CN107880206B - Durable antibacterial water-based acrylic resin and preparation method thereof - Google Patents
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Abstract
The invention relates to a durable antibacterial water-based acrylic resin which is prepared by reacting an acrylic soft monomer, an acrylic hard monomer, a Schiff base acrylic monomer, acrylic acid, azobisisobutyronitrile, a hydroxyl acrylate monomer, an emulsifier, a neutralizer and deionized water; the Schiff base acrylic monomer is prepared from waterSalicylaldehyde, R-NH2And acryloyl chloride through reaction; the invention also provides a preparation method of the durable antibacterial water-based acrylic resin; the durable antibacterial water-based acrylic resin prepared by the invention has good adhesive force, high gloss, corrosion resistance and the like, high cost performance and wide applicability; when the antibacterial paint is used as an antibacterial paint, no additional antibacterial agent is needed, the lasting antibacterial and bacteriostatic effects can be achieved, and the antibacterial paint can be used for internal and external wall paints, water-based wood paints, water-based industrial paints and the like.
Description
Technical Field
The invention relates to a modified water-based acrylic resin, in particular to a durable antibacterial water-based acrylic resin and a preparation method thereof, belonging to the technical field of functional resins.
Background
Because of the wide distribution of microorganisms in the environment, human survival and health have been threatened by various bacterial viruses, and almost all abiotic surfaces have microorganisms, such as: medical care institutions, high-risk infected public places, stations, hotels, airports, bathrooms in humid environments, hot spring locations, cooling towers, and the like. In the sensitive area, the growth tendency of multiple drug-resistant bacteria, pathogenic bacteria and fungi is existed; the surfaces of the places where bacteria grow threaten human health, and the surfaces of the places are affected by the practical use value of the surfaces of the objects or cause surface degeneration. The antibacterial coating can effectively kill mould and other bacteria in the air, and reduce the probability of cross infection.
At present, many antibacterial coatings are additive antibacterial coatings, and an additional antibacterial agent is adopted to achieve a certain antibacterial effect, and because the added antibacterial agent is not uniformly dispersed in a coating film, is easy to migrate, degrade and discolor, has a non-lasting effect, pollutes the environment and the like, the antibacterial performance of the antibacterial coating is attenuated, even loses the antibacterial performance, and the application of the antibacterial coating has great limitation; therefore, the groups with antibacterial performance are connected to the macromolecular chain through a chemical bond through a certain chemical reaction, and the macromolecular polymer is used as a base material to prepare the antibacterial coating, so that the antibacterial coating has important economic value and wide market space.
Therefore, the Schiff base structure with good antibacterial effect is introduced into the water-based acrylic resin through a chemical bond, so that the prepared acrylic resin high-molecular polymer not only has the advantages of common acrylic resin, but also has good antibacterial and bactericidal effects.
Disclosure of Invention
The Schiff base compound has certain bioactivity, firstly, the Schiff base compound has good bacteriostatic, bactericidal and antifungal effects, for example, the Schiff base compound has good bactericidal activity on staphylococcus aureus, bacillus subtilis, escherichia coli, gram-negative bacteria and the like, and also has good inhibitory effect on cryptococcus neoformans and candida albicans, the Schiff base has unique bioactivity different from other structures besides the application significance of general compounds, and polymer resin can be modified by utilizing the characteristics of diversity, selectivity and the like of functional group structures connected on carbonyl and amino substituents.
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor durability, easy elution, easy degradation and the like of the antibacterial effect of a physically-added antibacterial agent.
In addition, the Schiff base contains C ═ N double bonds and has unique corrosion inhibition performance, particularly aromatic Schiff bases, the benzene ring structure of the Schiff base is easy to form conjugated bonds with the C ═ N double bonds, the coordination capacity with metal ions is strong, stable complexes are easy to form with the metal ions, and a compact protective film is formed on the surface of the metal, so that the corrosion of the metal is prevented.
The invention firstly synthesizes acrylic acid monomer containing Schiff base structure, then carries out polymerization reaction, in the polymerization process, the Schiff base acrylic acid monomer is added finally, so that the Schiff base structure is connected on the end chain of the resin molecule, after the film is formed, the Schiff base structure is on the surface of the coating film, and the functions of antibiosis, bacteriostasis activity and corrosion prevention are fully exerted.
