CN115417828B - Antibacterial environment-friendly acrylic material and preparation method and application thereof - Google Patents

Antibacterial environment-friendly acrylic material and preparation method and application thereof Download PDF

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Publication number
CN115417828B
CN115417828B CN202210813547.8A CN202210813547A CN115417828B CN 115417828 B CN115417828 B CN 115417828B CN 202210813547 A CN202210813547 A CN 202210813547A CN 115417828 B CN115417828 B CN 115417828B
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compound
antibacterial
benzisothiazolinone
modified
resin
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CN115417828A (en
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蔡威
吕天一
黄若晨
杨卓妮
刘婷婷
卢微
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Guangdong Sky Dragon Printing Ink Co ltd
Tsinghua Innovation Center in Dongguan
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Guangdong Sky Dragon Printing Ink Co ltd
Tsinghua Innovation Center in Dongguan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses an antibacterial environment-friendly acrylic acid material, a preparation method and application thereof, wherein the method comprises the steps of mixing resin, an antibacterial metal compound and modified benzisothiazolinone, wherein the structural formula of the modified benzisothiazolinone is as follows

Description

Antibacterial environment-friendly acrylic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antibacterial environment-friendly acrylic acid material, and a preparation method and application thereof.
Background
The acrylic acid material has the advantages of lower price, better heat resistance, higher glossiness and the like, and is widely used in the fields of paint, ink, adhesive and the like. However, most of the traditional acrylic materials are solvent type, and have the defects of high content of volatile organic compounds, high foreign flavor and the like, and have high harm to human bodies and environment. Along with the enhancement of environmental protection consciousness, the preparation of environment-friendly acrylic materials has become a research hot spot.
The isothiazolinone compound has antibacterial function, and can delay release of the anti-fouling agent and prolong the anti-fouling life of the coating. Compared with the common ammonium borate, low-toxicity phenol, F-101 and other bacteriostats, the isothiazolinone compound has better environmental protection performance, can be rapidly degraded, has smaller toxicity to organisms, is widely applied to the fields of corrosion prevention, medicine and the like, and can be used as an environmental-friendly anti-fouling agent in anti-fouling paint.
The benzisothiazolinone has better high-temperature stability and acid and alkali resistance, can adapt to harsh processing environments, and is widely applied to products such as latex products, water-soluble resins, acrylic acid and the like. However, the antibacterial effect achieved by the current method of adding benzisothiazolinone to a material by a physical blending method and controlling the release of benzisothiazolinone by hydrolysis of the material is not ideal.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the antibacterial environment-friendly acrylic acid material, the preparation method and the application thereof, and the antibacterial environment-friendly acrylic acid material obtained by grafting the modified benzisothiazolinone on the environment-friendly acrylic acid material has better antibacterial effect on staphylococcus aureus and escherichia coli, improves the antibacterial performance of the environment-friendly acrylic acid material, has the characteristic of environmental friendliness, and has good application prospect in the field of paint.
In a first aspect of the present invention, there is provided a process for the preparation of a modified benzisothiazolinone, the process comprising the steps of: the compound I and potassium thiocyanate react in a solvent to prepare a compound II, and the compound II is hydrolyzed to prepare the modified benzisothiazolinone shown in the formula III.
According to a first aspect of the invention, in some embodiments of the invention, the compound I has the formula
In some embodiments of the invention, X in compound i is selected from any one of F, cl, br, I.
In some preferred embodiments of the invention, compound II is of the formula
In some preferred embodiments of the invention, X in compound II is selected from any one of F, cl, br, I.
In some preferred embodiments of the present invention, the modified benzisothiazolinone of compound III has the formula
In some preferred embodiments of the invention, the molar ratio of compound I to potassium thiocyanate is (4-6): (9-11).
In some preferred embodiments of the invention, the solvent comprises H 2 O, N at least one of N-dimethylformamide, dimethyl sulfoxide acetonitrile and methanol.
In some preferred embodiments of the present invention, catalysts, cross-linking agents and organic bases are also used in the process for the preparation of the modified benzisothiazolinone.
In some preferred embodiments of the invention, the catalyst comprises CuI, cuBr, cuCl, cuCl 2 、Cu(OAc) 2 At least one of them.
