CN111909347A - Antibacterial and antiviral anionic waterborne polyurethane resin and preparation method thereof - Google Patents
Antibacterial and antiviral anionic waterborne polyurethane resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an antibacterial and antiviral anionic waterborne polyurethane resin and a preparation method thereof, belonging to the field of high polymer materials. According to the preparation method, the extract caffeic acid of the solidago decurrens is introduced into the molecular chain of the anionic waterborne polyurethane, so that the wear resistance, water resistance and chemical resistance of the waterborne polyurethane resin are improved, the breaking strength of the waterborne polyurethane resin is improved, and the prepared waterborne polyurethane resin has antibacterial and antiviral effects; the raw material source of the preparation method is green and environment-friendly, and the prepared antibacterial and antiviral anionic waterborne polyurethane resin can be applied to the field of synthetic leather and has wide practicability.
Description
Technical Field
The invention relates to the field of high molecular polymers, in particular to an antibacterial and antiviral anionic waterborne polyurethane resin and a preparation method thereof.
Background
Caffeic acid has wide antibacterial and antiviral activity, and can be safely used in cosmetics. It has the following pharmacological actions: 1. antibacterial and antiviral: caffeic acid has wide bacteriostatic action, can be inactivated by protein in vivo, but has antiviral activity in vitro, has strong inhibitory action on vaccinia and adenovirus, and also has inhibitory action on poliomyelitis type I and parainfluenza type III viruses; 2. resisting snake venom; caffeic acid at a dose of 3 microgram can completely inhibit 20 microgram Crotalus venom phosphodiesterase, and can be used as an anti-snake poison.
The waterborne polyurethane is a non-toxic and environment-friendly novel material synthesized by taking water as a solvent, is applied more and more in recent years due to the environment-friendly property, has wider application fields, is greatly applied in the home decoration coating, synthetic leather industry and cosmetic industry at present, and brings great convenience and safety to the life of people. Along with the more and more strict requirements of the country on environmental protection, the spring of development of the water-based synthetic leather industry comes, the water-based clothing leather is in direct contact with human skin, the requirements on environmental protection are higher, the influence on human health is larger, in recent years, a plurality of virus outbreaks including Ebola virus, SARS virus and new crown virus appear in the world, and the infectivity is originally stronger.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of antibacterial and antiviral anionic waterborne polyurethane resin;
the invention aims to solve another technical problem and provide an antibacterial and antiviral anionic waterborne polyurethane resin to overcome the defects in the prior art.
In order to solve the technical problem of the invention, the technical scheme is a preparation method of antibacterial and antiviral anionic waterborne polyurethane resin, which comprises the following steps:
s1, mixing 120-140 parts by mass of macromolecular polyol and 30-40 parts by mass of isocyanate at 85-95 ℃, carrying out heat preservation reaction for 2-4h, measuring the NCO content, and cooling to 40-45 ℃ after reaching a set theoretical value;
s2, adding 4-6 parts by mass of hydrophilic chain extender, 1-2 parts by mass of micromolecule alcohol chain extender, 1.5-2.5 parts by mass of caffeic acid and 10-15 parts by mass of acetone into the reaction system cooled in the step S1, heating to 80-85 ℃, reacting for 1-3 hours, and cooling to room temperature;
s3, adding 0.3-0.5 part by mass of catalyst into the reaction system cooled in the step S2, heating to 65-75 ℃ for reaction for 2-4h, then measuring the NCO content, cooling after reaching a set theoretical value, adding 120-130 parts by mass of acetone to reduce the viscosity, and cooling to 0-5 ℃ to obtain a prepolymer;
s4, pouring the prepared prepolymer into a plum barrel, adding 2-4 parts by mass of a neutralizing agent at the rotating speed of 800-900r/min, neutralizing and dispersing for 5-10min, increasing the rotating speed to 1400-1500r/min, adding 230 parts by mass of 220-230 parts by mass of deionized emulsified water, slowly adding an amine chain extender solution at a constant speed within 2 min, diluting the amine chain extender solution by 2-6 parts by mass of an amine chain extender and 0-3 ℃ deionized emulsified water according to the proportion of 1:5, uniformly stirring a reaction system, dispersing for 5-10min, and removing acetone in the system through reduced pressure distillation to obtain the anionic waterborne polyurethane resin.
