CN109810221B - Preparation method and application of betaine antibacterial agent - Google Patents
Preparation method and application of betaine antibacterial agent Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a betaine antibacterial agent, and belongs to the field of textiles. The invention utilizes unsaturated tertiary amine monomer, acrylate monomer, monomer containing epoxy group and monomer containing sulfonic acid group or carboxylic acid group to polymerize to obtain the antibacterial polymer. The method has the advantages that the polymerized monomers are selected according to different fabrics and different purposes, a wider thought is provided for the synthesis of the antibacterial agent, the proportion of the different polymerized monomers can be regulated and controlled according to the performance requirements of the finally finished fabrics, the finished fabrics have high antibacterial rate and good fastness to washing, the antibacterial effect can still be good after 50 times of washing, and the physical and mechanical properties and the strength are not obviously lost. The antibacterial agent has wider application range and is harmless to the environment; the skin care product has no cytotoxicity and no stimulation to the skin; has no drug resistance and is suitable for wide use.
Description
Technical Field
The invention relates to a preparation method and application of a betaine antibacterial agent, and belongs to the field of textiles.
Background
With the development of modern environmental protection concept, textiles made of natural fibers are favored because of wearing comfort, reproducibility, easy biodegradation and the like. However, since the natural fiber macromolecule structure chain contains a plurality of hydrophilic groups such as amino (-NH2), carboxyl (-COOH), hydroxyl (-OH) and the like, the natural fiber macromolecule structure chain can easily absorb the secretion of a human body, thereby providing a good environment for the growth and the propagation of microorganisms. Microorganisms that colonize the fabric not only degrade the quality and physical properties of the fabric, but are more likely to be harmful to human health. Therefore, it is very important to perform antibacterial finishing on the fabric to make the fabric have the capability of inhibiting or killing microorganisms such as bacteria.
Currently, antibacterial finishing agents for textiles can be classified into two major classes, i.e., dissolution type (metals, antibiotics, etc.) and non-dissolution type (quaternary ammonium salts, chitosan, polymeric cations, antibacterial peptides, etc.), according to their dissolution properties. The dissolution type (metal, antibiotic and the like) antibacterial fabric achieves the purpose of bacteriostasis or sterilization by virtue of slowly releasing the antibacterial agent into the surrounding environment. However, as the number of washes increases, the less the antimicrobial agent remaining on the fabric, the less the antimicrobial activity of the fabric gradually decreases and eventually is lost completely, and the small amount of residual antibiotic is insufficient to kill the bacteria, but rather causes resistance and biofilm formation. And the nano Ag + still has a big debate in the aspects of cytotoxicity and genetic toxicity.
The non-dissolution type quaternary ammonium salt antibacterial agent has high water solubility, is easy to wash off, is not firmly combined with fibers directly, and needs to be pretreated to ensure that the fabric has poor hand feeling and yellowing and discoloration, and the quaternary ammonium salt antibacterial agent is proved to cause bacteria to generate drug resistance and has weak durability of antibacterial effect; the antibacterial peptide can interfere the exchange of divalent cations on cell membranes, thereby destroying the cytoplasmic membranes and achieving the bactericidal effect. CN201510595396.3 treats wool fabric with antibacterial peptide, and uses glutaraldehyde to crosslink the antibacterial peptide on the surface of the wool fabric, so as to obtain the antibacterial wool fabric. But the wastewater generated in the preparation process is harmful to the environment and pollutes the water body, and the antibacterial peptide is easily affected by enzymolysis, sensitive to salt and poor in stability.
