Preparation method and application of micro-crosslinking reaction type guanidine durable antibacterial finishing agent

Abstract

The invention discloses a preparation method and application of a micro-crosslinking reaction type guanidine durable antibacterial finishing agent, and relates to the field of high polymer material preparation.The preparation method comprises the steps that S1, aliphatic long-chain alkyl diamine, hexamethylenediamine and guanidine hydrochloride are added into a reaction container, and the mixture is stirred to be uniform; a water-soluble polyguanidine polymer with a linear structure is prepared through melt polycondensation by a gradient heating method, and a polymer aqueous solution is prepared after water is added for dilution; and S2, adjusting the pH value of the polymer aqueous solution to 9-10.5, slowly dropwise adding epichlorohydrin at the temperature of 20-25 DEG C, and carrying out heating reaction after dropwise adding to obtain the micro-crosslinking reaction type guanidine durable antibacterial finishing agent. The micro-crosslinking reaction type guanidine durable antibacterial finishing agent prepared by the preparation method disclosed by the invention has excellent antibacterial effect and washability, the color fastness of dyed fabrics is improved by half level or more while the finishing agent is antibacterial, and the finishing agent is a composite multifunctional antibacterial color-fixing finishing agent and has a relatively good market application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly to a preparation method and application of a micro-crosslinked reactive guanidine-based durable antibacterial finishing agent. Background Art

[0002] With the development of modern textile technology, textiles are increasingly used in medical, sanitary products and public places. The porous structure of textiles is extremely easy to be contaminated with impurities or human secretions, such as sebum and sweat, etc. during production or use, providing very good living conditions for microorganisms, resulting in the growth and reproduction of a large number of microorganisms, making the textiles in contact with the human body become an important medium for the breeding and transmission of various microorganisms, and having an adverse impact on human health. Therefore, the development and research of antibacterial textiles have become an urgent need in the fields of medical protection and health.

[0003] When using organic antibacterial agents for textiles, the following requirements are needed: 1. High antibacterial efficiency, and good antibacterial performance should be possessed at a relatively low concentration; 2. Wide antibacterial spectrum, showing antibacterial activity against a variety of microorganisms, having the function of inhibiting or killing bacteria, and antibacterial finishing agents with different antibacterial spectra can be selected according to the use occasions of textiles; 3. Good stability, its own physical and chemical properties remain relatively stable for a long time under a certain environment, do not react with common textile auxiliaries such as dyes during use, and do not affect the physical properties and appearance of textiles at the same time; 4. High safety, the chemical substances used are harmless to the human body; 5. The application process and equipment operation are simple, and it should meet the requirements of convenient processing, adapting to the processing technology, etc., and have good compatibility and strong binding ability with textiles.

[0004] In recent years, it has been found that non-releasing cationic polymers containing haloamine groups, quaternary ammonium salt groups, quaternary phosphonium salt groups and guanidine groups have good antibacterial properties. They not only have little toxicity to normal eukaryotic cells, but also bacteria will not develop drug resistance to them. The guanidine group-containing cationic antibacterial polymer is similar to the structure of natural antibacterial peptides, has high antibacterial efficiency and excellent biocompatibility. Compared with natural antibacterial polymers, the guanidine group-containing antibacterial polymer has better designability and controllability. Compared with the single hydrogen bond formed by the haloamine group-containing and quaternary ammonium (phosphonium) salt group-containing cationic polymers with the bacterial cell membrane, the guanidine group-containing polymer can more efficiently form a more stable bidentate hydrogen bond with carboxylates, phosphonates and sulfates on the bacterial cell membrane, making it have more efficient antibacterial performance than the haloamine group-containing and quaternary ammonium (phosphonium) salt group-containing cationic polymers. In addition, it has been found that the guanidine group-containing polymer has lower eukaryotic cell toxicity than the amine group-containing polymer. Therefore, the guanidine group-containing polymer has been widely used in fields such as wound dressings, textiles, drug delivery, pesticides and water treatment.

