Multifunctional modifier, multifunctional modifier finishing liquid and preparation method and application thereof

Abstract

The present invention belongs to the technical field of flame retardant modification, and relates to a multifunctional modifier, a multifunctional modifier finishing liquid, and a preparation method and application thereof. The method firstly coats and modifies hexachlorocyclotriphosphazene with polyhexamethylene biguanide hydrochloride to obtain modified cyclotriphosphazene; then, the modified cyclotriphosphazene is subjected to Maillard reaction with glucose under alkaline conditions to prepare a multifunctional modifier finishing liquid, and the multifunctional modifier finishing liquid is purified to obtain a multifunctional modifier; further, the multifunctional modifier finishing liquid is used to impregnate polyamide 6 fabric to obtain a durable flame retardant polyamide 6 fabric. The present invention obtains a multifunctional modifier having multiple functions of flame retardancy, antibacterial, adhesion and water solubility, and the flame retardant and anti-melting properties, antibacterial properties and water washability of the fabric are improved by using the multifunctional modifier finishing liquid.

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardant and antibacterial multifunctional modification, and relates to a multifunctional modifier, a multifunctional modifier finishing liquid, and a preparation method and application thereof. Background Art

[0002] In the field of textiles, the pursuit of high performance of materials has become an industry consensus, and the development of modifiers with multiple excellent properties is the key to achieving this goal. First of all, the safety of textiles is one of the aspects that consumers are most concerned about. Therefore, it is particularly urgent to develop modifiers with excellent flame retardant and anti-melt droplet properties. This modifier can respond quickly when a fire occurs, effectively curb the spread of the fire, and significantly reduce the secondary damage caused by melt droplets, building a solid safety line for the wearer. Secondly, as people's pursuit of healthy life is increasing, antibacterial properties have also become an indispensable part of textiles. Modifiers with antibacterial properties can significantly reduce the growth of pathogens on textiles and reduce the risk of pathogen transmission, thereby effectively protecting the health of the wearer and preventing the spread of diseases. Furthermore, in order to improve the overall performance of textiles, the application of modifiers has become a common practice in the industry. The good adhesion performance of the modifier is the key to whether it can play an effective role. Only by ensuring that the modifier can firmly adhere to the surface of the fabric and is not easy to fall off can it play its improvement role for a long time and improve the quality and service life of the textiles. Finally, we also need to pay attention to the environmental performance of the modifier. Water solubility is another important characteristic of modifiers, which not only simplifies the processing flow and improves production efficiency, but also facilitates subsequent environmental protection treatment. During the processing, water-soluble modifiers can be easily dissolved in water and evenly dispersed, while reducing pollution and damage to the environment.

[0003] In summary, the development of modifiers with excellent flame retardancy and anti-drip properties, antibacterial properties, good adhesion properties and water solubility is an inevitable choice for the pursuit of high-performance material standards in the textile field. Such modifiers will greatly improve the safety, health, durability and environmental protection of textiles, and bring consumers a better, safer and healthier wearing experience.

[0004] However, existing modifiers often find it difficult to simultaneously meet the above requirements.

[0005] Reference 1 (Hexachlorocyclotriphosphazene-modified graphene oxide flame retardant finishing of cotton fabric [J]. Printing and Dyeing, 2016, 42(16): 6-11, 18.) Hexachlorocyclotriphosphazene is combined with graphene oxide, and the hydroxyl content is increased by reacting the epoxy group on the graphene oxide with ethanolamine, and then further grafted with hexachlorocyclotriphosphazene, and finally used for flame retardant finishing of cotton fabric. However, the flame retardant and anti-drip performance of the modifier used is still not ideal. The cotton fabric after flame retardant finishing continues to burn after ignition, leaving only a small amount of residual carbon. At the same time, the adhesion performance of the modifier used is poor, resulting in weak bonding between the modifier and the cotton fabric, and the water washability needs to be improved. In addition, the modifier used does not have antibacterial properties.

[0006] Reference 2 (Preparation and Application of Melamine-Cyclotriphosphazene Flame Retardant [J]. Journal of South China Normal University (Natural Science Edition), 2015, 47(2): 78-83.) used hexahydroxymethylmelamine and hexachlorocyclotriphosphazene to synthesize a water-soluble, alcohol-soluble halogen-free phosphazene flame retardant through nucleophilic substitution and etherification reaction, and tried to use it for flame retardant treatment of medical pure cotton gauze, chemical fiber curtain fabric and other materials. Although the modifier used showed a certain degree of water solubility, the adhesion performance was poor, resulting in insufficient bonding strength with textiles and poor durability of the flame retardant effect. In addition, the modifier used did not have antibacterial properties.