Betaine, as a zwitterionic compound, has good hydrophilic properties, has equimolar amounts of uniformly distributed anionic and cationic groups, and is capable of resisting bacterial adhesion, preventing the formation of biofilm, and inhibiting the growth and reproduction of bacteria. Meanwhile, the antibacterial agent also has stronger thermal stability, chemical stability, biocompatibility and no cytotoxicity, and is an ideal antibacterial agent. CN201010116533.8 prepares an organosilicon sulfobetaine antibacterial agent, but siloxane betaine has poor storage stability, is easy to self-coagulate, has poor reaction activity, forms covalent bond combination with fabric at high temperature, and damages the physical and mechanical properties of the fabric. CN201580001138.6 develops a sulfopropyl betaine antibacterial agent with terminal isocyanate, but the preparation process is complex, the raw material cost is high, and the industrial application is difficult. Meanwhile, the prepared betaine antibacterial agents are short-chain micromolecular betaine and cannot penetrate through bacterial film layers, so that the bactericidal effect is poor. CN201711472560.7 polymerizes betaine monomer and maleic anhydride to obtain macromolecular betaine polymer, and then carboxylic acid group generated by maleic anhydride hydrolysis reacts with hydroxyl on cellulose fiber molecule to graft on cotton fabric in covalent bond mode. The obtained betaine polymer antibacterial agent penetrates cell membrane attached with bacteria, thereby enabling cell contents to flow out, killing bacteria and having good antibacterial effect. However, because the macromolecules of the betaine polymer have extremely many acidic carboxyl groups, the finished fabric is seriously yellowed, and the physical and mechanical properties of the fabric are greatly damaged, so that the strength of the fabric is seriously reduced, the requirement for taking the fabric cannot be met, and the practical value is not high. Therefore, how to overcome the defects of the existing antibacterial agent, and develop and research a new antibacterial agent which is curable, has long-acting property, does not damage the performance of the fabric and does not generate toxic or side effect on human bodies, becomes an urgent need for the functional development of the fabric.
Disclosure of Invention
In order to overcome the disadvantages of the prior antibacterial agents such as those described above, the present invention constructs a macromolecular polymer antibacterial agent having a betaine structure. The outer membrane of the microbial cell is a semipermeable membrane and consists of a fat layer and protein, the inner layer and the outer layer are the protein, and the middle layer is the fat, so that an antibacterial agent is required for permeating the microbial cell to kill bacteria, and the antibacterial agent has hydrophile lipophilicity. Therefore, the ideal fabric antibacterial agent is a macromolecular antibacterial agent which has both hydrophilic groups and hydrophobic groups and can be directly bonded with active groups on the fabric. According to the invention, the reactive functional group is firmly bonded with the macromolecular chain of the fabric in a covalent bond mode, and the unsaturated tertiary amine monomer, the acrylate monomer and the crosslinkable monomer are introduced to prepare the betaine antibacterial agent, so that the lasting antibacterial activity is obtained.
The first purpose of the invention is to provide an antibacterial polymer, which is prepared by using an unsaturated tertiary amine monomer A, an acrylate monomer B, an epoxy group-containing monomer C and a compound E containing a sulfonic acid group or a carboxylic acid group as raw materials.
In one embodiment of the present invention, the molar ratio of the unsaturated tertiary amine monomer to the acrylate monomer is 1: 9-9: 1.
in one embodiment of the present invention, the epoxy group-containing monomer is added in an amount of 1 to 20% by mass based on the total mass of the unsaturated tertiary amine monomer, the acrylate monomer and the epoxy group-containing monomer.
In one embodiment of the invention, the unsaturated tertiary amine monomer A comprises one or more of N, N-diethylallylamine, N-dimethylallylamine, allylamine, N-methylacrylamine, dimethylaminoethyl acrylate.
In one embodiment of the present invention, the acrylate monomer B includes one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate, or hydroxyethyl acrylate.
In one embodiment of the present invention, the epoxy group-containing monomer C comprises glycidyl methacrylate or allyl glycidyl ether.
In one embodiment of the invention, the compound E containing sulfonic acid groups or carboxylic acid groups is a saturated hydrocarbon compound containing sulfonic acid groups or carboxylic acid groups.
In one embodiment of the invention, the compound E comprises X- (CH)2)vCHCO2 -、X-(CH2)wCHSO3 -One or two of them; wherein v, w are positive integers greater than or equal to 1, and X is Cl, Br or I.
In one embodiment of the present invention, the method for preparing the antibacterial polymer comprises:
(1) preparing an intermediate polymer D by using an unsaturated tertiary amine monomer A, an acrylate monomer B and an epoxy group-containing monomer C;
(2) and (3) reacting the intermediate polymer D with a monomer E containing a sulfonic acid group or a carboxylic acid group to obtain the betaine antibacterial polymer F.
In one embodiment of the present invention, the step (1) specifically includes: mixing unsaturated tertiary amine monomer A, acrylate monomer B and epoxy group-containing monomer C in N2Reacting for 4-24h under the action of an initiator in the environment at the temperature of 20-80 ℃ to obtain an intermediate polymer D.
