阅读说明：本技术 一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法 (Water-based antibacterial and antiviral anionic polyurethane resin and preparation method thereof ) 是由 李浩扬 李桂军 张锋 冯会生 甄雷雷 于 2021-01-15 设计创作，主要内容包括：本发明公开了一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法,由以下原料及质量份组成：大分子多元醇30-35份、多异氰酸酯5-10份、亲水扩链剂2-6份、氢氧化锌1-2份、小分子醇类扩链剂0.5-2份、胺类扩链剂1-2份、催化剂0.01-0.5份、有机溶剂5-12份和去离子水45-55份,所述亲水扩链剂为咖啡酸。咖啡酸作为亲水扩链剂使用,其易溶于有机溶剂,能更充分地与多异氰酸酯进行反应,提高聚合反应稳定性,咖啡酸具有较广泛的抑菌和抗病毒活性,能吸收紫外线,并且能够提高水性聚氨酯树脂的着色能力,Zn离子拥有长效的抗菌活性,Zn离子拥有长效的抗菌活性,将咖啡酸与氢氧化锌通过中和反应的方式获得带有Zn离子的咖啡酸锌溶液改性水性聚氨酯使得水性聚氨酯不需要添加抗菌助剂就可以获得优秀的抑菌抗病毒能力且表现出更好的储存稳定性。(The invention discloses a water-based antibacterial antiviral anion polyurethane resin and a preparation method thereof, wherein the water-based antibacterial antiviral anion polyurethane resin comprises the following raw materials in parts by mass: 30-35 parts of macromolecular polyol, 5-10 parts of polyisocyanate, 2-6 parts of a hydrophilic chain extender, 1-2 parts of zinc hydroxide, 0.5-2 parts of a micromolecular alcohol chain extender, 1-2 parts of an amine chain extender, 0.01-0.5 part of a catalyst, 5-12 parts of an organic solvent and 45-55 parts of deionized water, wherein the hydrophilic chain extender is caffeic acid. Caffeic acid is used as a hydrophilic chain extender, is easy to dissolve in an organic solvent, can fully react with polyisocyanate, improves the stability of polymerization reaction, has wide antibacterial and antiviral activities, can absorb ultraviolet rays, and can improve the coloring capacity of the waterborne polyurethane resin, Zn ions have long-acting antibacterial activity, and caffeic acid and zinc hydroxide are subjected to neutralization reaction to obtain zinc caffeate solution modified waterborne polyurethane with Zn ions, so that the waterborne polyurethane can obtain excellent antibacterial and antiviral capacity without adding an antibacterial aid and shows better storage stability.)

1. The water-based antibacterial and antiviral anionic polyurethane resin is characterized in that: the composition comprises the following raw materials in parts by mass: 30-35 parts of macromolecular polyol, 5-10 parts of polyisocyanate, 2-6 parts of a hydrophilic chain extender, 1-3 parts of zinc hydroxide, 0.5-2 parts of a micromolecular alcohol chain extender, 1-2 parts of an amine chain extender, 0.01-0.5 part of a catalyst, 5-12 parts of an organic solvent and 45-55 parts of deionized water, wherein the hydrophilic chain extender is caffeic acid.

2. The aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in claim 1, wherein: the macromolecular polyol comprises one or more of polytetrahydrofuran ether polyol, polycarbonate polyol, polyester polyol, polycaprolactone polyol, poly adipic acid polyol, polyethylene oxide polyol, polypropylene oxide polyol and polysiloxane polyol.

3. The aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in claim 2, wherein: the molecular weight of the macromolecular polyol is between 1000-3000.

4. The aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in claim 1, wherein: the micromolecular alcohol chain extender comprises one or more of ethylene glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol, 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, sorbitol and trimethylol cyclohexane.

5. The aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in claim 1, wherein: the diisocyanate is an aliphatic diisocyanate, an aromatic diisocyanate, or a mixture thereof.

6. The aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in claim 5, wherein: the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, cyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate; the aromatic diisocyanate is selected from one or more of toluene-2, 4-diisocyanate, 4, 6-xylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, ethylbenzene diisocyanate, 3 ' -dimethylbiphenyl-4, 4 ' -diisocyanate and 3,3 ' -dimethyl-4, 4 ' -diphenylmethane diisocyanate.

7. The water-based antibacterial and antiviral anionic polyurethane resin and the preparation method thereof according to claim 1, wherein the polyurethane resin comprises the following components in percentage by weight: the amine chain extender comprises one or more of ethylenediamine, 1, 6-hexamethylenediamine, isophorone diamine and polyether amine; the catalyst is organic bismuth; the organic solvent is acetone.