The preparation method of the antibacterial and antiviral anionic waterborne polyurethane resin is further improved as follows:
preferably, the macropolyol in step S1 is one or two or more of polytetrahydrofuran ether polyol, polyethylene oxide polyol, polypropylene oxide polyol, polyester ether polyol and polysiloxane polyol, and the molecular weight of the macropolyol is 2000-4000.
Preferably, the isocyanate in step S1 is selected from one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, polymethylene polyphenyl isocyanate, tetramethylxylylene diisocyanate, methylcyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the hydrophilic chain extender in step S2 is dimethylolpropionic acid, and the small molecular alcohol chain extender is one or a combination of two 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, sorbitol, trimethylolpropane and dimethylolcyclohexane.
Preferably, the caffeic acid in the step S2 is extracted from Solidago decurrens.
Preferably, the reaction described in step S3 is carried out by adding 20 to 30 parts by mass of acetone simultaneously with the addition of the catalyst.
Preferably, the catalyst in step S3 is an organobismuth catalyst selected from any one of, or a combination of two or more of, organobismuth Coscat83, organobismuth 1610, organobismuth 2010, organobismuth 2810 and organobismuth 2808.
Preferably, the neutralizing agent in step S4 is triethylamine.
Preferably, the amine chain extender in step S4 is one or a combination of two or more of ethylenediamine, isophoronediamine, 1, 6-hexamethylenediamine, polyetheramine, 1, 3-cyclohexyldimethylamine and m-xylylenediamine.
In order to solve another technical problem of the invention, the technical scheme is that the antibacterial and antiviral anionic waterborne polyurethane resin prepared by the preparation method is adopted.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides an anionic waterborne polyurethane resin combined with a caffeic acid molecular chain, which has the characteristics of antibiosis and antivirus, greatly improves the performances of strength, wear resistance and the like, inhibits the propagation of bacteria, viruses and other microorganisms to a certain extent, and ensures the safety of users to a certain extent. Can be applied to the field of water-based synthetic leather and has wide practicability.
2) The invention provides a preparation method of antibacterial and antiviral anionic waterborne polyurethane resin, which takes waterborne polyurethane and caffeic acid extracted from solidago as raw materials, and has wide sources and environmental protection; sequentially carrying out prepolymerization reaction, chain extension reaction, post chain extension reaction and neutralization reaction, and introducing a caffeic acid molecular chain onto an anionic waterborne polyurethane molecular chain; the preparation method comprises the following steps of (1) carrying out prepolymerization reaction on macromolecular polyol and isocyanate to generate macromolecular prepolymer, carrying out chain extension reaction to further enlarge a molecular chain, introducing a hydrophilic group during further chain extension in post chain extension reaction, carrying out neutralization reaction to make polyurethane hydrophilic, and carrying out post chain extension by using an amine chain extender, wherein the preparation method is simple and easy to operate; the acetone is added in stages in the preparation process, so that the viscosity of the reaction solution can be effectively adjusted, the acetone is distilled and removed in the reduced pressure distillation stage, and can be collected and reused, and the production cost and the environmental pollution are reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
Heating 125g of polytetrahydrofuran ether polyol with the molecular weight of 3000 and 32g of toluene diisocyanate to 85 ℃, carrying out heat preservation reaction for 2h, measuring the NCO content within two hours, cooling to 40 ℃ after reaching a set theoretical value, adding 5.6g of dimethylolpropionic acid, 1.8g of 1, 4-butanediol, 1.58g of caffeic acid and a small amount of acetone to adjust the viscosity, heating to 80 ℃ for reaction for 2h, adding 0.5g of Coscat83 catalyst after reaching the time, heating to 70 ℃ for reaction for 3h, then testing the NCO value, cooling and adding 120g of acetone to reduce the viscosity after reaching the set theoretical value, and cooling to 0 ℃ to obtain a prepolymer; and pouring the prepolymer into a plum blossom barrel, adding 3.8g of triethylamine at the rotating speed of 800r/min, dispersing for 10min, increasing the rotating speed to 1500r/min, adding 226g of deionized emulsified water, adding 3g of ethylenediamine solution diluted by 5 times of deionized emulsified water, dispersing for 10min, and then distilling under reduced pressure to remove acetone in the system to obtain a sample 1.
Example 2
The preparation method was the same as example 1, with the formulation and process being kept unchanged, except that caffeic acid was not added during the preparation process, to produce sample 2.