In one embodiment of the present invention, the initiator includes one or both of a peroxide-based initiator and an azo-based initiator.
In one embodiment of the present invention, the peroxide initiator includes one or more of benzoyl peroxide, dialkyl peroxide, and diacyl peroxide.
In one embodiment of the present invention, the azo initiator includes one or both of azobisisobutyronitrile and azobisisoheptonitrile.
In one embodiment of the invention, the molar ratio of the compound E in the step (2) to the tertiary amine monomer contained in the intermediate polymer D is 1 (1-2).
In an embodiment of the present invention, the step (2) specifically includes: mixing the intermediate polymer D with the monomer E, and stirring for 2-10h under nitrogen at the temperature of 50-80 ℃ to obtain a betaine antibacterial polymer F;
in one embodiment of the present invention, the synthetic route of the method is as follows:
wherein m is 1-1000, n is 1-1000, and q is 1-1000;
R1is-H, -CH3Or CH2CH3；R2is-H, -CH3Or CH2CH3；R3Is- (CH2)p-, or-COO- (CH2)k-, where p is any one integer from 1 to 18, k is any one integer from 0 to 18; r4Is- (CH2)lCH3Or- (CH2)r-OH, wherein l, r are each any integer from 1 to 6; r5is-H, or-CH3；R6Is composed of
or-CH2-；R7is-H, or-CH3；R8is-CH2-, or-CH2CH3；R9Is- (CH2)tWherein t is a positive integer greater than or equal to 2;
X-is-COO-, -SO-3 -。
The second purpose of the invention is to provide an antibacterial polymer, which is a polymer shown in a formula (I),
wherein m is 1-1000, n is 1-1000, and q is 1-1000;
R1is-H, -CH3Or CH2CH3；R2is-H, -CH3Or CH2CH3；R3Is- (CH2)p-, or-COO- (CH2)k-, where p is any one integer from 1 to 18, k is any one integer from 0 to 18; r4Is- (CH2)lCH3Or- (CH2)r-OH, wherein l, r are each any integer from 1 to 6; r5is-H, or-CH3；R6Is composed of
or-CH2-；R7is-H, or-CH3；R8is-CH2-, or-CH2CH3；R9Is- (CH2)tWherein t is greater than or equal toA positive integer equal to 2;
X-is-COO-, -SO-3 -。
It is a third object of the present invention to provide an antibacterial agent comprising the above antibacterial polymer.
A fourth object of the present invention is to provide a method for antibacterial finishing of fabric, the method comprising:
(1) preparing the antibacterial polymer into antibacterial finishing liquid according to the proportion that the solid content is 1-25%;
(2) and soaking the fabric in the antibacterial finishing liquid, performing fabric rolling treatment, and baking to obtain the antibacterial fabric.
In one embodiment of the invention, the bath ratio of the textile to the antimicrobial finish is 1: (20-40).
In one embodiment of the invention, the temperature at the time of the fabric rolling treatment is 10 to 60 ℃.
In one embodiment of the present invention, the specific process of the rolled cloth treatment comprises: soaking the fabric into the antibacterial finishing liquid according to the bath ratio, controlling the temperature at 10-60 ℃, and keeping the temperature for 10-300 min; and taking out the fabric and carrying out cloth rolling treatment.
In an embodiment of the present invention, the rolled cloth may be subjected to a double-dipping and double-rolling method.
The invention has the following beneficial effects:
1. according to the invention, betaine monomers with good hydrophilicity and monomers with certain hydrophobicity are combined to prepare the polymer, and the polymer simultaneously has hydrophilic groups and hydrophobic groups, and the proportion is adjustable. Compared with the original hydrophilic betaine micromolecules, the hydrophobic structure is introduced according to the principle of similar compatibility, so that the hydrophobic structure can easily permeate a fat layer and a protein layer of a microbial cell outer membrane (the inner layer and the outer layer of the microbial cell membrane are protein layers, and the middle layer is a fat layer), and meanwhile, the antibacterial agent with a macromolecular chain has strong penetrating capacity on a biological membrane, and the sterilization effect is more obvious; epoxy groups (reactant C) are introduced into the polybetaine antibacterial agent, so that the polybetaine antibacterial agent is subjected to ring opening under appropriate conditions and is bonded with active groups on the fabric, and the antibacterial agent is firmly bonded on the fabric, and the antibacterial and washing resistance of the polybetaine antibacterial agent is enhanced.
