Grafting type antibacterial and deodorizing function integrated fabric and preparation method thereof

Abstract

The invention discloses a grafted antibacterial and deodorant function integrated fabric and a preparation method thereof.The preparation method comprises the steps that guanidine hydrochloride and hexamethylenamine are dissolved in N, N-dimethylformamide to obtain a clear solution, the clear solution reacts with polyethylene glycol to obtain polyhexamethyleneguanidine hydrochloride; the preparation method comprises the following steps: heating an absolute ethyl alcohol solution of polyhexamethylene guanidine hydrochloride and epoxypropane, and then adding triethylamine to obtain a PHMG-based antibacterial agent; the preparation method comprises the following steps: adding a PHMG-based antibacterial agent into an aqueous solution of an organic acid deodorant at 60-70 DEG C, uniformly mixing to obtain a mixed solution, adding a catalyst into the mixed solution, and adjusting the pH value to 5-6 to obtain an antibacterial and deodorizing function integrated mixed solution; and dipping the desized fabric in a solvent containing the antibacterial and deodorizing integrated mixed solution, drying, and carrying out heat treatment. According to the invention, a stable combination effect can be achieved between functional components and the fabric, and long-acting antibacterial, deodorizing and washing-resistant properties can be achieved at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a grafted antibacterial and deodorizing functional integrated fabric and a preparation method thereof. Background Art

[0002] Fabrics without antimicrobial finishing are prone to adsorb and breed bacteria due to their hygroscopic properties. Bacteria, as a microorganism, are the root cause of many diseases, which increases the risk of infection and disease transmission, and in severe cases can endanger the life and health of users. Therefore, it is particularly important to give fabrics antimicrobial properties to effectively reduce the harm of bacteria to the human body.

[0003] In addition, when textiles are attached by bacteria, odor molecules in daily life will also be constantly adsorbed on the surface of the fabric, such as kitchen fumes and the four major odors in life. These odors adhere to clothing, not only affecting people's comfort when wearing, but also harming human health to a certain extent. Therefore, while performing antibacterial finishing on fabrics, deodorizing finishing is also particularly necessary.

[0004] At present, the antibacterial and deodorizing textiles are prone to lose their antibacterial and deodorizing effects due to the weak adhesion of the antibacterial and deodorizing agents during washing or use. In order to enhance the binding force between the antibacterial and deodorizing agents and the fibers and improve the durability and antibacterial and deodorizing persistence of the antibacterial and deodorizing fabrics, it is necessary to develop a new method for preparing grafted antibacterial and deodorizing functional integrated fabrics. Summary of the invention

[0005] In order to solve the technical problem of poor antibacterial and deodorizing effects of antibacterial and deodorizing textiles in the prior art, the purpose of the present invention is to provide a grafted antibacterial and deodorizing functional integrated fabric and a preparation method. The integrated functional fabric has a good deodorizing effect, realizes the development and application of antibacterial and deodorizing protective fabrics, and meets the demand for antibacterial and deodorizing protective textiles in humid environments.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows: A method for preparing a grafted antibacterial and deodorizing functional integrated fabric comprises the following steps: dissolving guanidine hydrochloride and hexamethyleneamine in N,N-dimethylformamide to obtain a clear solution, and reacting the clear solution with polyethylene glycol to obtain polyhexamethyleneguanidine hydrochloride; The anhydrous ethanol solution of polyhexamethyleneguanidine hydrochloride and propylene oxide are heated and triethylamine is added to obtain a PHMG-based antibacterial agent; In 60-70 oC, adding a PHMG-based antibacterial agent to an aqueous solution of an organic acid deodorant, mixing uniformly to obtain a mixed solution, adding a catalyst to the mixed solution, adjusting the pH value to 5-6, mixing uniformly to obtain an antibacterial and deodorizing function integrated mixed solution; The desizing fabric is immersed in a solvent containing a mixed solution with integrated antibacterial and deodorizing functions, dried and then heat-treated to obtain a grafted antibacterial and deodorizing functional integrated fabric.

