Disclosure of Invention
The invention aims to solve the technical problems of providing an antibacterial polymer emulsion, antibacterial anti-bacterial adhesion cellulose-based fibers and a fabric, overcoming the defects that the existing fabric lacks the function of preventing bacterial adhesion and cannot be industrially produced, and the antibacterial polymerizable monomer of the emulsion is a guanidine salt antibacterial agent, is nontoxic and environment-friendly and has high-efficiency antibacterial effect; the antibacterial polymer emulsion contains zwitterionic components, so that bacterial adhesion can be effectively prevented, in addition, as the silane coupling agent is added to finish the fabric, the antibacterial emulsion coating and the fiber or the fabric are combined through covalent bonds, compared with the common antibacterial finishing, the antibacterial and antibacterial adhesion preventing effect is more durable, and the antibacterial and antibacterial adhesion preventing cellulose-based fiber and the fabric are obtained by adopting a one-dip one-roll process finishing.
The invention relates to an antibacterial polymer emulsion which is prepared by copolymerizing the following raw materials in parts by weight: 0.5-2 parts of antibacterial monomer, 0.5-2 parts of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate, 0.05-0.5 part of double-bond silane coupling agent, 0-0.05 part of surfactant, 0.02-0.1 part of initiator and 100 parts of solvent.
The raw material components by weight portion are as follows: 0.5-2 parts of antibacterial monomer, 1-2 parts of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate, 0.1-0.5 part of double-bond silane coupling agent, 0-0.05 part of surfactant, 0.07-0.1 part of initiator and 150 parts of solvent.
Preferably, the addition ratio of the acid anhydride modified poly-guanidine hexamethylene hydrochloride and the 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate component in the preparation process of the antibacterial polymer emulsion is 1:1-1:5, and the concentration of the mixture of the two accounts for 1-5% of the total mass of the antibacterial emulsion. The antibacterial monomer is anhydride modified poly hexamethylene guanidine hydrochloride.
The antibacterial monomer is methacrylic acid modified polyhexamethylene guanidine hydrochloride, acrylic acid modified polyhexamethylene guanidine hydrochloride and maleic acid modified polyhexamethylene guanidine hydrochloride.
The acid anhydride modified polyhexamethylene guanidine hydrochloride is prepared by the following method: dissolving polyhexamethylene guanidine hydrochloride in a solvent, adding triethylamine, dropwise adding free radical polymerizable anhydride, reacting for 12-24h at the dark normal temperature, purifying and drying; wherein the proportion of the poly hexamethylene guanidine hydrochloride, the solvent, the triethylamine and the free radical polymerization anhydride is 5-10g, 20-100mL, 2-4mL and 3-6 mL.
The solvent is dimethyl sulfoxide; the free radical polymerizable anhydride is one of methacrylic anhydride, acrylic anhydride and maleic anhydride.
The purification is dichloromethane purification; the drying is drying in an oven at normal temperature.
The silane coupling agent with double bonds is one or more of gamma-methacryloxypropyltrimethylsilane, vinyl tri (beta-methoxyethoxy) silane and vinyl trioxyethylsilane; the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and tween-80; the initiator is ammonium persulfate or potassium persulfate; the solvent is water.
Preferably, the surfactant accounts for 0.1-0.5 per mill of the total mass of the antibacterial emulsion.
The preparation method of the antibacterial polymer emulsion comprises the following steps:
adding an antibacterial monomer, 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, a double-bond silane coupling agent and a surfactant into a solvent, adding an initiator, initiating a free radical polymerization reaction at 40-80 ℃, and reacting for 2-8 h.
Preferably, the reaction is carried out at 60 ℃ for 2-8 h.
The antibacterial cellulose-based fibers and the fabric are prepared by a one-dip one-roll process, and the cellulose-based fibers or the fabric are put into the antibacterial polymer emulsion for finishing.
The fiber or the fabric is formed by blending one or more of cotton, viscose, modal, tencel and the like.
The one-dipping one-rolling process comprises the following specific steps: according to the proportion of 5-100g of the cellulose base material fabric to 100-10000mL of the antibacterial polymer emulsion, the cellulose base material fabric is placed in the antibacterial polymer emulsion for soaking for about 1-2min, the mangle rolling rate is 70% -90%, and the cellulose base material fabric is dried at 110 ℃ with the bath ratio of 1: 20.
The invention relates to an application of the antibacterial cellulose-based fiber and the fabric.