2. The invention designs the polymer structural formula of A-B-C, selects the polymerized monomers according to different fabrics and different purposes, provides a wider thought for the synthesis of the antibacterial agent, can regulate and control the proportion of different polymerized monomers according to the performance requirements of the finally finished fabrics, and has wider application range; the polybetaine antibacterial agent belongs to a non-dissolution type antibacterial agent and is harmless to the environment; the skin care product has no cytotoxicity and no stimulation to the skin; has no drug resistance and is suitable for wide use.
3. The preparation method of the poly betaine antibacterial agent has the advantages of easily controlled reaction process and high yield, and is very suitable for industrial production.
4. The fabric finished by the antibacterial agent has high antibacterial rate and good fastness to washing, has a good antibacterial effect after being washed for 30 times, and has no obvious loss of physical and mechanical properties and strength.
Drawings
FIG. 1: the antibacterial effect graph of the betaine antibacterial agent; wherein, 1a is a staphylococcus aureus growth blank without the antibacterial agent, and 1b is a staphylococcus aureus growth blank with the antibacterial agent prepared by 2.5 g/L; 2a is the growth blank of E.coli without the addition of the antimicrobial agent, and 2b is the growth blank of E.coli with the addition of 2.5g/L of the prepared antimicrobial agent.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
The determination method of the antibacterial rate comprises the following steps: reference is made to section 3 of evaluation of antibacterial properties of GB/T20944.3-2008-T textiles: and (4) testing the antibacterial performance of the fabric before and after the treatment by an oscillation method. When the bacteriostatic rate of the antibacterial agent on staphylococcus aureus and escherichia coli is more than or equal to 70%, the sample has an antibacterial effect. After the AAA product is washed by water for 50 times, the bacteriostasis rate to staphylococcus aureus is more than or equal to 80 percent, and the bacteriostasis rate to escherichia coli is more than or equal to 70 percent.
Example 1:
preparing a betaine antibacterial agent and finishing the fabric according to the following steps:
1) preparing an antibacterial finishing agent:
8.5g of dimethylallylamine (dissolved in acetone) are weighed out and introduced into a reaction vessel with mechanical stirring and reflux, under N2Under the environment, after 0.21g of benzoyl peroxide is added, 12.8g of butyl acrylate and 1.065g of glycidyl methacrylate are slowly dripped by a syringe under stirring at the temperature of 20 ℃, the reaction is stopped at room temperature after 24 hours, and the polymer is obtained after centrifugal separation and purification for a plurality of times; 21.3g of this polymer was taken and dissolved in tetrahydrofuran in N2Under the environment, slowly dripping 12.2g of propane sultone by using an injector under the stirring and 50 ℃, reacting for 10 hours to obtain white precipitate, extracting, removing reaction byproducts, and drying in vacuum to obtain the final product, namely the polybetaine antibacterial agent.
The obtained antibacterial agent has the effects shown in FIG. 1, wherein 1a and 2a are growth conditions of Escherichia coli and Staphylococcus aureus without antibacterial agent, and 1b and 2b are growth conditions of Escherichia coli and Staphylococcus aureus with antibacterial agent prepared at 5 g/L. The obtained antibacterial agent has obvious inhibition effect on the growth of staphylococcus aureus and escherichia coli (the inhibition rate on staphylococcus aureus is 99.9999%, and the inhibition rate on escherichia coli is 99.9984%), and the antibacterial effect is very good.
2) Preparing an antibacterial fabric:
weighing 10.5g of polybetaine antibacterial agent, and dissolving in 300mL of water to obtain an antibacterial agent solution; the bath ratio is 1: 30, soaking the fabric obtained in the step 2 in an antibacterial agent solution at the temperature of 20 ℃ for 30 min; and taking out the fabric, rolling the fabric, wherein the rolling residual rate is 100%, and sending the fabric to pre-baking at 80 ℃, 5min, baking at 130 ℃ and 3min to obtain the antibacterial fabric, wherein the antibacterial effect of the treated fabric is shown in table 1.