[0007] Furthermore, the mass ratio of guanidine hydrochloride to hexamethyleneamine is 1:1, the total mass fraction of guanidine hydrochloride and hexamethyleneamine in the clear solution is 15-30wt%, and the amount of polyethylene glycol used is 0.5-1% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0008] Further, the reaction temperature for preparing polyhexamethyleneguanidine hydrochloride is 120 o C, time is 3 h.

[0009] Further, the mass fraction of polyhexamethyleneguanidine hydrochloride in the anhydrous ethanol solution of polyhexamethyleneguanidine hydrochloride is 5-10wt%; The molar ratio of polyhexamethyleneguanidine hydrochloride to propylene oxide is 1:1.2; The concentration of triethylamine is 0.1 mol / L, and the mass ratio of triethylamine to polyhexamethyleneguanidine hydrochloride is 1:40; the heating temperature is 40-45 o C.

[0010] Furthermore, the organic acid deodorant is one of citric acid, tartaric acid and malic acid.

[0011] Furthermore, the mass concentration of the organic acid deodorant aqueous solution is 10-15%, and the total mass fraction of the PHMG-based antibacterial agent and the organic acid deodorant in the mixed solution is 0.5-2.5wt%.

[0012] Furthermore, the catalyst is one of sodium phosphate and sodium dihydrogen phosphate, and the amount of the catalyst used is 3-5% of the mass of the organic acid deodorant.

[0013] Further, the mass ratio of the PHMG-based antimicrobial agent to the organic acid deodorant is 5:1, 2:1, 1:1, 1:2 or 1:5; The heat treatment temperature is 150-170 o C, time is 10-20 min; The fabric is a cotton fabric, a cellulose-based fabric, or a fabric in which the mass ratio of the cellulose-based fabric in the fabric is greater than 20%.

[0014] Further, the raw material of the cellulose-based fabric is any one of cotton, viscose, modal, tencel, cupro and acetate; The solvent is one or a combination of deionized water, DMF and ethanol.

[0015] The invention discloses a grafted fabric with integrated antibacterial and deodorizing functions.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses PO modified PHMG to prepare a new polymer-based antibacterial agent; then an organic acid deodorant is mixed with PHMG-PO to prepare an antibacterial deodorant mixture; finally, the antibacterial deodorant mixture is grafted onto the surface of the fabric by a chemical grafting method to prepare an antibacterial deodorant fabric. Compared with the prior art, the present invention achieves a good combination between the antibacterial deodorant functional components and the fabric, solves the problem of easy dissolution of the traditional antibacterial deodorant on the fabric surface, has a broad-spectrum antibacterial property and washing resistance, and achieves a long-lasting antibacterial and deodorant effect; the present invention uses environmentally friendly organic acid deodorants and modified PHMG-based antibacterial agents, avoids the use of toxic and harmful substances, and conforms to the development trend of green environmental protection; the preparation process of the present invention is carried out under mild reaction conditions, reduces energy consumption and avoids damage to the fabric by high temperature, and improves production efficiency and market adaptability of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is the chemical reaction formula for synthesizing PHMG of the present invention; Figure 2 is the chemical reaction formula of propylene oxide modified PHMG; Figure 3 The chemical reaction formula contains the reaction between citric acid and PHMG-PO and the hydroxyl groups on the surface of cotton fabric; Figure 4 The chemical reaction formula contains the reaction between tartaric acid and PHMG-PO and the hydroxyl groups on the surface of cotton fabric; Figure 5 It is the chemical reaction formula of the reaction between malic acid and PHMG-PO and the hydroxyl groups on the surface of cotton fabric. Specific embodiments In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly and comprehensively understood.

[0019] The preparation method of the grafted antibacterial and deodorizing functional integrated fabric of the present invention breaks through the synthesis of highly efficient, durable, low-toxic and comfortable antibacterial and deodorizing finishing agents, and the green and environmentally friendly reactive processing technology of fabrics, and solves the technical bottleneck of the easy loss of antibacterial and deodorizing agents in traditional antibacterial and deodorizing fabrics, which greatly reduces the antibacterial and deodorizing performance, thereby realizing the development and application of a series of antibacterial and deodorizing protective fabrics to meet the demand for antibacterial and deodorizing protective textiles in humid environments.