Example 3
Heating 130g of polyoxypropylene diol with molecular weight of 2000 and 38g of isophorone diisocyanate to 90 ℃, carrying out heat preservation reaction for 2h, measuring NCO content within two hours, cooling to 40 ℃ after reaching a set theoretical value, adding 4.2g of dimethylolpropionic acid, 1.8g of 1, 4-butanediol, 1.65g of caffeic acid and a small amount of acetone to adjust viscosity, heating to 80 ℃ for reaction for 2h, adding 0.5g of Coscat83 catalyst and 45mL of acetone after reaching the set time, heating to 70 ℃ for reaction for 3h, testing NCO value, cooling after reaching the set theoretical value, adding 120g of acetone to reduce viscosity, and cooling to 0 ℃ to obtain a prepolymer; and pouring the prepolymer into a plum blossom barrel, adding 2.8g of triethylamine at the rotating speed of 800r/min, dispersing for 10min, increasing the rotating speed to 1500r/min, adding 225g of deionized emulsified water, adding 2.3g of ethylenediamine solution diluted by 5 times of deionized emulsified water, dispersing for 10min, and then distilling under reduced pressure to remove acetone in the system to obtain a sample 3.
Example 4
The preparation method was the same as example 3, and the formulation and process were kept the same, except that caffeic acid was not added during the preparation process, to obtain sample 4.
Example 5
Heating 122g of polytetrahydrofuran diol with molecular weight of 2000 and 38g of polymethylene polyphenyl isocyanate to 85 ℃, carrying out heat preservation reaction for 2h, measuring NCO content within two hours, cooling to 40 ℃ after reaching a set theoretical value, adding 3.7g of dimethylolpropionic acid, 1.2g of 1, 4-butanediol, 1.42g of caffeic acid and a small amount of acetone to adjust viscosity, heating to 80 ℃ for reaction for 2h, adding 0.5g of Coscat83 catalyst and 45mL of acetone after reaching the time, heating to 70 ℃ for reaction for 3h, testing NCO value, cooling after reaching the set theoretical value, adding 120g of acetone to reduce viscosity, and cooling to 0 ℃ to obtain a prepolymer; and pouring the prepolymer into a plum blossom barrel, adding 2.8g of triethylamine at the rotating speed of 800r/min, dispersing for 10min, increasing the rotating speed to 1500r/min, adding 220g of deionized emulsified water, adding 2.2g of ethylenediamine solution diluted by 5 times of deionized emulsified water, dispersing for 10min, and then distilling under reduced pressure to remove acetone in the system to obtain a sample 5.
Example 6
The preparation method was the same as example 5, and the formulation and process were kept the same, except that caffeic acid was not added during the preparation process, to obtain sample 6.
Example 7
Heating 130g of polyester ether polyol with the molecular weight of 2000 and 31g of toluene diisocyanate to 85 ℃, carrying out heat preservation reaction for 2h, measuring the NCO content within two hours, cooling to 40 ℃ after reaching a set theoretical value, adding 5.9g of dimethylolpropionic acid, 1.2g of 1, 4-butanediol, 1.8g of caffeic acid and a small amount of acetone to adjust the viscosity, heating to 80 ℃ for reaction for 2h, adding 0.5g of Coscat83 catalyst and 45mL of acetone after reaching the set time, heating to 70 ℃ for reaction for 3h, then testing the NCO value, cooling after reaching the set theoretical value, adding 120g of acetone to reduce the viscosity, and cooling to 0 ℃ to obtain a prepolymer; and pouring the prepolymer into a plum blossom barrel, adding 4g of triethylamine at the rotating speed of 800r/min, dispersing for 10min, increasing the rotating speed to 1500r/min, adding 225g of deionized emulsified water, adding 3.3g of ethylenediamine solution diluted by 5 times of deionized emulsified water, dispersing for 10min, and then distilling under reduced pressure to remove acetone in the system to obtain a sample 7.
Example 8
The preparation method was the same as example 7, and the formulation and process were kept the same, except that caffeic acid was not added during the preparation process, to obtain sample 8.
The 8 samples were tested for breaking strength, Martindale abrasion resistance, water resistance and chemical resistance, and the results are shown in Table 1 below:
table 1 performance testing of samples prepared in examples 1-8
From the test results in the table above, it can be seen that, in terms of breaking strength, wear resistance, water resistance and chemical resistance, samples 1,3, 5 and 7 into which caffeic acid is introduced are obviously equal to or higher than the corresponding samples without caffeic acid, which indicates that the preparation method of the present invention introduces caffeic acid molecular chains onto anionic waterborne polyurethane molecular chains, and effectively improves the performance of the anionic waterborne polyurethane resin.