8. A method for preparing the aqueous bacteriostatic antiviral anionic polyurethane resin as claimed in any one of claims 1 to 7, which is characterized in that: prepared according to the following steps

S1, adding the hydrophilic chain extender caffeic acid and excessive zinc hydroxide into a beaker filled with water at the temperature of 50-60 ℃, mixing, and uniformly stirring to obtain a zinc caffeate solution;

s2, reacting the macromolecular polyol, the zinc caffeate solution and the polyisocyanate for 2-4 hours at the temperature of 80-95 ℃; then adding a small molecular chain extender to react for 1-3 h at 70-80 ℃; then adding a catalyst and acetone to react for 2-4 h at 75-85 ℃; then cooling to 30 ℃, adding acetone, and stirring for 10-60min to obtain a prepolymer;

s3, emulsifying the prepolymer, wherein the emulsifying process is as follows: regulating the rotation speed to 1200r/min, adding deionized water into the prepolymer, continuously stirring for 5-10min after dispersing, regulating the rotation speed to 1800r/min, adding a rear chain extender, and continuously stirring for 1-2h to obtain a prepolymer emulsion;

s4, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

9. Use of the aqueous bacteriostatic antiviral anionic polyurethane resin as defined in claim 8 in the field of synthetic leather.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a water-based antibacterial and antiviral anionic polyurethane resin and a preparation method thereof.

Background

The polyurethane has the advantages of wide adjustable range of hardness, low temperature resistance, good flexibility, strong adhesive force and the like, and is widely applied to the fields of leather finishing, coatings, adhesives and the like. However, with the advent of environmental safety laws and regulations in various countries, many countries have limited the use of solvent-based polyurethanes.

The continuous phase of the waterborne polyurethane is water, so that the waterborne polyurethane is safe and easy to store and store, is convenient to use and low in cost, completely keeps the characteristics of the solvent type polyurethane, and is superior to the solvent type polyurethane in certain performance due to the coulomb force and hydrogen bond in the molecular chain of the waterborne polyurethane, so that the development and production of the waterborne polyurethane are paid attention by various countries in the world and are developed greatly. In the preparation of aqueous polyurethane, in order to obtain a stable polyurethane emulsion, a hydrophilic group is introduced into a prepolymer molecule of polyurethane, and the prepolymer molecule is emulsified in water. According to different electric properties of introduced groups, the waterborne polyurethane is divided into cationic waterborne polyurethane, anionic waterborne polyurethane, nonionic waterborne polyurethane and mixed waterborne polyurethane.

The anionic waterborne polyurethane comprises a sulfonic acid type and a carboxylic acid type, the preparation method of the carboxylic acid type waterborne polyurethane mainly depends on hydrophilic chain extenders such as dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA), but the production processes of the two hydrophilic chain extenders generate heavy pollution, the DMPA is most widely used at present, but the DMPA is difficult to dissolve in acetone, so the reaction is difficult to perform in the synthetic process of the waterborne polyurethane; DMBA has high solubility in acetone and low viscosity in the synthesis process, but has serious production pollution, complex synthesis technology and high difficulty, and at present, few manufacturers for large-scale production exist in China.

At present, many anionic waterborne polyurethanes do not have a bactericidal effect, so that the problem needs to be solved urgently.

Disclosure of Invention

The invention mainly aims to provide a water-based antibacterial antiviral anionic polyurethane resin and a preparation method thereof, which can effectively solve the problems in the background art.

The technical scheme of the invention is as follows:

the water-based antibacterial antiviral anion polyurethane resin is prepared from the following raw materials in parts by mass: 30-35 parts of macromolecular polyol, 5-10 parts of polyisocyanate, 2-6 parts of a hydrophilic chain extender, 1-3 parts of zinc hydroxide, 0.5-2 parts of a micromolecular alcohol chain extender, 1-2 parts of an amine chain extender, 0.01-0.5 part of a catalyst, 5-12 parts of an organic solvent and 45-55 parts of deionized water, wherein the hydrophilic chain extender is caffeic acid.

Further, the macromolecular polyol comprises any one or more of polytetrahydrofuran ether polyol, polycarbonate polyol, polyester polyol, polycaprolactone polyol, poly adipic acid polyol, polyethylene oxide polyol, polypropylene oxide polyol and polysiloxane polyol.

Preferably, the molecular weight of the macromolecular polyol is between 1000-3000.

