropwise adding 0.25ml of catalyst (dibutyltin dilaurate) after 5min, dropwise adding 15.54g of isophorone diisocyanate and equivalent acetone after 4 min; when the temperature in the four-mouth flask reaches about 70 ℃, condensation reflux begins to appear in the condensation tube, and 3.1703g of triethylamine and equivalent acetone are added after 4 hours of condensation reflux; stopping heating after triethylamine is added for one hour, taking down the condenser pipe when the temperature in the four-neck flask is reduced to below 10 ℃, connecting the condenser pipe to a constant-pressure funnel filled with 120ml of distilled water, and dropwise adding at the speed of 6ml/min (the rotating speed of a stirrer is adjusted to 900r/min before dropwise adding), wherein the solution in the flask can be thickened and thinned in the dropwise adding process, and the rotating speed of the stirrer is adjusted to 500r/min at the moment, so that the solution is prevented from splashing to the inner wall of the flask; and (3) reacting for 30min after the distilled water in the constant-pressure funnel is dripped, thus obtaining the aqueous polyurethane dispersion, and pouring the aqueous polyurethane dispersion into a silk-mouth bottle for sealed storage.
2) Preparing a chlorine dioxide-waterborne polyurethane antibacterial film:
measuring 60ml of the waterborne polyurethane dispersion prepared in the step 1) by using a measuring cylinder, adding 8ml of stable chlorine dioxide aqueous solution, stirring and mixing the two solutions uniformly, pouring the mixture into a horizontally placed square polytetrafluoroethylene mold, and naturally drying the mixture for 36 hours at room temperature to form a film, thereby obtaining the slow-release chlorine dioxide-waterborne polyurethane antibacterial film.
The tensile strength of the antibacterial film prepared in the embodiment 1 can reach 10.1MPa, the elongation at break is about 450%, and the water vapor transmission capacity of the film is 130 g/(m)224h) oxygen transmission rate of the membrane was 5.5cm3·m-2·24h-1The antibacterial rate of the antibacterial film can reach more than 99%.
Comparative example 1
The difference from example 3 is that the distilled water dropping operation was changed to direct mixing.
The water vapor transmission rate of the antibacterial film prepared in comparative example 1 was 89 g/(m)224h) oxygen transmission rate of the membrane was 1.5cm3·m-2·24h-1The antibacterial rate of the antibacterial film is more than 85%.
Comparative example 2
The difference from example 3 is that acetone was added in an amount of 3 times the amount of polytetrahydrofuran added in each case.
The water vapor transmission rate of the antibacterial film prepared in comparative example 2 was 89 g/(m)224h) oxygen transmission rate of the membrane was 1.8cm3·m-2·24h-1The antibacterial rate of the antibacterial film is more than 88%.
Comparative example 3
The difference from example 3 is that the amounts of acetone added in three times are different, and the amounts of acetone added from the first time to the third time are respectively 1 time, 1.3 times and 1.9 times of the amount of polytetrahydrofuran added.
Tests show that the antibacterial agent prepared in comparative example 3The water vapor transmission rate of the film was 78 g/(m)224h) oxygen transmission rate of the membrane was 2.1cm3·m-2·24h-1The antibacterial rate of the antibacterial film is more than 80%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (7)

1. A preparation method of a slow-release chlorine dioxide-waterborne polyurethane antibacterial film is characterized in that a stable chlorine dioxide aqueous solution is added into a waterborne polyurethane dispersion liquid, the mixture is stirred and mixed evenly, the mixture is placed into a mold, and the mold is dried at room temperature to form a film, so that the slow-release chlorine dioxide-waterborne polyurethane antibacterial film is obtained;
the preparation method of the aqueous polyurethane dispersion comprises the following steps:
adding a soft segment and 2, 2-dimethylolpropionic acid in a protective atmosphere, adding acetone under the stirring condition, carrying out first heating, stirring, dropwise adding a catalyst, adding a hard segment and acetone, carrying out condensation reflux, adding triethylamine and acetone, and carrying out second heating;
stopping heating, cooling, dripping distilled water, and reacting to obtain aqueous polyurethane dispersion;
in all raw materials, the total molar ratio of isocyanic acid radical to hydroxyl is 1.4:1, and the molar weight ratio of triethylamine to 2, 2-dimethylolpropionic acid is 1: 1;
when the acetone is added for the first time, the stirring speed under the stirring condition is 150-250r/min, the adding amount of the acetone is 10-200% of the soft segment molar weight, and the amount of the acetone added each time is the same;
the dropping process of the distilled water is carried out under the stirring state, and the cooling is carried out to be below 10 ℃;
before the distilled water is dripped, the stirring speed is 900-1100r/min, the dripping speed is 2-3 s/min, and when the solution system shows the phenomenon of thickening and thinning, the stirring speed is adjusted to 400-600 r/min.
2. The method for preparing the slow-release chlorine dioxide-waterborne polyurethane antibacterial film according to claim 1, wherein the first heating temperature is 40-50 ℃, and the stirring time after heating is 20-30 min.
3. The method for preparing a sustained-release chlorine dioxide-aqueous polyurethane antibacterial film according to claim 1, wherein the solution system is required to be colorless and transparent before the catalyst is added dropwise.
4. The preparation method of the slow-release chlorine dioxide-waterborne polyurethane antibacterial film according to claim 1, wherein the second heating temperature is 40-50 ℃ and the heating time is 1 h.
5. The preparation method of the slow-release chlorine dioxide-waterborne polyurethane antibacterial film according to claim 1, wherein the addition amount of the stable chlorine dioxide aqueous solution is 6-30% of the volume of the waterborne polyurethane dispersion liquid;
the catalyst is dibutyltin dilaurate, and the addition amount of the catalyst is 0.1-0.5% of the total amount of polyurethane.
6. The preparation method of the slow-release chlorine dioxide-waterborne polyurethane antibacterial film according to claim 1, wherein the hard segment is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the soft segment is one or more of polytetrahydrofuran with molecular weight of 1000-3000, polytrimethylene ether glycol, polycaprolactone glycol and polycarbonate glycol.
7. A slow-release chlorine dioxide-waterborne polyurethane antibacterial film prepared by the preparation method of the slow-release chlorine dioxide-waterborne polyurethane antibacterial film as defined in any one of claims 1 to 6.
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