In some preferred embodiments of the present invention, the crosslinking agent comprises at least one of Triethylenediamine (TMEDA), dimethylethylenediamine (DMEDA), tetramethylethylenediamine (TMEDA).
In some preferred embodiments of the present invention, the organic base comprises 1, 4-diazabicyclo [2.2.2]Octane (DABCO), triethylamine (Et) 3 N) at least one of the following.
In some preferred embodiments of the invention, compound i: potassium thiocyanate: catalyst: crosslinking agent: organic base: the mol ratio of the solvent is (4-6): (9-11): (0.5-2): (0.5-2): (1-3): (30-70).
In some more preferred embodiments of the invention, compound i: potassium thiocyanate: catalyst: crosslinking agent: organic base: the mole ratio of the solvent is 5:10:1:1:2:50.
in some preferred embodiments of the invention, the preparation of the modified benzisothiazolinone is carried out in an inert atmosphere.
In some preferred embodiments of the invention, the temperature of the reaction is 120 ℃ to 160 ℃.
In some preferred embodiments of the invention, the reaction time is from 48 hours to 72 hours.
In some preferred embodiments of the invention, compound I and potassium thiocyanate are reacted in a solvent, then washed with distilled water to remove impurities, and dried in vacuo to give compound II.
In some preferred embodiments of the invention, the drying temperature is 80 ℃ to 100 ℃.
In some preferred embodiments of the invention, the drying time is 24 hours to 72 hours.
In some preferred embodiments of the invention, the method of hydrolysis of compound II is hydrolysis using a strong base.
In some preferred embodiments of the invention, the temperature of hydrolysis of compound II is 130 to 160 ℃.
In some preferred embodiments of the invention, the pressure of the hydrolysis of compound II is 1500 to 2500Pa.
In some preferred embodiments of the invention, the molar ratio of strong base to compound ii is 1:1.
in some preferred embodiments of the invention, the time of hydrolysis is from 5 to 6 hours.
In some preferred embodiments of the invention, compound II is hydrolyzed and then washed with absolute ethanol to precipitate the solid.
In some preferred embodiments of the invention, the precipitated solid is dried to give compound III.
In some preferred embodiments of the invention, the drying means comprises vacuum drying.
In some preferred embodiments of the invention, the drying temperature is 70-100 ℃.
In some preferred embodiments of the invention, the drying time is 24 to 48 hours.
In a second aspect of the present invention, there is provided a modified benzisothiazolinone prepared by the method of the first aspect of the present invention, wherein the modified benzisothiazolinone has the structural formula of
In a third aspect of the invention, an antibacterial material is provided, wherein the preparation raw material of the antibacterial material comprises the modified benzisothiazolinone in the second aspect of the invention.
According to a third aspect of the present invention, in some embodiments of the present invention, the antibacterial material further comprises a resin and an antibacterial metal compound in the raw material for preparing the antibacterial material.
In some preferred embodiments of the invention, the molar ratio of the modified benzisothiazolinone to the resin is (100 to 120): (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antibacterial metal compound includes a Zn, ag, cu-containing compound.
In some more preferred embodiments of the present invention, the antibacterial metal compound is an Ag-containing compound.
In some preferred embodiments of the present invention, the antimicrobial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of the following.
In some preferred embodiments of the present invention, the resin comprises an environmentally friendly acrylic resin.
In a fourth aspect of the present invention, there is provided a method for producing the antibacterial material according to the third aspect of the present invention, which comprises mixing a resin, an antibacterial metal compound and the modified benzisothiazolinone according to the second aspect of the present invention.
After mixing, the modified benzisothiazolinone is grafted onto the resin through hydroxyl groups, and the antibacterial property of the prepared material can be mentioned.
According to a fourth aspect of the invention, in some embodiments of the invention, the molar ratio of the modified benzisothiazolinone to the resin is (100 to 120): (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antimicrobial metal compound includes a complex containing Zn, ag, cu.
In some more preferred embodiments of the present invention, the antibacterial metal compound is an Ag-containing compound.
In some preferred embodiments of the present invention, the antimicrobial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of the following.
In some preferred embodiments of the present invention, the resin comprises an environmentally friendly acrylic resin.