Preferably, the small-molecular alcohol chain extender comprises one or more of ethylene glycol, 2-methyl-1, 3-propanediol, diethylene glycol, 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, sorbitol and trimethylolcyclohexane.

Further, the diisocyanate is an aliphatic diisocyanate, an aromatic diisocyanate, or a mixture thereof.

Preferably, the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, cyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate; the aromatic diisocyanate is selected from one or more of toluene-2, 4-diisocyanate, 4, 6-xylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, ethylbenzene diisocyanate, 3 ' -dimethylbiphenyl-4, 4 ' -diisocyanate and 3,3 ' -dimethyl-4, 4 ' -diphenylmethane diisocyanate.

Further, the amine chain extender comprises one or more of ethylenediamine, 1, 6-hexamethylenediamine, isophoronediamine and polyetheramine; the catalyst is organic bismuth; the organic solvent is acetone.

A preparation method of water-based antibacterial and antiviral anionic polyurethane resin comprises the following steps

S1, adding the hydrophilic chain extender caffeic acid and excessive zinc hydroxide into a beaker filled with water of 50-60 ℃, mixing, and uniformly stirring to obtain a zinc caffeate solution.

S2, reacting the macromolecular polyol, the zinc caffeate solution and the polyisocyanate for 2-4 hours at the temperature of 80-95 ℃; then adding a small molecular chain extender to react for 1-3 h at 70-80 ℃; then adding a catalyst and acetone to react for 2-4 h at the temperature of 75-85 ℃; then cooling to 30 ℃, adding acetone, and stirring for 10-60min to obtain a prepolymer;

s3, emulsifying the prepolymer, wherein the emulsifying process is as follows: regulating the rotation speed to 1200r/min, adding deionized water into the prepolymer, continuously stirring for 5-10min after dispersing, regulating the rotation speed to 1800r/min, adding a rear chain extender, and continuously stirring for 1-2h to obtain a prepolymer emulsion;

s4, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

An application of antibacterial cationic waterborne polyurethane resin in the field of synthetic leather.

The chemical reaction involved above is as follows:

has the advantages that:

the invention provides an antibacterial anionic waterborne polyurethane resin and a preparation method thereof, wherein the waterborne polyurethane comprises the following raw material components: macromolecular polyol, polyisocyanate, a hydrophilic chain extender, zinc hydroxide, a micromolecular alcohol chain extender, an amine chain extender, a catalyst and deionized water. Wherein the hydrophilic chain extender is caffeic acid. Caffeic acid has a dihydroxyl structure and a carboxyl group, is similar to the conventional hydrophilic chain extender DMPA and DMBA, and can completely replace the conventional hydrophilic chain extender. According to the invention, caffeic acid and Zn ions are combined through ionic bonds and are introduced onto a cationic waterborne polyurethane molecular chain through chemical bonding, and zinc hydroxide which is not reacted with caffeic acid can react with isocyanate to form carbamido, so that the influence of a functional additive on the mechanical property of waterborne polyurethane is avoided, a good antibacterial effect can be realized, and the mechanical strength of the waterborne polyurethane is increased. Caffeic acid can be extracted from Solidago decurrens belonging to Compositae, has safe, environment-friendly and pollution-free source, is widely applied to medicine, cosmetics and other aspects, and has natural antibacterial and antiviral abilities. However, natural antibacterial groups have the defects of limitation, insufficient antibacterial lasting power, easy degradation and invalidation and the like. Therefore, Zn ions bonded with the carboxyl of the caffeic acid through ionic bonds are used as heavy metal ions, and have lasting bacteriostatic and antiviral effects. The modified caffeic acid reacts with isocyanate through hydroxyl, and the dihydroxyl structure enables the caffeic acid to be easily polymerized on a water-based polyurethane molecular chain. According to the invention, zinc caffeate with Zn ions and a part of zinc hydroxide are reacted with isocyanate, so that the water-based cationic polyurethane resin can achieve long-acting antibacterial and antiviral effects and excellent mechanical strength without adding a sterilization aid.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

Reaction raw materials:

polycarbonate polyol: dow, Shanghai and melt chemical industries, Ltd

Polytetrahydrofuran ether polyol: dow, Shanghai and melt chemical industries, Ltd

