阅读说明：本技术 一种抗菌型阳离子水性聚氨酯树脂及其制备方法 (Antibacterial cationic waterborne 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：本发明公开了一种抗菌型阳离子水性聚氨酯树脂及其制备方法,包括以下原料及质量份：大分子多元醇200-300份、多异氰酸酯100-160份、小分子醇类扩链剂2-10份、咖啡酸1-3份、氢氧化锌0.5-1份、催化剂0.5-1.5份、丙酮10-50份、亲水扩链剂8-15份、中和剂4-6份和去离子乳化水600-800份。本发明将咖啡酸与Zn离子通过离子键结合,并通过化学键合引入到阳离子水性聚氨酯分子链上,并且未与咖啡酸反应的氢氧化锌可以与异氰酸根反应形成脲基,从而避免功能添加剂对水性聚氨酯力学性能的影响,又可以实现良好的抗菌效果,同时增加了水性聚氨酯的机械强度。本发明既提高了水性聚氨酯树脂的交联度,同时也提高了水性聚氨酯树脂的耐水性、耐酸碱腐蚀性和机械强度,且赋予水性聚氨酯广谱的抗病毒、抗氧化和抗菌能力。(The invention discloses an antibacterial cationic waterborne polyurethane resin and a preparation method thereof, wherein the antibacterial cationic waterborne polyurethane resin comprises the following raw materials in parts by mass: 300 parts of macromolecular polyol 200-. 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. The invention not only improves the crosslinking degree of the waterborne polyurethane resin, but also improves the water resistance, acid and alkali corrosion resistance and mechanical strength of the waterborne polyurethane resin, and endows the waterborne polyurethane with broad-spectrum antiviral, antioxidant and antibacterial capabilities.)

1. An antibacterial cationic waterborne polyurethane resin is characterized in that: the feed comprises the following raw materials in parts by mass: 300 parts of macromolecular polyol 200-.

2. The antibacterial cationic aqueous polyurethane resin according to 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 antibacterial cationic aqueous polyurethane resin according to claim 2, wherein: the molecular weight of the macromolecular polyol is between 1000-3000.

4. The antibacterial cationic aqueous polyurethane resin according to 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 antibacterial cationic aqueous polyurethane resin according to claim 1, wherein: the hydrophilic chain extender comprises one or more of N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, diethanolamine and triethanolamine.

6. The antibacterial cationic aqueous polyurethane resin according to claim 1, wherein: the polyisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated phenyl methane diisocyanate.

7. The antibacterial cationic aqueous polyurethane resin according to claim 1, wherein: the catalyst is selected from organic bismuth.

8. The antibacterial cationic aqueous polyurethane resin according to claim 1, wherein: the neutralizer comprises one or more of glacial acetic acid, lactic acid, glycolic acid and acetic anhydride.

9. A method for preparing the antibacterial cationic aqueous polyurethane resin as described in any one of claims 1 to 8, characterized in that: adding caffeic acid and excessive zinc hydroxide into a beaker filled with water at 50-60 ℃, and uniformly stirring; placing macromolecular polyol in a reactor, heating to 100-120 ℃, dehydrating for 0.5-2h under the vacuum degree of > -0.09MPa, cooling to 60-80 ℃, adding polyisocyanate under the protection of nitrogen, reacting for 1-3h at 80-90 ℃, adding a small molecular alcohol chain extender and a zinc caffeate aqueous solution, reacting for 1-3h at 75-85 ℃, and cooling to 55 ℃; then adding a catalyst and acetone to react for 2-4 h at 75-85 ℃; adding a quaternary ammonium salt hydrophilic chain extender in multiple steps by using a seed emulsion method, reacting for 0.5-1.5 h at 70-80 ℃, cooling to 25-30 ℃, adding a neutralizing agent for neutralization, adding deionized emulsified water for uniform dispersion, and then carrying out reduced pressure distillation at-0.08 Mpa and 55 ℃ to obtain the antibacterial cationic waterborne polyurethane resin.

10. The use of the antibacterial cationic aqueous polyurethane resin according to claim 9 in the field of synthetic leather.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to an antibacterial cationic waterborne 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.