Example 2:
the molar fractions of butyl acrylate and dimethylallylamine were adjusted to 1:9, 2:3, 3:2 and 9:1 under the conditions of example 1, and the other conditions were not changed to prepare a polysulfonic betaine antibacterial agent.
The fabric was treated with the obtained polysulfonic betaine antimicrobial agent under the fabric treatment conditions of example 1, and the parameters of the treated fabric are shown in table 1.
TABLE 1 antimicrobial Effect of the treated fabrics
Note: the water washing resistance test is carried out according to GB/T20944.3-2008 < evaluation of antibacterial property of textile part 3: the test standard in the oscillatory method was conducted.
The product has the antibacterial effect: as can be seen from Table 1, the difference of the antibacterial effect of the fabric finished by the poly-sulfobetaine antibacterial agent prepared under different molar ratios of butyl acrylate and dimethyl allyl amine is large.
And fastness to washing of the product: after 50 times of water washing, when the molar ratio of butyl acrylate to dimethyl allyl amine is 2:3-3:2, the antibacterial rate of the fabric is higher than 70%, and the fabric has higher antibacterial property, which indicates that the fabric can achieve better washing resistance after being finished by the antibacterial agent prepared by the invention, wherein the washing resistance effect is better with the same dosage or with a little more tertiary amine. Excessive butyl acrylate or dimethyl allyl amine obviously reduces the fastness after 50 times of water washing.
Example 3:
preparing a betaine antibacterial agent and finishing the fabric according to the following steps:
1) preparing an antibacterial finishing agent:
14.3g of dimethylaminoethyl acrylate are weighed into a reaction vessel with mechanical stirring and reflux equipment and stirred under N2Under the environment, adding 0.27g of azobisisobutyronitrile, slowly dropwise adding 12.8g of butyl acrylate and 1.355g of allyl glycidyl ether by using a syringe under stirring at 80 ℃, reacting for 4 hours, stopping the reaction at room temperature, and carrying out centrifugal separation for several times to purify to obtain a polymer; taking 27g of the polymer, under N2Under the environment, slowly dripping 12.2g of propane sultone by using an injector under the condition of stirring and at the temperature of 80 ℃, reacting for 2 hours to obtain white precipitate, extracting, removing reaction byproducts, and drying in vacuum to obtain a final product, namely a polybetaine antibacterial agent;
2) preparing an antibacterial fabric:
weighing 10.5g of polybetaine antibacterial agent, and dissolving in 300mL of water to obtain an antibacterial agent solution; the bath ratio is 1: 30, soaking the fabric obtained in the step 2 in an antibacterial agent solution at the temperature of 20 ℃ for 30 min; and taking out the fabric, rolling the fabric, wherein the rolling residual rate is 100%, and sending the fabric to pre-baking at 80 ℃, 5min, baking at 130 ℃ and 3min to obtain the antibacterial fabric, wherein the antibacterial effect of the treated fabric is shown in table 2.
Example 4:
the polysulfonic acid betaine antibacterial agent was prepared by adjusting the mass fraction of allyl glycidyl ether to 0.25%, 1%, 10%, 20%, 50% under the conditions of example 3, and keeping the other conditions unchanged.
The fabric was treated with the resulting polysulfonate betaine antimicrobial under the fabric treatment conditions of example 3, and the parameters related to the treated fabric are shown in table 2.
TABLE 2 relevant parameters of the treated Fabric
Note: the whiteness value of the fabric before treatment is 73.2, the warp breaking strength is 795N, the weft breaking strength is 410N, and the water washing resistance test is carried out according to GB/T20944.3-2008 < evaluation 3 rd part of antibacterial performance of textiles: the test standard in the oscillatory method was conducted.
Example 5:
the molar ratio of the tertiary amine-containing monomer to propane sultone was adjusted to 1:2 under the conditions of example 3, and the polysulfonic betaine antibacterial agent was prepared under the same conditions as those of example 3.
The fabric was treated with the obtained polysulfonate betaine antimicrobial agent according to the fabric treatment conditions of example 3, and the parameters of the treated fabric are shown in table 3.