In some preferred embodiments of the present invention, the method for preparing the environmentally friendly acrylic resin comprises the steps of:
(1) Mixing methacrylate, acrylic ester, acrylic acid and an initiator to obtain a mixed solution;
(2) Dropwise adding the mixed solution obtained in the step (1) into a solvent to react, and drying after the reaction to obtain solid resin;
(3) And (3) reacting the solid resin in the step (2) with a pH regulator, and drying to obtain the environment-friendly acrylic acid material.
In some preferred embodiments of the present invention, the methacrylate in step (1) includes any one of methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
In some preferred embodiments of the present invention, the acrylic acid ester in step (1) includes any one of methyl acrylate, ethyl acrylate, and butyl acrylate.
In some preferred embodiments of the present invention, the molar ratio of methacrylate, acrylate and acrylic acid in step (1) is (70 to 80): (20-25): (5-10).
In some preferred embodiments of the present invention, the initiator comprises at least one of tetrabutyl titanate, dibenzoyl peroxide, and azobisisobutyronitrile.
In some preferred embodiments of the present invention, the initiator is added in an amount of 1 to 3% based on the total mass of methacrylate, acrylate, acrylic acid.
In some preferred embodiments of the present invention, the solvent in step (2) comprises at least one of toluene, butyl acetate, xylene, n-butanol, isobutanol, propylene glycol butyl ether, propylene glycol methyl ether.
In some preferred embodiments of the present invention, the reaction is performed in step (2) by adding the mixed solution dropwise to the solvent by means of heat refluxing.
In some preferred embodiments of the invention, the temperature of the heated reflux is 80 ℃ to 100 ℃.
In some preferred embodiments of the invention, the mixed solution is added dropwise over a period of 2 to 5 hours.
In some preferred embodiments of the invention, the mixed solution is reacted in the solvent for a period of time ranging from 1h to 3h.
In some preferred embodiments of the invention, the means of drying in step (2) comprises vacuum drying.
In some preferred embodiments of the invention, the temperature of the vacuum drying is 120℃to 150 ℃.
In some preferred embodiments of the invention, the time of vacuum drying is 24h to 72h.
In some preferred embodiments of the present invention, the pH adjuster in step (3) comprises dimethylethanolamine.
In some preferred embodiments of the present invention, the reaction temperature in step (3) is 60℃to 100 ℃.
In some preferred embodiments of the invention, the drying in step (3) comprises vacuum drying.
In some preferred embodiments of the present invention, the drying temperature in step (3) is 60 to 80 ℃.
In some preferred embodiments of the invention, the drying time described in step (3) is 24 to 48 hours.
In some preferred embodiments of the present invention, the pH adjuster in step (3) is used in an amount of 1% wt% to 2% by weight of the solid resin.
In some preferred embodiments of the present invention, in the preparation process of the environment-friendly acrylic resin, the modified benzisothiazolinone and the antibacterial metal compound according to the second aspect of the present invention are simultaneously added in the step (3), and the antibacterial material is prepared after drying.
In some preferred embodiments of the invention, the molar ratio of the modified benzisothiazolinone to the resin is (100 to 120): (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antimicrobial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of the following.
In a fifth aspect, the invention provides an application of the modified benzisothiazolinone in the second aspect in preparation of antibacterial materials.
According to a fifth aspect of the invention, in some embodiments of the invention, the antimicrobial material comprises an antimicrobial resin material.
In a sixth aspect, the invention provides an application of the antibacterial material in paint, ink and adhesive.
According to a sixth aspect of the invention, in some embodiments of the invention, the coating comprises an anti-fouling coating.
The beneficial effects of the invention are as follows:
according to the invention, the modified benzisothiazolinone is grafted on the environment-friendly acrylic acid material, so that the obtained antibacterial environment-friendly acrylic acid material has a good antibacterial effect on staphylococcus aureus and escherichia coli, the antibacterial performance of the environment-friendly acrylic acid material is improved, and the material has the characteristic of environmental friendliness and has a good application prospect in the field of paint.