Because the acrylic monomer containing the Schiff base structure has larger molecular weight and large steric hindrance in the post polymerization process, in order to solve the problem, the acrylic monomer containing the Schiff base and not containing methyl or branched chain structure is adopted, so that the reaction steric hindrance is reduced, and the reaction activity is improved.
Because the adhesive force of the acrylic resin is poor, a proper amount of cross-linking agent monomer hydroxy acrylic acid is added, and the hydroxy group of the cross-linking agent monomer hydroxy acrylic acid can form a hydrogen bond with the base material, so that the adhesive force of the cross-linking agent monomer hydroxy acrylic acid is increased; in the later polymerization stage, the hydroxyl acrylic monomer and the Schiff base acrylic monomer are mixed and dripped, and the effect is best.
The invention aims to provide a durable antibacterial water-based acrylic resin and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a durable antibacterial water-based acrylic resin which comprises the following components in percentage by weight: 8.0-15.0% of acrylic acid soft monomer, 12.0-25.0% of acrylic acid hard monomer, 3.0-6.0% of Schiff base acrylic acid monomer, 1.5-2.5% of acrylic acid, 0.4-1.0% of azodiisobutyronitrile, 1.5-3.5% of cross-linking agent monomer, 1.0-2.0% of emulsifier, 1.0-3.0% of neutralizer and the balance of deionized water.
Wherein, the acrylic acid hard monomer is one or a combination of several of methyl acrylate, methyl methacrylate, isobornyl methacrylate and 2-propyl heptyl acrylate.
The acrylic acid soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, cyclohexyl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate.
The Schiff base acrylic monomer is synthesized according to the following reaction formula:
the Schiff base acrylic acid monomer comprises the following components in percentage by weightThe method comprises the following steps: salicylaldehyde 15.0-25.0%, R-NH214.0 to 42.0 percent of acryloyl chloride, 11.0 to 19.0 percent of acryloyl chloride, 4.0 to 8.0 percent of N, N-dimethylformamide, 0.02 to 0.1 percent of potassium iodide, 8.0 to 15.0 percent of potassium carbonate, 15.0 to 35.0 percent of ethanol and 0.5 to 1.0 percent of glacial acetic acid.
Wherein, the R-NH2Is N, N-dimethyl-1, 3-propane diamine, isopropanol amine, dodecylamine, octadecylamine, aniline and hydrazide.
The Schiff base acrylic monomer is prepared by the following steps:
a) sequentially weighing salicylaldehyde and potassium carbonate in a reaction kettle, adding N, N-dimethylformamide with the formula amount, stirring and dissolving uniformly, heating to 80 ℃ for reacting for 1h, adding acryloyl chloride and potassium iodide, keeping reflux reaction for 12h, cooling, performing suction filtration, washing with water to be neutral, drying, and recrystallizing to obtain a reactant intermediate I;
b) adding the reactant intermediate I and ethanol into a reaction kettle provided with a thermometer, a stirrer and a condenser, heating to 80 ℃, and stirring to dissolve uniformly; separately weighing R-NH2And after the Schiff base and the ethanol are uniformly dissolved, slowly dropwise adding the mixture into a reaction kettle, after the dropwise adding is finished, adding glacial acetic acid, keeping reflux reaction for 4-5 h, cooling to room temperature after the reaction is completed, standing overnight, performing suction filtration, recrystallizing, and performing vacuum drying to obtain the Schiff base acrylic acid monomer.
The cross-linking agent monomer is one or a combination of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The invention provides a preparation method of a durable antibacterial water-based acrylic resin, which comprises the following steps:
a) weighing the components according to a formula ratio, sequentially adding acrylic acid soft monomer, acrylic acid hard monomer and azodiisobutyronitrile into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) weighing the components according to a formula ratio, sequentially adding a hydroxyl acrylate monomer, a Schiff base acrylic acid monomer and azodiisobutyronitrile into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding part of deionized water and an emulsifier into a reaction kettle, heating to 76-78 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution I, reacting for 0.5h, then dropwise adding the rest mixed solution I at a constant speed, controlling the dropwise adding time to be 2.5-3.5 h, and controlling the temperature to be 75-80 ℃ in the dropwise adding process;
d) and after the dropwise addition of the mixed solution I is finished, dropwise adding the mixed solution II at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 78-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding a neutralizing agent and the rest deionized water, and stirring for 0.5h to obtain the durable antibacterial water-based acrylic resin.