[0005] At present, there are mainly two problems with polyguanidine-based high-molecular organic antibacterial agents for textiles on the market: 1. Poor wash resistance; 2. The synthetic process of the improved technical solution for improving wash resistance is complex and not environmentally friendly, and organic solvents need to be used. The removal and recycling of organic solvents are the biggest constraints restricting its industrial production and product promotion and application. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation method and application of a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent to solve the problems in the background technology.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is: a preparation method of a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent, comprising the following steps: S1, Add aliphatic long-chain alkyl diamine, hexamethylenediamine and guanidine hydrochloride into a reaction vessel, and prepare a water-soluble polyguanidine polymer with a linear structure by melt polycondensation using the gradient heating method. After dilution with water, a polymer aqueous solution is obtained. Among them, the molar ratio of the sum of the molar amounts of the aliphatic long-chain alkyl diamine and hexamethylenediamine to the molar amount of guanidine hydrochloride is (1 - 1.1):1; S2, Adjust the pH value of the polymer aqueous solution to 9 - 10.5, slowly dropwise add epichlorohydrin, the dropping temperature is 20 - 25 °C, and after the dropping is completed, carry out a temperature-raising reaction to obtain a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent. Among them, the molar ratio of the water-soluble polyguanidine polymer to epichlorohydrin is 1:(0.01 - 2.5).

[0008] In the above reaction process, by controlling the reaction pH value and the dosage of epichlorohydrin, a product with the following molecular structural formula can be obtained: , where n is 10 or 12, and m is an integer from 10 to 16. Since an epoxy group is formed at one end of the molecular main chain, it can form a micro-crosslinking effect with the fabric.

[0009] Furthermore, when the dosage of epichlorohydrin is further increased, such as when the molar ratio of the above-mentioned water-soluble polyguanidine polymer to epichlorohydrin is less than 1:2, a product with the following molecular structural formula can be obtained: , where n is 10 or 12, and m is an integer from 10 to 16. The formation process of this product is that an intermediate is formed by connecting one epoxy group to each end of 1 polyguanidine polymer, and a micro-crosslinking effect occurs between the epoxy groups existing in the 2 intermediates to form the above product; the above product forms a longer carbon chain, and the epoxy group located at the end of the above product itself can form a micro-crosslinking effect with the fabric, and the hydroxyl group in the middle can also form a micro-crosslinking effect with the fabric.

[0010] As a further optimization, the molar dosage of the long-chain alkyl diamine accounts for 10-30% of the sum of the molar dosages of the long-chain alkyl diamine and hexamethylenediamine.

[0011] As a further optimization, the long-chain alkyl diamine in S1 includes decanediamine or 1,12-diaminododecane.

[0012] As a further optimization, the steps of the gradient heating method in S1 are as follows: reacting at 120 °C for 2-2.5 h, with a heating gradient of 10 °C, heating every 30 min until the temperature is raised to 160-180 °C, and maintaining the reaction for 2-4 h.

[0013] As a further optimization, the degree of polymerization of the water-soluble poly-monoguanidine polymer in S1 is 10-16, and the preferred degree of polymerization is 15.

[0014] As a further optimization, the method for adjusting the pH value in S2 is: adding hydrochloric acid for adjustment, and the concentration of the hydrochloric acid is 18%.

[0015] As a further optimization, the temperature for the heating reaction in S2 is 50-70 °C, and the reaction time is 0.5-2 h.

[0016] The present invention also provides an application of the micro-crosslinked reaction-type guanidine durable antibacterial finishing agent. The prepared micro-crosslinked reaction-type guanidine durable antibacterial finishing agent is used for antibacterial and color fixation finishing of fabrics. The antibacterial and color fixation finishing process is as follows: padding or impregnating the fabric with an aqueous solution of the micro-crosslinked reaction-type guanidine durable antibacterial finishing agent and then drying it, where the fabric includes cellulose fiber fabrics, protein fiber fabrics, or fabrics blended or interwoven with chemical fibers of any one of the two.