[0020] The method for preparing a grafted antibacterial and deodorizing integrated fabric of the present invention comprises the following steps: firstly, chemically modifying polyhexamethyleneguanidine hydrochloride (PHMG) with propylene oxide (PO) to prepare a PHMG-based antibacterial agent (PHMG-PO) with antibacterial function; secondly, uniformly mixing PHMG-PO with an organic acid deodorant, and combining the above-mentioned components with antibacterial and deodorizing functions onto the fabric surface by a chemical grafting method, so as to prepare a fabric with antibacterial and deodorizing integrated function. The method specifically comprises the following steps: 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF) to obtain a clear solution, wherein the total mass fraction of the above solutes (guanidine hydrochloride and hexamethyleneamine) is 15-30wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) as a precipitate.

[0021] The usage amount of the polyethylene glycol catalyst is 0.5-1% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0022] The degree of polymerization of polyhexamethyleneguanidine hydrochloride is greater than 1,000.

[0023] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of solute PHMG is 5-10wt%), then slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0024] The reaction mechanism in step 1) is that the epoxy group opens the ring to form new hydroxyl and ether bonds, which react with the amino group (-NH 2 ) or guanidinyl (-C(NH)-NH 2 ) undergo nucleophilic reaction and covalent bonding to form a stable modified polymer chain.

[0025] The key to the reaction process in step 1) is to control the reaction conditions to avoid all epoxy groups from reacting with the amine groups of PHMG by adjusting the reactant ratio, reaction time, temperature and other conditions.

[0026] 2) Dissolve the organic acid deodorant in deionized water to obtain a solution with a mass fraction of 10-15% (w / v), and then heat the solution to 60 o C and stir evenly; then add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add the catalyst, adjust the pH of the solution to 5-6, continue to stir for 5-10 min, and mix the solution completely to obtain an integrated mixed solution with antibacterial and deodorizing functions, and the total mass fraction of the solute (the sum of PHMG-PO and organic acid deodorant) is 0.5-2.5wt%.

[0027] Among them, the organic acid deodorant is one of citric acid, tartaric acid and malic acid.

[0028] The catalyst is one of sodium phosphate and sodium dihydrogen phosphate, and the amount of the catalyst used is 3-5% of the mass of the organic acid deodorant, which accelerates the esterification reaction between the carboxyl group and the hydroxyl group on the fabric.

[0029] The ratio of antibacterial agent to deodorant is 1-5:1-5, preferably 5:1, 2:1, 1:1, 1:2, 1:5.

[0030] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in a solvent containing the antibacterial and deodorizing integrated mixed solution prepared in step 2), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric is placed in an oven at 150-170 o The antibacterial deodorant is heat treated at 400 °C for 10-20 min to fully react with the fabric to form a strong covalent bond, thereby preparing a grafted antibacterial deodorant functional integrated fabric. The grafting rate of the antibacterial agent on the textile is 4-21.5%.

[0031] The fabric is a cotton fabric, a cellulose-based fabric, or a fabric in which the mass ratio of the cellulose-based fabric in the fabric is greater than 20%.

[0032] Cellulose-based fabrics are made from any of cotton, viscose, modal, tencel, cupro and acetate The solvent may be one or a combination of deionized water, DMF and ethanol.

[0033] The grafting reaction between the antibacterial and deodorizing mixture and the fabric in step 3) occurs through a reaction between the hydroxyl and carboxyl groups on the fabric polymer chain. The organic acid deodorant acts as a bridging molecule to connect the cotton fiber and PHMG-PO together to achieve a stable antibacterial and deodorizing effect. Its carboxyl group (-COOH) undergoes an esterification reaction with the hydroxyl group on the cotton fiber to form an ester bond (-CO-O-); at the same time, its hydroxyl group is covalently bonded with the epoxy group to complete the grafting.

[0034] The step 3) of grafting the antibacterial and deodorizing functional integrated mixed solution with the fabric is a reaction between the hydroxyl and carboxyl groups on the fabric polymer chain. The organic acid deodorant acts as a bridging molecule to connect the cotton fiber and the PHMG-based antibacterial agent together to achieve a stable antibacterial and deodorizing effect. Its carboxyl group (-COOH) undergoes an esterification reaction with the hydroxyl group on the cotton fiber to form an ester bond (-CO-O-); at the same time, its hydroxyl group is covalently bonded with the epoxy group to complete the grafting.