Example 6:
preparing a betaine antibacterial agent and finishing the fabric according to the following steps:
1) preparing an antibacterial finishing agent:
11.3g of N, N-diethylallylamine were weighed out and added to the beltIn a reaction vessel having a mechanical stirring and refluxing apparatus, in2Under the environment, after 0.23g of azobisisobutyronitrile is added, 11.8g of isooctyl acrylate and 1.355g of allyl glycidyl ether are slowly dripped by a syringe under stirring at 60 ℃, the reaction lasts for 10 hours, the reaction is stopped at room temperature, and the polymer is obtained after centrifugal separation and purification for a plurality of times; taking 23g of the polymer, under N2Under the environment, slowly dripping 8.6g of B-butyrolactone by using an injector under the condition of stirring and at the temperature of 60 ℃, reacting for 2 hours to obtain white precipitate, extracting, removing reaction byproducts, and drying in vacuum to obtain a final product, namely a polybetaine antibacterial agent;
2) preparing an antibacterial fabric:
weighing 10.5g of polybetaine antibacterial agent, and dissolving in 300mL of water to obtain an antibacterial agent solution; the bath ratio is 1: 30, soaking the fabric obtained in the step 2 in an antibacterial agent solution at the temperature of 20 ℃ for 30 min; and taking out the fabric, rolling the fabric, wherein the rolling residual rate is 100%, and sending the fabric to pre-baking at 80 ℃, 5min, baking at 130 ℃ and 3min to obtain the antibacterial fabric, wherein the antibacterial effect of the treated fabric is shown in table 3.
Comparative example 1:
the polysulfonic acid betaine antibacterial agent is prepared according to the following steps:
referring to example 1, only in the first step of preparing the polymer, no glycidyl methacrylate was added, and the other conditions were not changed, to prepare a polysulfonate betaine antibacterial agent.
The method for preparing the antibacterial agent finished fabric comprises the following steps:
the finishing method of the fabric is the same as that of the example 1, and the relevant parameters of the fabric after treatment are shown in a table 3.
Comparative example 2:
the polysulfonic acid betaine antibacterial agent is prepared according to the following steps:
referring to example 6, only when the polymer was synthesized in the first step, the polysulfonic betaine antibacterial agent was prepared without adding isooctyl acrylate and without changing other conditions.
The method for preparing the antibacterial agent finished fabric comprises the following steps:
the finishing method of the fabric is the same as that of example 6, and the relevant parameters of the fabric after treatment are shown in Table 3.
Comparative example 3:
the polysulfonic acid betaine antibacterial agent is prepared according to the following steps:
referring to example 6, only when the polymer was synthesized in the first step, isooctyl acrylate and allyl glycidyl ether were not added, and other conditions were not changed, to prepare a polysulfonic betaine antibacterial agent.
The method for preparing the antibacterial agent finished fabric comprises the following steps:
the finishing method of the fabric is the same as that of example 6, and the relevant parameters of the fabric after treatment are shown in Table 3.
Comparative example 4:
the preparation method of the antibacterial agent comprises the following steps: weighing 25.55g of dimethylallylamine, adding the dimethylallylamine into a four-neck flask, slowly dropwise adding propane sultone (36.6g, dissolved in 300mL of absolute ethyl alcohol) by using an injector under the nitrogen environment at the temperature of 50 ℃, reacting for 2 hours, and repeatedly purifying to obtain a betaine monomer. Weighing 62.1g of betaine monomer, 29.4g of maleic anhydride and a certain amount of ammonium persulfate, dissolving in deionized water, carrying out polymerization reaction for 2 hours at 90 ℃, purifying and drying to obtain the betaine antibacterial finishing agent.
The preparation method of the antibacterial agent finished fabric comprises the following steps:
the finishing method of the fabric is the same as that of example 6, and the relevant parameters of the fabric after treatment are shown in Table 3.
TABLE 3 parameters relating to the treated fabrics
Note: the whiteness value of the fabric before treatment is 73.2, the warp breaking strength is 795N, the weft breaking strength is 410N, and the water washing resistance test is carried out according to GB/T20944.3-2008 < evaluation 3 rd part of antibacterial performance of textiles: the test standard in the oscillatory method was conducted.