Polycaprolactone polyol: dow, Shanghai and melt chemical industries, Ltd

Isophorone diisocyanate: dow, Shanghai and melt chemical industries, Ltd

Hexamethylene diisocyanate: dow, Shanghai and melt chemical industries, Ltd

Toluene diisocyanate: dow, Shanghai and melt chemical industries, Ltd

1, 4-butanediol: shanghai Shunya chemical import and export Limited

Ethylene glycol: suzhou Kangshuo chemical Co., Ltd

1, 6-hexanediol: shandong Kepler Biotech Co., Ltd

Dimethylolbutyric acid: shandong Kepler Biotech Co., Ltd

Caffeic acid: aladdin reagent (Shanghai) Co., Ltd

Zinc hydroxide: aladdin reagent (Shanghai) Co., Ltd

Acetone: aladdin reagent (Shanghai) Co., Ltd

Ethylene diamine: aladdin reagent (Shanghai) Co., Ltd

Organic bismuth: shanghai-jin chemical trade company Limited

Example 1

Preparation method of water-based antibacterial and antiviral anionic polyurethane resin

S1, adding 3g of caffeic acid and 1.5g of zinc hydroxide into a beaker containing 10g of water at 50-60 ℃, mixing, and uniformly stirring to obtain a 14.5g zinc caffeate solution with ph being 9.

S2, putting 300g of polycarbonate polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding 14.5g of zinc caffeate solution, stirring uniformly, putting 70g of isophorone diisocyanate, and reacting for 2h at 90 ℃. And cooling to 70 ℃, adding 5g of micromolecular chain extender ethylene glycol, and continuing to react for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 0.5g of catalyst organic bismuth and 40ml of acetone, stirring and heating to 75 ℃ for reaction for 4 hours. Then cooling to 20 ℃, adding 80ml of acetone, and stirring for 30min to obtain a prepolymer;

s3, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 500g of deionized water into a dispersion tank, opening stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 10g of ethylene diamine aqueous solution serving as a post-chain extender, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s4, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

Example 2

Preparation method of water-based antibacterial and antiviral anionic polyurethane resin

S1, adding 4g of caffeic acid and 1.75g of zinc hydroxide into a beaker containing 10g of water at 50-60 ℃, mixing, and uniformly stirring to obtain a 15.75g zinc caffeate solution with the ph of 8.7.

S2, putting 310g of polytetrahydrofuran ether polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding 15.75g of zinc caffeate solution, stirring uniformly, putting 72g of isophorone diisocyanate, and reacting for 2h at 90 ℃. And cooling to 70 ℃, adding 6g of micromolecular chain extender ethylene glycol, and continuing to react for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 0.7g of catalyst organic bismuth and 40ml of acetone, stirring, heating to 75 ℃ and reacting for 4 hours. Then cooling to 20 ℃, adding 80ml of acetone, and stirring for 30min to obtain a prepolymer;

s3, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 550g of deionized water into a dispersion tank, opening stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 11g of ethylene diamine aqueous solution serving as a post-chain extender, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s4, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

Example 3

Preparation method of water-based antibacterial and antiviral anionic polyurethane resin

S1, adding 4.5g of caffeic acid and 1.9g of zinc hydroxide into a beaker containing 10g of water at 50-60 ℃, mixing, and uniformly stirring to obtain a 16.4g zinc caffeate solution with the ph of 8.8.

S2, putting 315g of polytetrahydrofuran ether polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding 16.4g of zinc caffeate solution, stirring uniformly, adding 56g of hexamethylene diisocyanate, and reacting for 2h at 90 ℃. The temperature is reduced to 70 ℃, 7.8g of micromolecular chain extender 1, 4-butanediol is added, and the reaction is continued for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 0.8g of catalyst organic bismuth and 40ml of acetone, stirring, heating to 75 ℃ and reacting for 4 hours. Then cooling to 20 ℃, adding 80ml of acetone, and stirring for 30min to obtain a prepolymer;

s3, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 540g of deionized water into a dispersion tank, starting stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 10.3g of a post-chain extender, namely ethylene diamine aqueous solution, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s4, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

Comparative example 1

S1, putting 300g of polycarbonate polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding dried anionic chain extender DMBA5g, stirring uniformly, putting 70g of isophorone diisocyanate, and reacting for 2h at 90 ℃. And cooling to 70 ℃, adding 5g of micromolecular chain extender ethylene glycol, and continuing to react for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 0.5g of catalyst organic bismuth and 40ml of acetone, stirring and heating to 75 ℃ for reaction for 4 hours. Then cooling to 20 ℃, adding 7g of neutralizing agent triethylamine and 80ml of acetone, and stirring for 30min to obtain a prepolymer;

s2, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 500g of deionized water into a dispersion tank, opening stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 10g of ethylene diamine aqueous solution serving as a post-chain extender, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s3, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based anionic polyurethane resin.

Comparative example 2

The resin of comparative example 1 was added with a conventional commercially available bacteriostatic and antiviral functional filler.