Advantageous effects
(1) The polymer antibacterial emulsion is prepared from the organic guanidine salt antibacterial monomer, 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate and a double-bond silane coupling agent, and has the advantages of good antibacterial effect, lasting effect, washing resistance and wearing resistance;
(2) the fabric prepared by the invention has the antibacterial function and also has the function of preventing bacteria from adhering, and in addition, the fabric prepared by the invention has good hygroscopicity due to the existence of the zwitterion 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, so that the comfort of the fabric can be enhanced to a certain degree;
(3) the finishing method of the antibacterial anti-bacterial adhesion fiber or fabric has the advantages of simple preparation process, easy operation, low energy consumption and easy industrial production.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The specific implementation method of the anti-bacterial adhesion experiment in the embodiment is as follows: performing activation culture on Staphylococcus aureus according to the method specified in GBT 20944.1-2007, taking a pure cotton untreated fabric and an antibacterial and antibacterial adhesion-preventing cotton fabric as test samples, and putting the test samples into bacterial liquid (10)7CFU/mL) for 30min, taking out the test sample, naturally drying, treating the test sample with 2.5% paraformaldehyde PBS solution for 10min, dehydrating the test sample with 10%, 20%, 50%, 70%, 100% ethanol aqueous solution, drying, and testing with a scanning electron microscope.
In the examples, antibacterial experiments are carried out according to the method of GBT 20944.3-2007 to carry out quantitative tests of bacteriostasis rate. The antibacterial performance test of the antibacterial fabric after washing is carried out according to the FZ/T73023 and 2006 standard.
Example 1
(1) Adding 5g of polyhexamethylene guanidine hydrochloride into 20mL of dimethyl sulfoxide, fully stirring and dissolving, adding 3mL of triethylamine, dropwise adding 4mL of methacrylic anhydride, reacting for 24 hours in a dark place, precipitating the mixture after reaction by using dichloromethane, and drying in a vacuum drying oven to obtain the antibacterial anhydride modified polyhexamethylene guanidine hydrochloride monomer.
(2) 0.5g of anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer, 1g of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, 0.1g of gamma-methacryloyloxypropyl trimethyl silane and 0.02g of surfactant sodium dodecyl benzene sulfonate are added into 100mL of deionized water, 70mg of ammonium persulfate is added, the mixture reacts for 4 hours at the temperature of 60 ℃, and the reacted polymer is rapidly cooled to room temperature to prepare the antibacterial polymer emulsion.
(3) And (3) putting 10g of pure cotton fabric into 200mL of antibacterial emulsion, treating for 2min by adopting a one-dip-one-rolling process, taking out the fabric, and quickly drying the fabric at 110 ℃ to prepare the antibacterial anti-adhesion cotton fabric.
The preparation of the anhydride modified poly-guanidine-hexamethylenehydrochloride with antibacterial function is shown in figure 1, methacrylic anhydride can react with amino at the tail end of the poly-guanidine-hexamethylenehydrochloride, and an antibacterial polymerizable monomer with a carbon-carbon double bond functional group can be synthesized.
Method for preparing anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer1The H-NMR spectrum is shown in FIG. 2, and the data are as follows: δ (H, integral value) 5.84(a1, 1); 5.72(a2, 0.97); 1.81(b, 2.12); 2.56(c, 1.96); 1.44(d, 18.55); 1.42(e, 18.25); 2.96(f, 16.60);1H-NMR test results show that the carbon-carbon double bond is successfully inserted into the polyhexamethylene guanidine hydrochloride.
The bacteria anti-adhesion effect test is shown in fig. 3, and the adhesion effect is as follows: a large amount of bacteria can adhere to the surface of the pure cotton fabric when the pure cotton fabric is not treated, but the bacterial adhesion effect is obviously improved after the cotton fabric is finished by the antibacterial anti-adhesion emulsion.
The antibacterial test is shown in figure 4, and the bacteriostasis rate can reach 98 percent (staphylococcus aureus) and 99 percent (escherichia coli).
Example 2
(1) Adding 5g of polyhexamethylene guanidine hydrochloride into 20mL of dimethyl sulfoxide, fully stirring and dissolving, adding 3mL of triethylamine, dropwise adding 4mL of methacrylic anhydride, reacting for 24 hours in a dark place, precipitating the mixture after reaction by using dichloromethane, and drying in a vacuum drying oven to obtain the antibacterial anhydride modified polyhexamethylene guanidine hydrochloride monomer.
(2) 0.5g of anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer, 1g of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate and 0.1g of vinyl tri (beta-methoxyethoxy) silane are added into 100mL of deionized water, 70mg of ammonium persulfate is added, the mixture reacts for 4 hours at the temperature of 60 ℃, and the polymer after the reaction is rapidly cooled to room temperature to prepare the antibacterial polymer emulsion.
(3) And (3) putting 10g of pure cotton fabric into 200mL of antibacterial emulsion, treating for 2min by adopting a one-dip-one-rolling process, taking out the fabric, and quickly drying the fabric at 110 ℃ to prepare the antibacterial anti-adhesion cotton fabric.