At present, the research on the water-based polyurethane is mostly found in the water-based polyurethane of the anion type, the product of the water-based polyurethane is also industrialized, and the report on the water-based polyurethane of the cation type is less. The cationic waterborne polyurethane has positive charge on molecular chains, has good wettability to base materials, is insensitive to the hardness of water, and can be used under acidic conditions, so that the cationic waterborne polyurethane has wide application prospects in the fields of textiles, adhesives, leather, papermaking and the like. As the cationic waterborne polyurethane is generally in a quaternary ammonium salt type, the procedure of quaternizing the prepolymer is complex, the cost is high, and sometimes an emulsified product is not stable enough, so that difficulty is brought to industrial production. Therefore, the cationic waterborne polyurethane with simple preparation process and excellent performance is developed, and the market prospect is very wide.

The cationic waterborne polyurethane has excellent performance, and the molecules contain quaternary ammonium salt groups with positive charges, so that the cationic waterborne polyurethane has better affinity to cotton fibers with negative charges, and is easy to form hydrogen bonds with hydroxyl groups in cellulose, so that the finished fabric has better durability; meanwhile, due to the existence of quaternary ammonium salt groups, the cationic polyurethane has a certain antibacterial effect, but the antibacterial types are less, and the antibacterial capability is weaker.

In the prior art, polyester diol and 2, 4-toluene diisocyanate are added into a reaction kettle according to a certain proportion to perform prepolymerization reaction at 45-55 ℃ under the protection of nitrogen, then the temperature is raised to 60-70 ℃, 1, 4-butanediol is added into a polyurethane prepolymer, the temperature is reduced to 50-60 ℃ after reaction for a certain time, a hydrophilic chain extender N-methyldiethanolamine is added, the temperature is reduced to 20 ℃, glacial acetic acid is added for neutralization, acetone is added for dilution, water is added after proper viscosity for high-speed shearing emulsification, and acetone is removed to obtain cationic polyurethane emulsion.

Disclosure of Invention

The invention mainly aims to provide an antibacterial cationic waterborne polyurethane resin and a preparation method thereof, which can effectively solve the problems in the background art.

In order to achieve the purpose, the invention adopts the technical scheme that:

an antibacterial cationic waterborne polyurethane resin comprises the following raw materials in parts by mass: 300 parts of macromolecular polyol 200-.

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.

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

Further, the small molecular 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 trimethylolcyclohexane.

Further, the hydrophilic chain extender comprises one or more of N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, diethanolamine and triethanolamine.

Preferably, the polyisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated phenyl methane diisocyanate.

Preferably, the catalyst is selected to be organobismuth.

Further, the neutralizing agent comprises one or more of glacial acetic acid, lactic acid, glycolic acid and acetic anhydride.

A preparation method of antibacterial cationic waterborne polyurethane resin comprises the following steps:

caffeic acid is dissolved in hot water at 60 deg.C to obtain caffeic acid solution, and zinc hydroxide is added into the solution until pH is 9.

Reacting macromolecular polyol with polyisocyanate at 80-95 ℃ for 2-4 h; then adding a micromolecular alcohol chain extender and a zinc caffeate solution to react for 1-3h at the temperature of 75-85 ℃; then adding a catalyst to react for 2-4 h at 75-85 ℃; adding a quaternary ammonium salt hydrophilic chain extender by a seed emulsion method in multiple steps, reacting for 0.5-1.5 h at 70-80 ℃, cooling to 25-30 ℃, adding a neutralizing agent for neutralization, adding deionized emulsified water for uniform dispersion, and then distilling under reduced pressure at-0.08 Mpa and 55 ℃ to obtain the cationic waterborne polyurethane resin.

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

Compared with the prior art, the invention has the following beneficial effects:

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. The invention not only improves the crosslinking degree of the waterborne polyurethane resin, but also improves the water resistance, acid and alkali corrosion resistance and mechanical strength of the waterborne polyurethane resin, and endows the waterborne polyurethane with broad-spectrum antiviral, antioxidant and antibacterial capabilities. 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. Caffeic acid has a dihydroxy structure, is natural dihydric alcohol, and is very suitable to be used as a chain extender in the synthesis of waterborne polyurethane. 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 zinc caffeate reacts with isocyanate through hydroxyl, and the dihydroxyl structure enables 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.