[0035] The following are specific embodiments.

[0036] Example 1 1) See Figure 1 , guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 were dissolved in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes (guanidine hydrochloride and hexamethyleneamine) was 20wt%; then, the above clear solution was poured into a reactor, and a certain concentration of polyethylene glycol was added, and the temperature was raised to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0037] See also Figure 2 , PHMG was uniformly dissolved in anhydrous ethanol (the mass fraction of solute PHMG was 7wt%), propylene oxide was slowly added dropwise (the molar ratio of PHMG to propylene oxide was 1:1.2), and heated to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0038] 2) See Figure 3 , dissolve citric acid in deionized water to a mass fraction of 10% (w / v), and heat to 60 oC, stirring evenly; secondly, adding the PHMG-PO prepared in step 1), and continuing to stir evenly; finally, adding sodium phosphate, adjusting the pH of the solution to 6, and continuing to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions.

[0039] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0040] The mass ratio of the antibacterial agent to citric acid in the antibacterial deodorant in step 2) is 5:1.

[0041] Example 2 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes is 20wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0042] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, and triethylamine solution (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction. After the reaction was completed, an appropriate amount of hydrochloric acid was added for neutralization, washing, and filtering to obtain a PHMG-based antibacterial agent PHMG-PO.

[0043] 2) See Figure 4 , dissolve tartaric acid in deionized water to a mass fraction of 10% (w / v), and heat to 60 o C, stirring evenly; secondly, adding the PHMG-PO prepared in step 1), and continuing to stir evenly; finally, adding sodium dihydrogen phosphate, adjusting the pH of the solution to 6, and continuing to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions.

[0044] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0045] The mass ratio of the antibacterial agent to tartaric acid in the antibacterial deodorant in step 2) is 5:1.

[0046] Example 3 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes is 20wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0047] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0048] 2) See Figure 5 , dissolve malic acid in deionized water to a mass fraction of 10% (w / v), and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add disodium hydrogen phosphate to adjust the pH of the solution to 6, and continue to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions.

[0049] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 oC oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0050] The mass ratio of the antibacterial agent to malic acid in the antibacterial deodorant in step 2) is 5:1.

[0051] Example 4 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes is 20wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0052] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0053] 2) Dissolve citric acid in deionized water to a mass fraction of 10% (w / v) and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium phosphate to adjust the pH of the solution to 6, and continue to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions (the preparation mass ratio is PHMG-based antibacterial agent: citric acid = 2:1).

[0054] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0055] Example 5 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes is 20wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0056] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0057] 2) Dissolve citric acid in deionized water to a mass fraction of 10% (w / v) and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium phosphate to adjust the pH of the solution to 6, and continue to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions (the preparation mass ratio is antibacterial agent: citric acid = 1:1).

[0058] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0059] Example 6 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes is 20wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 oC and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0060] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0061] 2) Dissolve citric acid in deionized water to a mass fraction of 10% (w / v) and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium phosphate to adjust the pH of the solution to 6, and continue to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions (the preparation mass ratio is antibacterial agent: citric acid = 1:2).

[0062] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0063] Example 7 Guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 were dissolved in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes was 20wt%; then, the above clear solution was poured into a reactor, and a certain concentration of polyethylene glycol was added, and the temperature was raised to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.8% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0064] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of the solute is 7wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 oC and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0065] 2) Dissolve citric acid in deionized water to a mass fraction of 10% (w / v) and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium phosphate to adjust the pH of the solution to 6, and continue to stir for 10 min to completely mix the solution to obtain an integrated mixed solution with antibacterial and deodorizing functions (the preparation mass ratio is antibacterial agent: citric acid = 1:5).

[0066] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2 wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 150 o C for 20 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0067] Example 8 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes (guanidine hydrochloride and hexamethyleneamine) is 15wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.5% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0068] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of solute PHMG is 5wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 40 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0069] 2) Dissolve tartaric acid in deionized water to a mass fraction of 15% (w / v) and heat to 70o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium phosphate to adjust the pH of the solution to 6, continue to stir for 5 minutes, and mix the solution completely to obtain an integrated antibacterial and deodorizing mixed solution. The mass ratio of the antibacterial agent to citric acid in the antibacterial deodorant is 5:1.