[0017] As a further optimization, the solid content of the aqueous solution of the micro-crosslinked reaction-type guanidine durable antibacterial finishing agent is 20-25%, the concentration is 10-30 g / L, and the drying temperature is 120-180 °C.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. By introducing the long-chain alkyl diamine, the hydrophilic part (guanidine group) and the hydrophobic part (long-chain alkyl group) are alternately arranged on the main chain skeleton of the guanidine polymer, and a high-molecular poly-monoguanidine polymer with amphiphilic characteristics of hydrophilic-hydrophobic alternation is prepared, forming a structure of directional and close arrangement. This kind of directional and close arrangement structure has a strong ability to bind bacteria and better antibacterial effects; 2. By controlling the pH value of the polymerization system, epichlorohydrin is added dropwise to the aqueous solution of polybiguanide polymer to graft and introduce reactive epoxy groups. The epoxy groups can improve the binding ability with the fabric, and by further controlling the amount of epichlorohydrin, the above-mentioned intermediate products can be micro-crosslinked to form hydroxyl groups. The presence of hydroxyl groups, in combination with the epoxy groups, can achieve micro-crosslinking and binding with the fabric at multiple positions on the long-chain structure, with stronger binding ability, effectively improving the wash resistance of the treated fabric; 3. Long-chain alkyl groups are connected between the guanidine double chains. The introduction of hydrophobic long-chain alkyl groups can effectively improve the color fixation performance and wet treatment color fastness of the treated fabric; and the introduction of epoxy groups can, to a certain extent, cause micro-crosslinking of the polybiguanide polymer, improve its film-forming performance, and ensure the stability of film formation by virtue of the binding ability of the epoxy groups (or including hydroxyl groups) with the fabric, further improving the color fastness of the treated fabric; 4. The synthesis process of the present invention is environmentally friendly, does not require organic solvents, and the process is simple and mild. Description of the Drawings

[0019] Appendix Figure 1 It is the thermogravimetric curve and thermogravimetric differential curve of the micro-crosslinked reactive guanidine durable antibacterial finishing agent prepared in Example 4 of the present invention. Detailed Embodiments

[0020] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0021] Example 1: S1, Add 10.02 g of 1,12-diaminododecane, 52.29 g of hexamethylenediamine, and 47.77 g of guanidine hydrochloride into a reaction vessel, heat up to 80 °C, and after the reactants are all melted, gradually heat up to 120 °C and react for 2 h, then increase the temperature at a gradient of 10 °C every 30 min until the temperature reaches 160 °C, and keep the temperature for reaction for 3 h to obtain a water-soluble polybiguanide polymer with a linear structure. After the reaction is completed, cool down to 100 °C and add 110.08 g of deionized water to obtain an aqueous polymer solution; S2, Adjust the pH value of the aqueous polymer solution to 9, slowly add 46.26 g of epichlorohydrin dropwise, the dropping temperature is 20 - 25 °C, and after the dropping is completed, heat up to 60 °C and react for 2 h to obtain a micro-crosslinked reactive guanidine durable antibacterial finishing agent.

[0022] Example 2: S1. Add 18.09 g of decanediamine, 48.81 g of hexanediamine, and 47.77 g of guanidine hydrochloride into a reaction vessel, heat up to 80 °C, and after the reactants are all melted, gradually heat up to 120 °C and react for 2 h. Then, with a temperature increase gradient of 10 °C, increase the temperature every 30 min until it reaches 160 °C, keep the temperature for reaction for 4 h to obtain a water-soluble poly-monoguanidine polymer with a linear structure. After the reaction is completed, cool down to 100 °C and add 114.67 g of deionized water to obtain an aqueous polymer solution; S2. Adjust the pH value of the aqueous polymer solution to 9.5, slowly dropwise add 69.39 g of epichlorohydrin, with the dropping temperature being 20 - 25 °C. After the dropping is completed, heat up to 55 °C and react for 2 h to obtain a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent.

[0023] Example 3: S1. Add 25.85 g of 1,12-diaminododecane, 40.67 g of hexanediamine, and 47.77 g of guanidine hydrochloride into a reaction vessel, heat up to 80 °C, and after the reactants are all melted, gradually heat up to 120 °C and react for 2 h. Then, with a temperature increase gradient of 10 °C, increase the temperature every 30 min until it reaches 160 °C, keep the temperature for reaction for 3 h to obtain a water-soluble poly-monoguanidine polymer with a linear structure. After the reaction is completed, cool down to 100 °C and add 114.29 g of deionized water to obtain an aqueous polymer solution; S2. Adjust the pH value of the aqueous polymer solution to 10, slowly dropwise add 23.13 g of epichlorohydrin, with the dropping temperature being 20 - 25 °C. After the dropping is completed, heat up to 65 °C and react for 2 h to obtain a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent.