[0007] Reference 3 (Electrostatic self-assembly of polyhexamethylene biguanide hydrochloride on cotton fabric and its antibacterial properties [J]. Journal of Textile Research, 2012, 33(4): 86-90.) polyhexamethylene biguanide hydrochloride (rich in amino and imino groups and has strong antibacterial properties) and sodium polystyrene sulfonate were constructed on the surface of cotton fibers by electrostatic self-assembly to give the fibers antibacterial properties. However, the flame retardant and anti-drip properties of the modifiers used are still not ideal, and the adhesion performance is poor, resulting in insufficient bonding strength with textiles and poor antibacterial durability.

[0008] In summary, the existing modifiers all have certain limitations, and it is necessary to develop a modifier with excellent flame retardancy and anti-drip properties, antibacterial properties, good adhesion properties and water solubility. Summary of the invention

[0009] The purpose of the present invention is to solve the problems existing in the prior art and to provide a multifunctional modifier, a multifunctional modifier finishing liquid and a preparation method and application thereof.

[0010] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] A method for preparing a multifunctional modifier finishing liquid, comprising the following steps:

[0012] (1) Polyhexamethylene biguanide hydrochloride (general structural formula: ) Hexachlorocyclotriphosphazene is coated and modified to obtain modified cyclotriphosphazene. The chain segment of polyhexamethylene biguanide hydrochloride is longer and has more active groups. Its single molecular chain can form multiple covalent bonds with hexachlorocyclotriphosphazene, and the coating efficiency is high;

[0013] (2) preparing a reaction system b containing modified cyclotriphosphazene, solvent b (a mixed solution of tetrahydrofuran and water, wherein the volume proportion of tetrahydrofuran in solvent b is 20-30%), glucose and a pH value > 7 (which can be adjusted by adding sodium hydroxide), and reacting at 75-85°C to obtain a multifunctional modifier finishing liquid.

[0014] The invention firstly adopts polyhexamethylene biguanide hydrochloride to coat and modify hexachlorocyclotriphosphazene to obtain modified cyclotriphosphazene, and then carries out Maillard reaction on the modified cyclotriphosphazene and glucose under alkaline conditions (pH value>7) and high temperature (75-85°C), wherein the polyhexamethylene biguanide hydrochloride is a polymer long-chain compound, is rich in imino groups and amino groups, has a long chain segment, can undergo a nucleophilic substitution reaction with the active chlorine of hexachlorocyclotriphosphazene, forms a uniform coating on the hexachlorocyclotriphosphazene, and makes the surface of the hexachlorocyclotriphosphazene rich in imino groups and amino active groups, and the Maillard product generated by the subsequent reaction with glucose can also form a uniform coating on the hexachlorocyclotriphosphazene.

[0015] As the preferred technical solution:

[0016] The method for preparing a multifunctional modifier finishing liquid as described above, the specific process of step (1) is: after polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, acid binding agent, and solvent a (tetrahydrofuran) are uniformly mixed to obtain a reaction system a, the mixture is reacted at 55-65° C. for 4-5 hours, and post-treated (cooling, filtration, removal of solvent, washing with distilled water and ethanol) to obtain modified cyclotriphosphazene.

[0017] According to the method for preparing a multifunctional modifier finishing liquid, the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1-2:5, the molar ratio of the acid binding agent to hexachlorocyclotriphosphazene is 6-7:1, and the dosage ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:40-50 mL.

[0018] In the method for preparing a multifunctional modifier finishing liquid as described above, in step (2), in the reaction system b, the content of modified cyclotriphosphazene is 40-60 g / L, and the content of glucose is 80-100 g / L; the pH value of the reaction system b is 11-12; and the reaction time is 2-3 h.

[0019] The present invention also provides a multifunctional modifier finishing liquid, which is prepared by the preparation method of a multifunctional modifier finishing liquid as described in any one of the above items.

[0020] The present invention also provides a method for preparing a multifunctional modifier, and the multifunctional modifier can be obtained by purifying the multifunctional modifier finishing liquid as described above.