The 8 samples are subjected to antibacterial and antiviral tests, and the test results are as follows: the prepared antibacterial and antiviral waterborne polyurethane has the antibacterial rate of more than 96 percent on staphylococcus aureus, escherichia coli, candida albicans and mould; the antiviral rates of the viruses such as influenza A virus, influenza B virus, respiratory syncytial virus, adenovirus and the like are all more than 95 percent, and the antibacterial and antiviral rates of the waterborne polyurethane are all more than 95 percent, so that the waterborne polyurethane can be used in the antibacterial and antiviral fields of medical instruments, personal hygiene products, home furnishing and the like.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of antibacterial and antiviral anionic waterborne polyurethane resin is characterized by comprising the following steps:
s1, mixing 120-140 parts by mass of macromolecular polyol and 30-40 parts by mass of isocyanate at 85-95 ℃, carrying out heat preservation reaction for 2-4h, measuring the NCO content, and cooling to 40-45 ℃ after reaching a set theoretical value;
s2, adding 4-6 parts by mass of hydrophilic chain extender, 1-2 parts by mass of micromolecule alcohol chain extender, 1.5-2.5 parts by mass of caffeic acid and 10-15 parts by mass of acetone into the reaction system cooled in the step S1, heating to 80-85 ℃, reacting for 1-3 hours, and cooling to room temperature;
s3, adding 0.3-0.5 part by mass of catalyst into the reaction system cooled in the step S2, heating to 65-75 ℃ for reaction for 2-4h, then measuring the NCO content, cooling after reaching a set theoretical value, adding 120-130 parts by mass of acetone to reduce the viscosity, and cooling to 0-5 ℃ to obtain a prepolymer;
s4, pouring the prepared prepolymer into a plum barrel, adding 2-4 parts by mass of a neutralizing agent at the rotating speed of 800-900r/min, neutralizing and dispersing for 5-10min, increasing the rotating speed to 1400-1500r/min, adding 230 parts by mass of 220-230 parts by mass of deionized emulsified water, slowly adding an amine chain extender solution at a constant speed within 2 min, diluting the amine chain extender solution by 2-6 parts by mass of an amine chain extender and 0-3 ℃ deionized emulsified water according to the proportion of 1:5, uniformly stirring a reaction system, dispersing for 5-10min, and removing acetone in the system through reduced pressure distillation to obtain the anionic waterborne polyurethane resin.
2. The method as claimed in claim 1, wherein the polyol of step S1 is one or more selected from polytetrahydrofuran ether polyol, polyethylene oxide polyol, polypropylene oxide polyol, polyester ether polyol and polysiloxane polyol, and the molecular weight of the polyol is 2000-4000.
3. The method of claim 1, wherein the isocyanate in step S1 is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, polymethylene polyphenyl isocyanate, tetramethylxylylene diisocyanate, methylcyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
4. The method of claim 1, wherein the hydrophilic chain extender in step S2 is dimethylolpropionic acid, and the small alcohol chain extender is one or a combination of two 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, sorbitol, trimethylolpropane, and dimethylolcyclohexane.
5. The method for preparing antibacterial and antiviral anionic aqueous polyurethane resin according to claim 1, wherein the caffeic acid in step S2 is extracted from solidago decurrens.
6. The method for preparing antibacterial and antiviral anionic aqueous polyurethane resin according to claim 1, wherein 20 to 30 parts by mass of acetone is added to the reaction in step S3 while adding the catalyst.
7. The method for preparing antibacterial and antiviral anionic waterborne polyurethane resin as claimed in claim 1, wherein the catalyst of step S3 is an organic bismuth catalyst selected from any one or a combination of two or more of organic bismuth Coscat83, organic bismuth 1610, organic bismuth 2010, organic bismuth 2810 and organic bismuth 2808.
8. The method for preparing the antibacterial and antiviral anionic aqueous polyurethane resin as claimed in claim 1, wherein the neutralizing agent of step S4 is triethylamine.
9. The method of claim 1, wherein the amine chain extender of step S4 is one or a combination of two or more selected from ethylenediamine, isophoronediamine, 1, 6-hexanediamine, polyetheramine, 1, 3-cyclohexyldimethylamine and m-xylylenediamine.
10. An antibacterial and antiviral anionic aqueous polyurethane resin obtained by the production method of any one of claims 1 to 9.
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