[0024] Example 4: S1. Add 20.04 g of 1,12-diaminododecane, 46.48 g of hexanediamine, and 47.77 g of guanidine hydrochloride into a reaction vessel, heat up to 80 °C, and after the reactants are all melted, gradually heat up to 120 °C and react for 2 h. Then, with a temperature increase gradient of 10 °C, increase the temperature every 30 min until it reaches 160 °C, keep the temperature for reaction for 4 h to obtain a water-soluble poly-monoguanidine polymer with a linear structure. After the reaction is completed, cool down to 100 °C and add 114.29 g of deionized water to obtain an aqueous polymer solution; S2. Adjust the pH value of the aqueous polymer solution to 9, slowly dropwise add 97.15 g of epichlorohydrin, with the dropping temperature being 20 - 25 °C. After the dropping is completed, heat up to 65 °C and react for 2 h to obtain a micro-crosslinked reaction-type guanidine durable antibacterial finishing agent.

[0025] Comparative Example 1: S1. Add 61.01 g of hexamethylenediamine and 47.77 g of guanidine hydrochloride into a reaction vessel, heat up to 80 °C, and after the reactants are all melted, gradually heat up to 120 °C and react for 2 h. Then, with a heating gradient of 10 °C, heat up every 30 min until the temperature reaches 160 °C, and keep the temperature for reaction for 4 h to obtain a water-soluble poly-monoguanidine polymer with a linear structure. After the reaction is completed, cool down to 100 °C and add 108.78 g of deionized water to obtain an aqueous polymer solution; S2. Adjust the pH value of the aqueous polymer solution to 10, slowly dropwise add 46.26 g of epichlorohydrin at a dropping temperature of 20 - 25 °C. After the dropping is completed, heat up to 65 °C and react for 2 h to obtain a guanidine-based antibacterial finishing agent.

[0026] Application example: Use the micro-crosslinked reactive guanidine-based durable antibacterial finishing agents prepared in Examples 1 to 4 above, the guanidine-based antibacterial finishing agent prepared in Comparative Example 1, and the commercially available guanidine-based antibacterial agent PHMG-PTG for antibacterial and color fixation finishing of cellulose fiber fabrics, protein fiber fabrics, or any one of them blended or interwoven with chemical fibers. In this application example, a bright red dyed cotton fabric is selected as an example.

[0027] Prepare an antibacterial and color fixation finishing aqueous solution, and its solid content is uniformly applied after being converted based on 25%. The antibacterial and color fixation finishing process for the bright red dyed cotton fabric is as follows: Prepare a working solution with a concentration of 30 g / L from the antibacterial and color fixation finishing aqueous solution, and use the one-dip-one-roll method and dry at 120 - 180 °C.

[0028] Test the antibacterial performance and color fixation performance of the bright red dyed cotton fabric after antibacterial and color fixation finishing. Among them, the antibacterial performance refers to GB / T 20944.3 - 2008 "Textiles - Evaluation of antibacterial properties - Part 3: Oscillation method", and the evaluation is carried out after 50 washes by the washing method of a household twin-tub washing machine in this standard; the color fixation performance refers to GB / T 3920 - 2008 "Textiles - Tests for color fastness - Color fastness to rubbing" and GB / T 3921 - 2008 "Textiles - Tests for color fastness - Color fastness to soaping" for evaluation. The antibacterial performance and color fixation performance of the bright red dyed cotton fabric after antibacterial and color fixation finishing are shown in Table 1 and Table 2 respectively as follows.

[0029] Table 1 Comparison of antibacterial performance after antibacterial and color fixation finishing , Table 2 Comparison of color fixation performance after antibacterial and color fixation finishing .