[0021] The present invention also provides a multifunctional modifier, which is prepared by the preparation method of the multifunctional modifier as described above; in the structure of the multifunctional modifier, the cyclotriphosphazene structure serves as an acid source and a gas source, the polyhexamethylene biguanide structure serves as a gas source, and the Maillard product polysaccharide ring serves as a carbon source; multiple components are organically combined to construct an expansion flame retardant system with strong charring performance; at the same time, the cyclotriphosphazene structure and the polyhexamethylene biguanide hydrochloride structure can produce a phosphorus-nitrogen synergistic effect, giving the multifunctional modifier a higher flame retardant and anti-melting droplet performance; the polyhexamethylene biguanide hydrochloride structure has excellent antibacterial performance, giving the multifunctional modifier a higher antibacterial performance; the Maillard product structure has strong adhesion, giving the multifunctional modifier a higher adhesion performance; the polyhexamethylene biguanide hydrochloride structure and the Maillard product structure both have strong water solubility, giving the multifunctional modifier a higher water solubility.

[0022] The present invention also provides a method for preparing a durable flame-retardant polyamide 6 fabric, comprising adding the polyamide 6 fabric into a finishing solution of a multifunctional modifier as described above, reacting at 75-85°C, and obtaining the durable flame-retardant polyamide 6 fabric through post-treatment (taking out, washing, and drying); in this process, the Maillard product in the multifunctional modifier adheres to the polyamide 6 fabric by virtue of its own high adhesion performance, and on the other hand, its aldehyde group undergoes a covalent reaction with the amino group of the polyamide 6 fiber and is grafted onto the polyamide 6 fabric.

[0023] Polyamide 6 fabric is high-strength and wear-resistant, and is widely used in textiles and clothing, aerospace, construction and engineering, and other fields. In the current field of textile technology, giving polyamide 6 fabrics high flame retardancy, high antibacterial properties, and high water washability has become a key issue to be solved. These excellent properties can not only significantly improve the safety and durability of the fabric, but also broaden its application areas and meet more stringent market demands. However, unfortunately, although impregnation finishing, as a widely used fabric post-treatment process, can effectively improve certain properties of the fabric, the existing technical bottlenecks limit the possibility of simultaneously giving polyamide 6 fabrics all of the above-mentioned high performances. The present invention prepares a multifunctional modifier, which is then used to impregnate polyamide 6 fabrics, filling the gap in the prior art and achieving comprehensive performance improvement of polyamide 6 fabrics in flame retardancy, antibacterial properties, and water washability.

[0024] As the preferred technical solution:

[0025] In the method for preparing a durable flame-retardant polyamide 6 fabric as described above, the bath ratio of the polyamide 6 fabric to the multifunctional modifier finishing liquid is 1:40-50, and the reaction time is 1.5-2 hours.

[0026] The present invention also provides a durable flame retardant polyamide 6 fabric, which is prepared by the method for preparing a durable flame retardant polyamide 6 fabric as described in any one of the above items.

[0027] As the preferred technical solution:

[0028] The durable flame retardant polyamide 6 fabric as described above has a limiting oxygen index of not less than 30.1%, a damaged length of not more than 11.3 cm, no droplets are generated, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are both above 99.9%. After 30 times of water washing, the damaged length is still less than 14.4 cm, no droplets are generated, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are still above 97.0%. The fabric has excellent flame retardant and anti-droplet properties, antibacterial properties and water washability.

[0029] Beneficial effects:

[0030] (1) The present invention obtains a multifunctional modifier finishing liquid by coating and modifying hexachlorocyclotriphosphazene with polyhexamethylene biguanide hydrochloride, and then undergoing a Maillard reaction with glucose under alkaline conditions. The multifunctional modifier finishing liquid is purified to obtain a multifunctional modifier having multiple functions such as flame retardancy, antibacterial, adhesion and water solubility.

[0031] (2) The present invention utilizes a multifunctional modifier finishing liquid to perform impregnation finishing on polyamide 6 fabric, thereby significantly improving the flame retardant and anti-melting dripping properties, antibacterial properties, and water washability of the fabric, thereby broadening the application field of the fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a surface morphology of the durable flame retardant polyamide 6 fabric of Example 1 of the present invention;

[0033] Figure 2 This is a diagram showing the vertical burning test results of the durable flame retardant polyamide 6 fabric of Example 1 of the present invention. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0035] The following are the test methods for the relevant performance indicators in each embodiment:

[0036] Limiting oxygen index: Tested in accordance with GB / T 5454-1997 "Oxygen Index Method for Textile Combustion Performance Test".