The product has the antibacterial effect: the antibacterial performance data of the fabric treated by the antibacterial agent are shown in tables 1-3, and as can be seen from comparative examples 1-6 and comparative examples 1-3, the fabric treated by the poly sulfobetaine antibacterial agent designed by the invention has better antibacterial effect than the antibacterial agent of which the polymerized monomer only contains tertiary amine and crosslinking monomer, and the antibacterial agent of which the polymerized monomer only contains tertiary amine and acrylic ester and only contains tertiary amine monomer.
Water washing resistance: reference is made to GB/T20944.3-2008 < evaluation of antibacterial properties of textiles section 3: and (4) carrying out a washing fastness test on the fabric after being finished by the antibacterial agent according to the standard of the oscillatory method. After the water washing was completed, the antibacterial effect of the fabric was measured. Comparing the fabrics finished in the examples 1-6 with the comparative examples 1-4, the fabrics treated by the antibacterial agent designed by the invention still have higher antibacterial performance, which indicates that the antibacterial agent has better water washing resistance.
Other properties: the fabric before and after finishing of the polysulfonate betaine antibacterial agent is subjected to a breaking strength test by referring to GB/T3923 and 2013 'determination strip sample method for tensile property, breaking strength and breaking elongation of fabric'. As can be seen from the data in table 3, the loss of breaking strength is less for the fabric finished with polysulfonate betaine. Especially, compared with the comparative example 4, the strong retention rate is much higher than that of the antibacterial cotton fabric prepared by the comparative example 4.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. An antibacterial polymer is characterized in that the polymer is prepared by using an unsaturated tertiary amine monomer, an acrylate monomer, an epoxy group-containing monomer, and a compound containing a sulfonic acid group or a carboxylic acid group as raw materials;
the preparation method of the antibacterial polymer comprises the following steps:
(1) preparing an intermediate polymer by using an unsaturated tertiary amine monomer, an acrylate monomer and an epoxy group-containing monomer;
(2) reacting the intermediate polymer obtained in the step (1) with a compound containing a sulfonic acid group or a carboxylic acid group to obtain a betaine antibacterial polymer;
the molar ratio of the unsaturated tertiary amine monomer to the acrylate monomer is 2:3-3: 2;
the addition amount of the epoxy group-containing monomer accounts for 1-20% of the total mass of the unsaturated tertiary amine monomer, the acrylate monomer and the epoxy group-containing monomer;
the acrylate monomer comprises one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate or hydroxyethyl acrylate.
2. The polymer of claim 1, wherein the unsaturated tertiary amine monomer comprises one or more of N, N-diethylallylamine, N-dimethylallylamine, dimethylaminoethyl acrylate.
3. The polymer of claim 1, wherein the epoxy group-containing monomer comprises glycidyl methacrylate or allyl glycidyl ether.
4. The antimicrobial polymer of claim 1, wherein the polymer is a polymer of formula (I),
wherein m is 1-1000, n is 1-1000, and q is 1-1000;
R1is-H, -CH3Or CH2CH3；R2is-H, -CH3Or CH2CH3；R3Is- (CH)2)p-, or-COO- (CH)2)k-, where p is any one integer from 1 to 18, k is any one integer from 0 to 18; r4Butyl, isooctyl, ethyl, hydroxyethyl; r5is-H; r6Is composed of
or-CH2-；R7is-H, or-CH3；R8is-CH2-, or-CH2CH2-；R9Is- (CH)2)t-, where t is a positive integer greater than or equal to 2;
X-is-COO-，-SO3 -。
5. An antimicrobial agent comprising the antimicrobial polymer of any one of claims 1 to 4.
6. A method of antimicrobial finishing of a fabric, the method comprising:
(1) preparing the antibacterial polymer of any one of claims 1 to 4 into an antibacterial finishing liquid according to a solid content of 1 to 25 percent;
(2) and soaking the fabric in the antibacterial finishing liquid, performing fabric rolling treatment, and baking to obtain the antibacterial fabric.
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| CN103524652B (en) * | 2013-09-30 | 2016-02-03 | 江南大学 | A kind of halogen amine polymer antiseptic-germicide containing quaternary ammonium salt group and its preparation method and application |
| CN107383283A (en) * | 2017-08-23 | 2017-11-24 | 广州科迩博新材料科技有限公司 | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application |
| CN108219065B (en) * | 2017-12-29 | 2019-06-07 | 江南大学 | A kind of betaine type antibacterial finishing agent and preparation method thereof |
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