The durable antibacterial water-based acrylic resin prepared by the invention has good adhesive force, high gloss, corrosion resistance and the like; the cost performance is high, and the applicability is wide; when the antibacterial paint is used as an antibacterial paint, no additional antibacterial agent is needed, the lasting antibacterial and bacteriostatic effects can be achieved, and the antibacterial paint can be used for internal and external wall paints, water-based wood paints, water-based industrial paints and the like.
Detailed Description
The present invention will be further described with reference to the following examples for the preparation of the durable antibacterial aqueous acrylic resin. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A Schiff base acrylic monomer A is prepared by the following steps:
a) sequentially weighing 18.0 parts of salicylaldehyde and 10.2 parts of potassium carbonate into a reaction kettle, adding 5.0 parts of N, N-dimethylformamide, uniformly stirring for dissolving, heating to 80 ℃ for reaction for 1 hour, then adding 13.3 parts of acryloyl chloride and 0.06 part of potassium iodide, keeping reflux reaction for 12 hours, then cooling, washing with water to be neutral, drying, and recrystallizing to obtain a reactant intermediate I;
b) adding the reactant intermediate I and 10.0 parts of ethanol into a reaction kettle provided with a thermometer, a stirrer and a condenser, heating to 80 ℃, and stirring to dissolve uniformly; and weighing 27.3 parts of dodecylamine and 15.44 parts of ethanol, uniformly dissolving, then dropwise adding into the reaction kettle at a constant speed, adding 0.7 part of glacial acetic acid after dropwise adding, keeping reflux reaction for 4-5 h, cooling to room temperature after complete reaction, standing overnight, performing suction filtration, recrystallizing, and performing vacuum drying to obtain the Schiff base acrylic monomer A.
Example 2
A Schiff base acrylic monomer B is prepared by the following steps:
a) sequentially weighing 20.0 parts of salicylaldehyde and 11.4 parts of potassium carbonate into a reaction kettle, adding 6.0 parts of N, N-dimethylformamide, uniformly stirring for dissolving, heating to 80 ℃ for reaction for 1 hour, then adding 14.8 parts of acryloyl chloride and 0.05 part of potassium iodide, keeping reflux for reaction for 12 hours, then cooling, washing with water to be neutral, drying, and recrystallizing to obtain a reactant intermediate I;
b) adding the reactant intermediate I and 20.0 parts of ethanol into a reaction kettle provided with a thermometer, a stirrer and a condenser, heating to 80 ℃, and stirring to dissolve uniformly; and weighing 15.2 parts of aniline and 11.85 parts of ethanol, uniformly dissolving, then dropwise adding into the reaction kettle at a constant speed, adding 0.7 part of glacial acetic acid after dropwise adding, keeping reflux reaction for 4-5 h, cooling to room temperature after complete reaction, standing overnight, performing suction filtration, recrystallizing, and performing vacuum drying to obtain the Schiff base acrylic acid monomer B.
Example 3
A Schiff base acrylic monomer C prepared by the following steps:
a) sequentially weighing 25.0 parts of salicylaldehyde and 14.2 parts of potassium carbonate into a reaction kettle, adding 8.0 parts of N, N-dimethylformamide, uniformly stirring for dissolving, heating to 80 ℃ for reaction for 1 hour, then adding 18.5 parts of acryloyl chloride and 0.06 part of potassium iodide, keeping reflux reaction for 12 hours, then cooling, washing with water to be neutral, drying and recrystallizing to obtain a reactant intermediate I;
b) adding the reactant intermediate I and 10.0 parts of ethanol into a reaction kettle provided with a thermometer, a stirrer and a condenser, heating to 80 ℃, and stirring to dissolve uniformly; and weighing 15.4 parts of isopropanolamine and 7.94 parts of ethanol, uniformly dissolving, then dropwise adding into the reaction kettle at a constant speed, adding 0.9 part of glacial acetic acid after dropwise adding, keeping reflux reaction for 4-5 h, cooling to room temperature after complete reaction, standing overnight, performing suction filtration, recrystallizing, and performing vacuum drying to obtain the Schiff base acrylic acid monomer C.