Drawings
FIG. 1 is a statistical graph of the antibacterial activity against Staphylococcus aureus of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2;
FIG. 2 is a statistical graph showing the antibacterial activity against E.coli of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will be more apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
EXAMPLE 1 preparation of modified benzisothiazolinone
(1) By reacting compound IAnd potassium thiocyanate are put into a reaction kettle filled with N, N-Dimethylformamide (DMF), and are added with a catalyst CuI, a cross-linking agent N, N' -dimethylethylenediamine (DMEDA) and an organic base triethylamine (Et) 3 N), the molar ratio of the substances is that of a compound I: potassium thiocyanate: cuI: DMEDA: et (Et) 3 N: dmf=5: 10:1:1:2:50, the above materials were stirred in DMF for 0.5h and then reacted at 140℃for 48h under nitrogen atmosphere with stirring and heating to 140 ℃. After the reaction, cooling the mixture to 25 ℃, washing off impurities with distilled water, drying under vacuum at 80 ℃ for 48 hours to obtain a compound II
(2) Adding NaOH to hydrolyze the compound II at 140 ℃ and 2000Pa, wherein the mol ratio of the NaOH to the compound II is 1:1, after hydrolysis for 5 hours, washing the precipitated solid by using absolute ethyl alcohol, drying the washed solid under vacuum condition at 80 ℃ for 48 hours to obtain the compound III
I.e. modified benzisothiazolinones.
Example 2
(1) 75mL of methyl methacrylate, 20mL of methyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of toluene into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding the mixture solution in the step (1), dripping 150mL of toluene in 3 hours, reacting at 80 ℃ for 2 hours to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum condition to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 50g of the modified benzisothiazolinone in the example 1, 1g of ZnOH and 100g of the solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the reaction until the solution becomes clear and transparent, and vacuum drying at 80 ℃ for 48 hours after the reaction is finished when no water is generated, thus obtaining the antibacterial environment-friendly acrylic acid material.
Example 3
(1) 75mL of methyl methacrylate, 15mL of butyl acrylate, 10mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of propylene glycol methyl ether into a round-bottomed flask, heating and refluxing at 80 ℃, dropwise adding 300mL of toluene into the mixed solution in the step (1), finishing dripping in 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48h;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 60g of the modified benzisothiazolinone in the example 1, 1g of ZnO and 100g of the solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the reaction is clear and transparent, and carrying out vacuum drying at 80 ℃ for 48 hours after the reaction is finished when no water is generated, thus obtaining the antibacterial environment-friendly acrylic material.
Example 4
(1) 75mL of methyl methacrylate, 20mL of ethyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding 150mL of toluene into the mixed solution in the step (1), finishing dripping in 3 hours, reacting at 80 ℃ for 2 hours to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) 10mL of dimethylethanolamine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of ZnCl were added 2 100g of the solid resin in the step (2) is heated to 80 ℃ for reaction, the temperature is raised to 120 ℃ for dehydration after the solution becomes clear and transparent, the reaction is finished when no water is generated in the reaction, and the vacuum drying is carried out for 48 hours at 80 ℃ to obtain the antibacterial environment-friendly acrylic acid material.
Example 5
(1) 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of toluene into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding the mixture solution in the step (1), dripping 150mL of toluene in 3 hours, reacting at 80 ℃ for 2 hours to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum condition to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) 10mL of dimethylethanolamine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of CuCl were added 2 100g of the solid resin in the step (2) is heated to 80 ℃ for reaction, the temperature is raised to 120 ℃ for dehydration after the solution becomes clear and transparent, the reaction is finished when no water is generated in the reaction, and the vacuum drying is carried out for 48 hours at 80 ℃ to obtain the antibacterial environment-friendly acrylic acid materialAnd (5) material.
Example 6
(1) 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of a toluene and xylene mixed solvent into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding the mixture into the mixed solution in the step (1), finishing dripping 150mL of toluene within 3 hours, reacting for 2 hours at 80 ℃ to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 70g of the modified benzisothiazolinone in the example 1, 1g of AgCl and 100g of the solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the reaction is clear and transparent, and carrying out vacuum drying at 80 ℃ for 48 hours after the reaction is finished when no water is generated, thus obtaining the antibacterial environment-friendly acrylic acid material.
Example 7
(1) 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding 150mL of toluene into the mixed solution in the step (1), finishing dripping in 3 hours, reacting at 80 ℃ for 2 hours to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) 10mL of dimethylethanolamine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of Ag were added 2 O, 100g of the solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the reaction until the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and vacuum drying at 80 ℃ for 48 hours to obtainAntibacterial environment-friendly acrylic material.