[0070] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 0.5wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 170 o C for 10 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0071] Example 9 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes (guanidine hydrochloride and hexamethyleneamine) is 30wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 1% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0072] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of solute PHMG is 8wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 42 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0073] 2) Dissolve malic acid in deionized water at a mass fraction of 12% (w / v) and heat to 65 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium dihydrogen phosphate to adjust the pH of the solution to 5, continue to stir for 8 minutes, and mix the solution completely to obtain an integrated antibacterial and deodorizing mixed solution. The mass ratio of the antibacterial agent to citric acid in the antibacterial deodorant is 1:1.

[0074] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 1.5wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 160 o C for 15 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0075] Example 10 1) Dissolve guanidine hydrochloride and hexamethyleneamine in a mass ratio of 1:1 in N,N-dimethylformamide (DMF), and the total mass fraction of the above solutes (guanidine hydrochloride and hexamethyleneamine) is 25wt%; then, pour the above clear solution into a reactor, add a certain concentration of polyethylene glycol, and heat to 120 o C and reacted for 3 h to obtain polyhexamethyleneguanidine hydrochloride (PHMG) by precipitation. The amount of polyethylene glycol used was 0.7% of the total mass of guanidine hydrochloride and hexamethylenediamine.

[0076] Dissolve PHMG evenly in anhydrous ethanol (the mass fraction of solute PHMG is 10wt%), slowly add propylene oxide (the molar ratio of PHMG to propylene oxide is 1:1.2), and heat to 45 o C and slowly stirred, triethylamine (molar concentration of 0.1 mol / L, wherein the mass ratio of triethylamine to PHMG is 1:40) was added during the reaction, and after the reaction was completed, appropriate amount of hydrochloric acid was added for neutralization, washing and filtering to obtain the PHMG-based antibacterial agent PHMG-PO.

[0077] 2) Dissolve citric acid in deionized water to a mass fraction of 13% (w / v) and heat to 60 o C, stir evenly; secondly, add the PHMG-PO prepared in step 1) and continue to stir evenly; finally, add sodium dihydrogen phosphate to adjust the pH of the solution to 5, continue to stir for 7 minutes, and mix the solution completely to obtain an integrated antibacterial and deodorizing mixed solution. The mass ratio of the antibacterial agent to citric acid in the antibacterial deodorant is 1:2.

[0078] 3) Desizing a certain mass of fabric to ensure surface cleanliness and improve reaction effect; then immerse the fabric in the antibacterial and deodorizing integrated mixed solution prepared in step 2) (the total mass fraction of the solute is 2.5wt%), take out the fabric after immersion for 1 hour, and place it at 40 o C oven to remove excess solution; then, the dried fabric was placed in an oven at 170o C for 15 min to allow the antibacterial deodorant to fully react with the fabric to form a strong covalent bond, thus preparing a grafted antibacterial and deodorizing functional integrated fabric.

[0079] The present invention conducted antibacterial and deodorizing tests on the antibacterial and deodorizing fabrics described in the above Examples 1, 4-7 and the pure cotton fabric without grafting, that is, the antibacterial fabrics were tested for their inhibitory and killing effects on Staphylococcus aureus, Escherichia coli, and Candida albicans, as well as their antifungal activity on Trichophyton rubrum, and the results were shown in Table 1. The deodorizing rates of the sample fabrics on ammonia, isovaleric acid, and acetic acid were tested, and the results were shown in Table 2. (The antibacterial and deodorizing fabrics of Examples 1 and Examples 4-7 are numbered 1, 2, 3, 4, and 5, respectively; the cotton fabric is numbered 6) Table 1 Antibacterial properties of antibacterial deodorizing fabrics of Example 1 and Examples 4-7