Comparative example 3

S1, putting 323g of polycaprolactone polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding 5g of dried anionic chain extender chlorogenic acid, stirring uniformly, adding 30g of isophorone diisocyanate and 23g of hexamethylene diisocyanate, and reacting for 2h at 90 ℃. The temperature is reduced to 70 ℃, 8.2g of micromolecular chain extender 1, 6-hexanediol is added, and the reaction is continued for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 1.0g of catalyst organic bismuth and 40ml of acetone, stirring and heating to 75 ℃ for reaction for 4 hours. Then cooling to 20 ℃, adding 10.2g of neutralizing agent triethylamine and 70ml of acetone, and stirring for 30min to obtain a prepolymer;

s2, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 538g of deionized water into a dispersion tank, starting stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 12.2g of aqueous solution of ethylene diamine serving as a post-chain extender, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s3, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

Comparative example 4

S1, putting 320g of polycaprolactone polyol into a 1000mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 60 ℃, adding 5g of dried anionic chain extender caffeic acid, stirring uniformly, adding 25g of isophorone diisocyanate and 25g of hexamethylene diisocyanate, and reacting for 2h at 90 ℃. The temperature is reduced to 70 ℃, 7.5g of micromolecule chain extender 1, 6-hexanediol is added, and the reaction is continued for 1 hour at 70 ℃. Cooling to less than 50 ℃, adding 1.0g of catalyst organic bismuth and 40ml of acetone, stirring and heating to 75 ℃ for reaction for 4 hours. Then cooling to 20 ℃, adding 9.1g of neutralizing agent triethylamine and 70ml of acetone, and stirring for 30min to obtain a prepolymer;

s2, emulsifying the prepolymer, wherein the emulsifying process is as follows: adding 538g of deionized water into a dispersion tank, starting stirring, adjusting the rotating speed to 1200r/min, adding the prepolymer into the dispersion tank, continuously stirring for 5-10min after dispersion, then adjusting the rotating speed to 1800r/min, adding 12.2g of aqueous solution of ethylene diamine serving as a post-chain extender, and continuously stirring for 1-2h to obtain prepolymer emulsion;

s3, desolventizing the prepolymer emulsion, wherein the desolventizing process comprises the following steps: heating the prepolymer emulsion to 55 ℃ and removing acetone in the emulsion under the condition of-0.08 MPa to obtain the water-based antibacterial and antiviral anionic polyurethane resin.

Quality identification

Performance tests were conducted on the aqueous polyurethanes obtained in examples 1 to 3 and comparative examples 1 to 3

And (3) testing the bacteriostatic activity: the test was carried out according to GB/T21866-2008.

And (3) testing the physical properties of the synthetic leather: the test was carried out according to QB/T4197-2011 using 0.80mm as a standard thickness.

And (3) testing the bacteriostatic activity: the test was carried out according to GB/T21866-2008.

And (3) testing the physical properties of the synthetic leather: the test was carried out according to the QB/T5143-2017 using 0.80mm as the standard thickness.

TABLE 1 antibacterial Property test results

TABLE 2 tensile, tear and folding resistance test results

Table 3 monitoring the properties of the antibacterial anionic waterborne polyurethane resin obtained

As can be seen from table 1, the zinc caffeate and zinc hydroxide modified aqueous antibacterial and antiviral anionic aqueous polyurethane resin with Zn ions of the examples of the present invention has excellent antibacterial and antiviral abilities, antibacterial activity and killing rate are both higher than those of the common resin added with the antibacterial function aid and the aqueous polyurethane modified by chlorogenic acid or caffeic acid, and the antibacterial rate is significantly higher than that of the comparative resin. .

As can be seen from table 2, compared with the conventional resin as the wet process resin for synthetic leather, the products prepared by the examples of the present invention have slightly improved physical properties, and have excellent physical properties such as folding fastness, peel strength, tear strength, tensile strength, etc. Completely meets the physical property requirement of the water-based wet synthetic leather.

As can be seen from Table 3, the invention has a plurality of advantages compared with the prior invention patent in which chlorogenic acid is used as an antibacterial chain extender by using zinc caffeate as the antibacterial aqueous polyurethane chain extender. The chlorogenic acid has five hydroxyl groups and asymmetric hydroxyl groups, and the chlorogenic acid is used as a chain extender, so that the molecular weight of the waterborne polyurethane is uncontrollable, the distribution of the molecular particle size is uneven, and the film forming property and the storage stability of the waterborne polyurethane emulsion are greatly influenced.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.