Example 8
(1) 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide are added into a three-neck flask and stirred and mixed for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding 150mL of toluene into the mixed solution in the step (1), finishing dripping in 3 hours, reacting at 80 ℃ for 2 hours to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under vacuum to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃ and the drying time is 48 hours;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 70g of the modified benzisothiazolinone in the example 1, 1g of AgOH and 100g of the solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the reaction until the solution becomes clear and transparent, and vacuum drying at 80 ℃ for 48 hours after the reaction is finished when no water is generated, thus obtaining the antibacterial environment-friendly acrylic acid material.
Comparative example 1
The method for producing the acrylic material in comparative example 1 was the same as in example 6, except that the modified benzisothiazolinone and AgCl in example 1 were not added in step (3) in the production of the acrylic material in comparative example 1.
Comparative example 2
The preparation of the acrylic material in comparative example 2 was the same as in example 6, except that in the preparation of the acrylic material in comparative example 2, the modified benzisothiazolinone was replaced with an equivalent amount of commercially available benzisothiazolinone in step (3), which was a chemically pure reagent with a purity of 98% and was purchased from a network of a Ding Shiji.
Test of antibacterial Properties
The antibacterial properties of the acrylic materials provided in examples and comparative examples against Staphylococcus aureus and Escherichia coli were measured with reference to GB/T31402-2015 standard.
The results of the antibacterial tests of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 against Staphylococcus aureus and Escherichia coli are shown in Table 1 and FIGS. 1 to 2, FIG. 1 is a statistical chart of antibacterial ratios of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 against Staphylococcus aureus, and FIG. 2 is a statistical chart of antibacterial ratios of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 against Escherichia coli.
Table 1 results of antibacterial tests of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 against staphylococcus aureus and escherichia coli
As can be seen from the data in Table 1, the acrylic acid material prepared in the embodiment of the invention has higher antibacterial rate for staphylococcus aureus and escherichia coli, which shows that the addition of the modified benzisothiazolinone in the embodiment 1 of the invention improves the antibacterial performance of the acrylic acid material, and the larger the addition amount of the modified benzisothiazolinone is, the better the antibacterial performance is, and the highest antibacterial rate can reach 99.9%; as can be seen from comparative examples 4, 5 and 6, ag + And the antibacterial performance of the modified benzisothiazolinone after being compounded is good.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (5)

1. An antibacterial material is characterized in that the preparation raw materials of the antibacterial material comprise modified benzisothiazolinone, resin and antibacterial metal compound;
the structural formula of the modified benzisothiazolinone is as follows:
the preparation method of the modified benzisothiazolinone comprises the following steps:
the compound I and potassium thiocyanate react in a solvent to prepare a compound II, and the compound II is hydrolyzed to prepare modified benzisothiazolinone shown in a formula III;
wherein the structural formula of the compound I isX is selected from any one of F, cl, br, I;
wherein the structural formula of the compound II isX is selected from any one of F, cl, br, I;
the method for hydrolyzing the compound II comprises the step of hydrolyzing by using strong alkali;
the hydrolysis temperature of the compound II is 130-160 ℃;
the hydrolysis pressure of the compound II is 1500-2500 Pa;
the resin comprises environment-friendly acrylic resin;
the preparation method of the environment-friendly acrylic resin comprises the following steps:
(1) Mixing methacrylate, acrylic ester, acrylic acid and an initiator to obtain a mixed solution;
(2) Dropwise adding the mixed solution obtained in the step (1) into a solvent to react, and drying after the reaction to obtain solid resin;
(3) Reacting the solid resin in the step (2) with a pH regulator, and drying to obtain an environment-friendly acrylic material;
the antibacterial metal compound is selected from Ag 2 O, agCl, agOH.
2. The method for producing an antibacterial material according to claim 1, characterized in that the method comprises mixing a resin, an antibacterial metal compound and a modified benzisothiazolinone to produce the antibacterial material.
3. The method of claim 2, wherein the molar ratio of the modified benzisothiazolinone to the resin is (100 to 120): (50-80).
4. The method according to claim 2, wherein the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
5. Use of the antibacterial material according to claim 1 in paints, inks, adhesives.
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