[0080] Table 2 Deodorization rate of ammonia, isovaleric acid and acetic acid

[0081] From the test results of Table 1 and Table 2, it can be seen that the inhibitory and killing effect of the original fabric obtained by No. 6 on pathogens and the deodorization rate are basically 0, indicating that the original fabric generally does not have an antibacterial and deodorizing effect. Therefore, it is necessary to treat the original fabric. The present invention mixes and grafts the antibacterial and deodorizing agent on the fabric, so that the textile has a lasting and significant broad-spectrum antibacterial, sterilizing and deodorizing effect. In addition, in the grafted antibacterial and deodorizing functional integrated fabric prepared by the present invention, the organic deodorant acts as a bridging molecule to connect the fabric surface and the antibacterial functional group molecule together. After multiple washings with water, the grafted antibacterial and deodorizing functional integrated fabric provided by the present invention still has an excellent antibacterial and deodorizing effect.

[0082] The above description is only for the best embodiment of the present invention, but it should not be understood as limiting the claims. The present invention is not limited to the above embodiments, and its specific structure is allowed to be changed. However, all changes made within the protection scope of the independent claims of the present invention are within the protection scope of the present invention.

[0083] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

Claims

1. A method for preparing a grafted antibacterial and deodorizing functional integrated fabric, characterized in that: The steps include: dissolving guanidine hydrochloride and hexamethyleneamine in N,N-dimethylformamide to obtain a clear solution, and reacting the clear solution with polyethylene glycol to obtain polyhexamethyleneguanidine hydrochloride; The anhydrous ethanol solution of polyhexamethyleneguanidine hydrochloride and propylene oxide are heated and triethylamine is added to obtain a PHMG-based antibacterial agent; In 60-70 o C, adding a PHMG-based antibacterial agent to an aqueous solution of an organic acid deodorant, mixing uniformly to obtain a mixed solution, adding a catalyst to the mixed solution, adjusting the pH value to 5-6, mixing uniformly to obtain an antibacterial and deodorizing function integrated mixed solution; The desizing fabric is immersed in a solvent containing a mixed solution with integrated antibacterial and deodorizing functions, dried and then heat-treated to obtain a grafted antibacterial and deodorizing functional integrated fabric.

2. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The mass ratio of guanidine hydrochloride to hexamethyleneamine is 1:1, the total mass fraction of guanidine hydrochloride and hexamethyleneamine in the clear solution is 15-30wt%, and the amount of polyethylene glycol used is 0.5-1% of the total mass of guanidine hydrochloride and hexamethylenediamine.

3. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The reaction temperature for preparing polyhexamethyleneguanidine hydrochloride is 120 o C, time is 3 h.

4. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The mass fraction of polyhexamethyleneguanidine hydrochloride in the anhydrous ethanol solution of polyhexamethyleneguanidine hydrochloride is 5-10wt%; The molar ratio of polyhexamethyleneguanidine hydrochloride to propylene oxide is 1:1.2; The concentration of triethylamine is 0.1 mol / L, and the mass ratio of triethylamine to polyhexamethyleneguanidine hydrochloride is 1:40; the heating temperature is 40-45 o C.

5. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The organic acid deodorant is one of citric acid, tartaric acid and malic acid.

6. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The mass concentration of the organic acid deodorant aqueous solution is 10-15%, and the total mass fraction of the PHMG-based antibacterial agent and the organic acid deodorant in the mixed solution is 0.5-2.5wt%.

7. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The catalyst is one of sodium phosphate and sodium dihydrogen phosphate, and the amount of the catalyst used is 3-5% of the mass of the organic acid deodorant.

8. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 1, characterized in that: The mass ratio of PHMG-based antimicrobial agent to organic acid deodorant is 5:1, 2:1, 1:1, 1:2 or 1:5; The heat treatment temperature is 150-170 o C, time is 10-20 min; The fabric is a cotton fabric, a cellulose-based fabric, or a fabric in which the mass ratio of the cellulose-based fabric in the fabric is greater than 20%.

9. The method for preparing the grafted antibacterial and deodorizing functional integrated fabric according to claim 8, characterized in that: The raw material of the cellulose-based fabric is any one of cotton, viscose, modal, tencel, cupro and acetate; The solvent is one or a combination of deionized water, DMF and ethanol.

10. A grafted antibacterial and deodorizing functional integrated fabric prepared according to the method according to any one of claims 1 to 9.

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