The cotton fabric has good antibacterial effect on escherichia coli and staphylococcus aureus, and the antibacterial rate of the staphylococcus aureus can reach 99%; the antibacterial rate of escherichia coli can reach 98%, and the antibacterial rate of the cotton fabric after being washed for 50 times on staphylococcus aureus and escherichia coli can still reach over 86%.
Example 3
(1) Adding 5g of polyhexamethylene guanidine hydrochloride into 20mL of dimethyl sulfoxide, fully stirring and dissolving, adding 3mL of triethylamine, dropwise adding 4mL of methacrylic anhydride, reacting for 24 hours in a dark place, precipitating the mixture after reaction by using dichloromethane, and drying in a vacuum drying oven to obtain the antibacterial anhydride modified polyhexamethylene guanidine hydrochloride monomer.
(2) 0.5g of anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer, 1g of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, 0.1g of vinyl triethoxysilane and 0.02g of surfactant sodium dodecyl benzene sulfonate are added into 100mL of deionized water, 70mg of ammonium persulfate is added, the mixture reacts for 4 hours at the temperature of 60 ℃, and the polymer after the reaction is rapidly cooled to the room temperature to prepare the antibacterial polymer emulsion.
(3) And (3) putting 10g of viscose fabric into 200mL of antibacterial emulsion, treating for 2min by adopting a one-dip-one-rolling process, taking out the fabric, and quickly drying at 110 ℃ to prepare the antibacterial anti-adhesion viscose fabric.
The result of the bacteriostatic experiment is as follows: the bacteriostasis rate of the golden gluconococcus is 99.2 percent; the colibacillus can reach 97.3%.
Example 4
(1) Adding 5g of polyhexamethylene guanidine hydrochloride into 20mL of dimethyl sulfoxide, fully stirring and dissolving, adding 3mL of triethylamine, dropwise adding 4mL of methacrylic anhydride, reacting for 24 hours in a dark place, precipitating the mixture after reaction by using dichloromethane, and drying in a vacuum drying oven to obtain the antibacterial anhydride modified polyhexamethylene guanidine hydrochloride monomer.
(2) 0.5g of anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer, 1g of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, 0.1g of gamma-methacryloyloxypropyl trimethyl silane and a surfactant Tween-800.02 g are added into 100mL of deionized water, 70mg of ammonium persulfate is added, the mixture reacts for 4 hours at the temperature of 60 ℃, and the reacted polymer is rapidly cooled to room temperature to prepare the antibacterial polymer emulsion.
(3) And (3) putting 10g of pure cotton fabric into 200mL of antibacterial emulsion, treating for 2min by adopting a one-dip-one-rolling process, taking out the fabric, and quickly drying the fabric at 110 ℃ to prepare the antibacterial anti-adhesion cotton fabric.
The result of the bacteriostatic experiment is as follows: the hydrogel has antibacterial effect on escherichia coli and staphylococcus aureus, has certain antibacterial performance, and the antibacterial rate of the staphylococcus aureus can reach 98.4%; the colibacillus can reach 96.3%.
Example 5
(1) Adding 5g of polyhexamethylene guanidine hydrochloride into 20mL of dimethyl sulfoxide, fully stirring and dissolving, adding 3mL of triethylamine, dropwise adding 4mL of acrylic anhydride, reacting for 24 hours in a dark place, precipitating the mixture after reaction by using dichloromethane, and drying in a vacuum drying oven to obtain the antibacterial anhydride modified polyhexamethylene guanidine hydrochloride monomer.
(2) 0.5g of anhydride modified poly hexamethylene guanidine hydrochloride antibacterial monomer, 1g of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, 0.1g of vinyl trioxyethylene silicon and 0.02g of surfactant sodium dodecyl benzene sulfonate are added into 100mL of deionized water, 70mg of ammonium persulfate is added, the mixture reacts for 4 hours at the temperature of 60 ℃, and the polymer after the reaction is rapidly cooled to the room temperature to prepare the antibacterial polymer emulsion.
(3) And (3) putting 10g of pure cotton fabric into 200mL of antibacterial emulsion, treating for 2min by adopting a one-dip-one-rolling process, taking out the fabric, and quickly drying the fabric at 110 ℃ to prepare the antibacterial anti-adhesion cotton fabric.
The antibacterial test result shows that the bacteriostasis rate of the escherichia coli is 97.8 percent, and the bacteriostasis rate of the staphylococcus aureus is 94.5 percent. After washing for 50 times, the bacteriostasis rate of the modified cotton fabric to staphylococcus aureus and escherichia coli can still reach more than 88.5 percent.