[0030] As can be seen from Table 1 and Table 2, when the micro-crosslinked reactive guanidine-based durable antibacterial finishing agent prepared by the present invention is used for antibacterial and color fixation finishing of cellulose fiber fabrics, the finished fabrics have excellent antibacterial properties, with a bacteriostatic rate ≥ 99%, and the bacteriostatic rate ≥ 95% after 50 standard washings. They have excellent durability, and at the same time, they can improve the color fastness performance of dyed fabrics by half a grade or more during antibacterial treatment. It is a composite multi-functional antibacterial and color fixation finishing agent with good market application prospects.

[0031] Combined with Figure 1 As shown, especially for the micro-crosslinked reactive guanidine-based durable antibacterial finishing agent prepared in Example 4, due to its ability to form longer long-chain structures and the larger molecular weight possessed by the long-chain structures, it can have a relatively high decomposition temperature (about 375 °C). The long-chain structures and the larger molecular weight can better achieve its color fixation performance. In addition, it can not only be applied to antibacterial and color fixation finishing during the post-finishing process, but also be added as an additive to the spinning solution during the spinning stage. Its relatively high decomposition temperature ensures that it will not decompose at the relatively high temperature during the spinning stage, enabling the raw materials to have better antibacterial effects after spinning.

[0032] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. A method for preparing a micro-crosslinking reactive guanidine durable antibacterial finishing agent, characterized in that: The steps include: S1, adding aliphatic long-chain alkyl diamine, hexamethylenediamine and guanidine hydrochloride into a reaction container, preparing a water-soluble polymonoguanidine polymer having a linear structure by melt polycondensation by a gradient temperature rising method, and preparing a polymer aqueous solution after dilution with water, wherein the ratio of the sum of the molar amounts of the aliphatic long-chain alkyl diamine and hexamethylenediamine to the molar amount of guanidine hydrochloride is (1-1.1):1; S2, adjusting the pH value of the polymer aqueous solution to 9-10.5, slowly adding epichlorohydrin at a temperature of 20-25°C, and heating the reaction after the addition is completed to obtain a slightly cross-linked reactive guanidine durable antibacterial finishing agent, wherein the molar ratio of the water-soluble polymonoguanidine polymer to epichlorohydrin is 1:(0.01-2.5).

2. The method for preparing the micro-crosslinking reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The molar amount of the aliphatic long-chain alkyl diamine accounts for 10-30% of the sum of the molar amounts of the aliphatic long-chain alkyl diamine and hexamethylene diamine.

3. The method for preparing the micro-crosslinking reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The aliphatic long-chain alkyl diamine in S1 is decanediamine or 1,12-diaminododecane.

4. The method for preparing the micro-crosslinking reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The steps of the gradient temperature rise method in S1 are: react at 120°C for 2-2.5h, increase the temperature by 10°C every 30 min until the temperature reaches 160-180°C, and keep the temperature for 2-4h.

5. The method for preparing the micro-crosslinking reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The degree of polymerization of the water-soluble polymonoguanidine polymer in S1 is 10-16.

6. The method for preparing the micro-crosslinked reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The method for adjusting the pH value in S2 is: adding hydrochloric acid for adjustment, and the concentration of the hydrochloric acid is 18%.

7. The method for preparing the micro-crosslinking reactive guanidine durable antibacterial finishing agent according to claim 1, characterized in that: The temperature of the heating reaction in S2 is 50-70°C, and the reaction time is 0.5-2 h.

8. Application of micro-crosslinked reactive guanidine durable antibacterial finishing agent, characterized in that: The micro-cross-linked reactive guanidine durable antibacterial finishing agent prepared by the preparation method of the micro-cross-linked reactive guanidine durable antibacterial finishing agent according to any one of claims 1 to 7 is used for antibacterial color-fixing finishing of fabrics, and the antibacterial color-fixing finishing process is: padding or immersing the fabric in an aqueous solution of the micro-cross-linked reactive guanidine durable antibacterial finishing agent and drying it, wherein the fabric includes cellulose fiber fabric, protein fiber fabric, or a fabric blended or interwoven with chemical fiber.

9. The use of the micro-crosslinked reactive guanidine durable antibacterial finishing agent according to claim 8, characterized in that: The aqueous solution of the micro-crosslinking reactive guanidine durable antibacterial finishing agent has a solid content of 20-25%, a concentration of 10-30 g / L, and a drying temperature of 120-180°C.

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