The following examples refer to the starting materials for the reactions:

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

Polytetrahydrofuran ether 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

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

N-methyldiethanolamine: shandong Kepler Biotech Co., Ltd

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

Acetone: aladdin reagent (Shanghai) Co., Ltd

Glacial acetic acid: aladdin reagent (Shanghai) Co., Ltd

Isopropyl alcohol: aladdin reagent (Shanghai) Co., Ltd

Organic bismuth: shanghai-jin chemical trade company Limited

Example 1

A preparation method of antibacterial cationic waterborne polyurethane resin comprises the following steps:

1. caffeic acid 2g was dissolved in hot water 10g at 60 deg.C to give caffeic acid solution, and zinc hydroxide 0.5g was added to give zinc caffeate solution with pH of 9.

2. 240g of polycarbonate polyol (2000 molecular weight) was put into a 1500mL four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 160g of isophorone diisocyanate to react for 2h at 85 ℃ under the protection of nitrogen, adding 12.5g of zinc caffeate solution, 3.6g of 1, 4-butanediol to react for 2h at 80 ℃, then cooling to 55 ℃, dripping 1g of organic bismuth catalyst and 50ml of acetone, reacting for 3h at 80 ℃, adding 10.4g of N-methyldiethanolamine and 30ml of isopropanol in three batches by a seed emulsion method, reacting for 1h at 75 ℃ after the addition is finished, cooling to 30 ℃, adding 5.4g of glacial acetic acid to neutralize the pH value to about 7, then adding 680ml deionized water, stirring at 1500rpm for 2h, and removing acetone under reduced pressure to obtain the antibacterial cationic waterborne polyurethane resin.

Example 2

A preparation method of antibacterial cationic waterborne polyurethane resin comprises the following steps:

1.3g caffeic acid was dissolved in 10g hot water at 60 deg.C to give caffeic acid solution, and 0.75g zinc hydroxide was added to give zinc caffeate solution with pH of 9.

2. 250g of polycarbonate polyol (2000 molecular weight) was put into a 1500mL four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 144g of hexamethylene diisocyanate to react for 2h at 85 ℃ under the protection of nitrogen, adding 13.75g of zinc caffeate solution, 3.6g of 1, 6-hexanediol to react for 2h at 80 ℃, then cooling to 55 ℃, dripping 1.2g of organic bismuth catalyst and 50ml of acetone, reacting for 3h at 80 ℃, adding 10g of N-methyldiethanolamine and 30ml of isopropanol in three batches by using a seed emulsion method, reacting for 1h at 75 ℃ after the addition is finished, cooling to 30 ℃, adding 4.8g of glacial acetic acid to neutralize the pH value to about 7, then 740ml deionized water is added, stirring is carried out at 1500rpm for 2h, and acetone is removed under reduced pressure, thus obtaining the antibacterial cationic waterborne polyurethane resin.

Example 3

A preparation method of antibacterial cationic waterborne polyurethane resin comprises the following steps:

1.3g caffeic acid was dissolved in 10g hot water at 60 deg.C to give caffeic acid solution, and 0.75g zinc hydroxide was added to give zinc caffeate solution with pH of 9.

2. 264g of polytetrahydrofuran ether polyol (2000 molecular weight) was put into a 1500mL four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 154g of isophorone diisocyanate to react for 2h at 85 ℃ under the protection of nitrogen, adding 13.75g of zinc caffeate solution and 2.6g of ethylene glycol to react for 2h at 80 ℃, then cooling to 55 ℃, dripping 1.3g of organic bismuth catalyst and 50ml of acetone, reacting for 3h at 80 ℃, adding 9.6g of N-methyldiethanolamine and 30ml of isopropanol in three batches by a seed emulsion method, reacting for 1h at 75 ℃ after the addition is finished, cooling to 30 ℃, adding 4g of glacial acetic acid to neutralize the pH value to about 7, and adding 724ml of deionized water, stirring at 1500rpm for 2h, and removing acetone under reduced pressure to obtain the antibacterial cationic waterborne polyurethane resin.