Example 4
Durable antibacterial water-based acrylic resin A1The method comprises the following steps:
a) weighing 16.0 parts of methyl methacrylate, 2.0 parts of acrylic acid, 4.5 parts of butyl acrylate, 6.0 parts of lauryl methacrylate and 0.4 part of azodiisobutyronitrile in sequence according to the formula ratio, adding the mixture into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) weighing 2.5 parts of hydroxyethyl methacrylate, 4.5 parts of Schiff base acrylic monomer A and 0.3 part of azodiisobutyronitrile according to the formula proportion, sequentially adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 45.0 parts of deionized water and 1.2 parts of emulsifier into a reaction kettle, heating to 76-78 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution I, reacting for 0.5h, then dropwise adding the rest of mixed solution I at a constant speed, controlling the dropwise adding time to be 3h, and controlling the temperature to be 75-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution I is finished, dropwise adding the mixed solution II at a constant speed, controlling the dropwise adding time to be 3 hours, keeping the reaction at 78-82 ℃ for 2 hours after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding 1.7 parts of triethylamine serving as a neutralizing agent and the rest 15.9 parts of deionized water, and stirring for 0.5 hour to obtain the durable antibacterial water-based acrylic resin A1。
Example 5
Durable antibacterial water-based acrylic resin B1The method comprises the following steps:
a) weighing 14.0 parts of isobornyl methacrylate, 1.8 parts of acrylic acid, 5.2 parts of butyl methacrylate, 6.5 parts of isooctyl methacrylate and 0.4 part of azodiisobutyronitrile according to the proportion of the formula, sequentially adding the mixture into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) weighing 3.0 parts of hydroxyethyl acrylate, 4.0 parts of Schiff base acrylic monomer B and 0.3 part of azodiisobutyronitrile according to the formula proportion, sequentially adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 47.0 parts of deionized water and 1.3 parts of emulsifier into a reaction kettle, heating to 76-78 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution I, reacting for 0.5h, then dropwise adding the rest of mixed solution I at a constant speed, controlling the dropwise adding time to be 3.5h, and controlling the temperature to be 75-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution I is finished, dropwise adding the mixed solution II at a constant speed, controlling the dropwise adding time to be 3 hours, keeping the reaction at 78-82 ℃ for 2 hours after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding 1.5 parts of triethylamine serving as a neutralizing agent and the rest 15.0 parts of deionized water, and stirring for 0.5 hour to obtain the durable antibacterial water-based acrylic resin B1。
Example 6
Durable antibacterial water-based acrylic resin C1The method comprises the following steps:
a) weighing 20.0 parts of methyl acrylate, 2.2 parts of acrylic acid, 8.0 parts of butyl methacrylate, 2.5 parts of octadecyl acrylate and 0.5 part of azodiisobutyronitrile according to the proportion of the formula, sequentially adding into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) weighing 3.0 parts of hydroxypropyl methacrylate, 3.5 parts of Schiff base acrylic monomer and 0.3 part of azodiisobutyronitrile according to the formula proportion, sequentially adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 45.0 parts of deionized water and 1.5 parts of emulsifier into a reaction kettle, heating to 76-78 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution I, reacting for 0.5h, then dropwise adding the rest of mixed solution I at a constant speed, controlling the dropwise adding time to be 3h, and controlling the temperature to be 75-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution I is finished, dropwise adding the mixed solution II at a constant speed, controlling the dropwise adding time to be 3 hours, keeping the reaction at 78-82 ℃ for 2 hours after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding 1.9 parts of triethylamine serving as a neutralizing agent and the rest 11.6 parts of deionized water, and stirring for 0.5 hour to obtain the durable antibacterial water-based acrylic resin C1。
The antibacterial performance of the emulsion coating film of the durable antibacterial water-based acrylic resin prepared by the invention is tested according to the standard of HG/T3950-2007 antibacterial paint, and the test result is shown in Table 1.