Comparative example 1

A preparation method of cationic waterborne polyurethane resin comprises the following steps:

putting 240g of polycarbonate polyol (2000 molecular weight) into a 1500mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser tube, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 160g of isophorone diisocyanate under the protection of nitrogen, reacting for 2h at 85 ℃, 5.6g of 1 and 4-butanediol, reacting for 2h at 80 ℃, then cooling to 55 ℃, dropwise adding 1g of organic bismuth catalyst, 50mL of acetone, reacting for 3h at 80 ℃, adding 10.4g of N-methyldiethanolamine and 30mL of isopropanol in three batches by using a seed emulsion method, reacting for 1h at 75 ℃ after the addition is finished, cooling to 30 ℃, adding 5.4g of glacial acetic acid to neutralize the pH value to about 7, then adding 680mL of deionized water, stirring for 2h at 1500rpm, and removing the acetone under reduced pressure to obtain the cationic waterborne polyurethane resin.

Comparative example 2

In comparative example 1, a general antibacterial performance assistant was added.

Comparative example 3

A preparation method of cationic waterborne polyurethane resin comprises the following steps:

putting 240g of polycarbonate polyol (2000 molecular weight) into a 1500mL four-neck flask provided with a thermometer, a stirrer and a reflux condenser tube, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 160g of isophorone diisocyanate under the protection of nitrogen, reacting for 2h at 85 ℃, 2.6g of 1, 4-butanediol, 3g of chlorogenic acid, reacting for 2h at 80 ℃, then cooling to 55 ℃, dropwise adding 1g of organic bismuth catalyst, 50mL of acetone, reacting for 3h at 80 ℃, adding 10.4g of N-methyldiethanolamine and 30mL of isopropanol in three batches by a seed emulsion method, reacting for 1h at 75 ℃ after adding, cooling to 30 ℃, adding 5.4g of glacial acetic acid for neutralizing to about pH 7, then adding 680mL of deionized water, stirring for 2h at 1500rpm, and removing the acetone under reduced pressure to obtain the cationic waterborne polyurethane resin.

Comparative example 4

A preparation method of cationic waterborne polyurethane resin comprises the following steps:

230g of polytetrahydrofuran polyol (2000 molecular weight) was put into a 1500mL four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, heating to 110 ℃, dehydrating for 1h under the vacuum degree of > -0.09MPa, cooling to 70 ℃, adding 158g of isophorone diisocyanate to react for 2h at 85 ℃ under the protection of nitrogen, reacting for 2h at 2g of 1, 4-butanediol and 3g of caffeic acid at 80 ℃, then cooling to 55 ℃, dripping 1.1g of organic bismuth catalyst and 50ml of acetone, reacting for 3h at 80 ℃, adding 9.8g of N-methyldiethanolamine and 30ml of isopropanol in three batches by a seed emulsion method, reacting for 1h at 75 ℃ after the addition is finished, cooling to 30 ℃, adding 5.2g of glacial acetic acid to neutralize the pH value to about 7, 694ml deionized water is added, stirring is carried out at 1500rpm for 2h, and acetone is removed under reduced pressure, thus obtaining the cationic waterborne polyurethane resin.

Performance detection

The cationic aqueous polyurethane resins obtained in examples 1 to 3 and comparative examples 1 to 4 were examined in the following manner, and the results of the examination are shown in tables 1, 2 and 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.

TABLE 1

TABLE 2

Table 3 shows the performance of the antibacterial cationic aqueous polyurethane resin

As can be seen from table 1, the zinc caffeate and zinc hydroxide modified waterborne antibacterial and antiviral cationic waterborne polyurethane resin of each example of the invention has excellent antibacterial and antiviral capabilities, not only has higher bacterial killing rate than the common resin added with the antibacterial auxiliary agent and the waterborne polyurethane modified by chlorogenic acid or caffeic acid, but also has significantly higher antibacterial rate than the resin of the comparative example.

As can be seen from table 2, compared to the conventional resin used as wet process resin for synthetic leather, the examples of the present invention have slightly improved physical properties, excellent folding fastness, peel strength, tear strength, tensile strength, etc., and higher mechanical strength than the comparative resin. 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. Chlorogenic acid has five hydroxyl groups, the hydroxyl groups are asymmetric and are easily degraded, and the chlorogenic acid is used as a chain extender, so that the molecular weight of the waterborne polyurethane is uncontrollable, the distribution of molecular particle sizes 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.