TABLE 1 result of antibacterial property test of durable antibacterial water-based acrylic resin coating film
The lasting antibacterial type water-based acrylic resin in the embodiment of the invention and the conventional water-based acrylic resin plus antibacterial agent (comparative example) are subjected to lasting antibacterial performance test on a coating film according to the standard of HG/T3950-2007 antibacterial paint, and the tested bacteria is escherichia coli. Firstly, the antibacterial performance of the coating film is detected, after the test is finished, the coating film is subjected to ultrasonic oscillation cleaning for 2 hours and then is subjected to the antibacterial performance test, and the test results are shown in table 2.
TABLE 2 durable antibacterial property of water-based acrylic resin coating film
Note that the negative control sample refers to a control sample containing only the culture medium and no antimicrobial agent.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A preparation method of a durable antibacterial water-based acrylic resin is characterized by comprising the following steps: the preparation method comprises the following steps:
a) weighing according to the formula ratio, sequentially adding acrylic acid soft monomer, acrylic acid hard monomer and azodiisobutyronitrile into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) weighing the components according to a formula ratio, sequentially adding a hydroxyl acrylate monomer, a Schiff base acrylic acid monomer and azodiisobutyronitrile into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding part of deionized water and an emulsifier into a reaction kettle, heating to 76-78 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution I, reacting for 0.5h, then dropwise adding the rest mixed solution I at a constant speed, controlling the dropwise adding time to be 2.5-3.5 h, and controlling the temperature to be 75-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution I is finished, dropwise adding the mixed solution II at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 78-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding a neutralizing agent and the rest deionized water, and stirring for 0.5h to obtain the durable antibacterial water-based acrylic resin;
the raw materials comprise the following components in percentage by weight:
8.0 to 15.0 percent of acrylic acid soft monomer
Acrylic acid hard monomer 12.0-25.0%
3.0-6.0% of Schiff base acrylic acid monomer
Acrylic acid 1.5-2.5%
0.4 to 1.0 percent of azobisisobutyronitrile
1.5 to 3.5 percent of hydroxyl acrylate monomer
1.0-2.0% of emulsifier
1.0-3.0% of neutralizer
The balance of deionized water;
wherein the Schiff base acrylic monomer is synthesized according to the following reaction formula:
the preparation method of the Schiff base acrylic monomer comprises the following steps:
a) sequentially weighing salicylaldehyde and potassium carbonate in a reaction kettle, adding N, N-dimethylformamide with the formula amount, stirring and dissolving uniformly, heating to 80 ℃ for reacting for 1h, adding acryloyl chloride and potassium iodide, keeping reflux reaction for 12h, cooling, performing suction filtration, washing with water to be neutral, drying, and recrystallizing to obtain a reactant intermediate I;
b) adding the reactant intermediate I and ethanol into a reaction kettle provided with a thermometer, a stirrer and a condenser, heating to 80 ℃, and stirring to dissolve uniformly; separately weighing R-NH2Dissolving the acrylic acid monomer and ethanol uniformly, slowly dropwise adding the acrylic acid monomer into a reaction kettle, adding glacial acetic acid after dropwise adding, keeping reflux reaction for 4-5 h, cooling to room temperature after complete reaction, standing overnight, performing suction filtration, recrystallizing, and performing vacuum drying to obtain a Schiff base acrylic acid monomer;
the raw materials comprise the following components in percentage by weight:
15.0-25.0% of salicylaldehyde
R-NH214.0～42.0％
11.0 to 19.0 percent of acryloyl chloride
4.0 to 8.0 percent of N, N-dimethylformamide
0.02-0.1% of potassium iodide
8.0 to 15.0 percent of potassium carbonate
15.0 to 35.0 percent of ethanol
Glacial acetic acid 0.5-1.0%;
the R-NH2Is one of N, N-dimethyl-1, 3-propane diamine, isopropanol amine, dodecylamine, octadecylamine, aniline and hydrazide.
2. The method of claim 1, wherein: the acrylic acid hard monomer is one or a combination of methyl acrylate, methyl methacrylate, isobornyl methacrylate and 2-propyl heptyl acrylate; the acrylic acid soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, cyclohexyl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate.
3. The method of claim 1, wherein: the hydroxyl acrylate monomer is one or a combination of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
4. The method of claim 1, wherein: the neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
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