[0037] Damage length and the presence of molten droplets: Determine the damage length, smoldering and afterflaming time in the vertical direction of the combustion performance of textiles according to GB / T 5455-2014. Observe the presence of molten droplets during the test.

[0038] Antibacterial rate: measured in accordance with GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method".

[0039] Damaged length and presence of molten droplets after 30 washes: First wash the fabric 30 times with water according to AATCC 61-2013 "Accelerated test for color fastness to household and commercial washing" standard, and then test the damaged length of the fabric with reference to GB / T 5455-2014 "Determination of vertical direction damage length, smoldering and afterflaming time of textile combustion performance" standard, and observe whether there are molten droplets during the test.

[0040] Antibacterial rate after 30 washes: First wash the fabric 30 times with water according to AATCC 61-2013 "Accelerated test for color fastness to household and commercial washing" standard, and then measure it according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method" standard.

[0041] Example 1

[0042] A method for preparing a durable flame-retardant polyamide 6 fabric, the specific steps are as follows:

[0043] (1) Preparation of raw materials;

[0044] Polyhexamethylene biguanide hydrochloride: manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd., product number is P910103;

[0045] Hexachlorocyclotriphosphazene;

[0046] Acid binding agent: triethylamine;

[0047] Solvent a: tetrahydrofuran;

[0048] Solvent b: a mixed solution of tetrahydrofuran and water, with tetrahydrofuran accounting for 30% by volume;

[0049] glucose;

[0050] Sodium hydroxide;

[0051] Polyamide 6 fabric: Manufacturer: Wujiang Fuhua Weaving Co., Ltd., weight: 112.8g / m 2, the damage length is 30cm, and the limiting oxygen index is 20.1%;

[0052] (2) preparing a multifunctional modifier finishing liquid;

[0053] (2.1) After uniformly mixing polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and solvent a to obtain a reaction system a, the mixture is reacted at 65°C for 4 hours, and after post-treatment, a modified cyclotriphosphazene is obtained; wherein the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1.5:5, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6.5:1, and the amount ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:50 mL;

[0054] (2.2) preparing a reaction system b consisting of modified cyclotriphosphazene, solvent b, glucose and sodium hydroxide with a pH value of 12, and reacting at 80°C for 2.5 hours to obtain a multifunctional modifier finishing liquid (the multifunctional modifier finishing liquid can be purified to obtain a multifunctional modifier); wherein, in the reaction system b, the content of modified cyclotriphosphazene is 50 g / L, and the content of glucose is 90 g / L;

[0055] (3) Preparation of durable flame retardant polyamide 6 fabric;

[0056] Add polyamide 6 fabric into a multifunctional modifier finishing solution, react at 80°C for 1.7 hours, and obtain durable flame retardant polyamide 6 fabric through post-treatment; wherein the bath ratio of polyamide 6 fabric to the multifunctional modifier finishing solution is 1:50.

[0057] The surface morphology of the final durable flame retardant polyamide 6 fabric is as follows: Figure 1 As shown; the limiting oxygen index of the durable flame retardant polyamide 6 fabric is 32.6%, and the damaged length is 9.7cm (the vertical burning test results are shown in Figure 2 As shown in the figure, no droplets were generated during the vertical burning test; the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 99.9%, and the antibacterial rate against Staphylococcus aureus was 99.9%;

[0058] After 30 times of washing, the damaged length of the durable flame retardant polyamide 6 fabric was 13.4 cm, and no molten droplets were generated during the vertical burning test; after 30 times of washing, the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 98.9%, and the antibacterial rate against Staphylococcus aureus was 98.1%.

[0059] After the raw material polyamide 6 fabric is flame-retardantly finished in this embodiment, the degree of damage of the obtained durable flame-retardant polyamide 6 fabric is significantly reduced, and the damage length after 30 washings is still only 13.4 cm, which fully proves the effectiveness of the multifunctional modifier finishing liquid of this embodiment in improving the flame retardant properties of polyamide 6 fabric.

[0060] Example 2

[0061] A method for preparing a durable flame-retardant polyamide 6 fabric, the specific steps are as follows:

[0062] (1) Preparation of raw materials;

[0063] Polyhexamethylene biguanide hydrochloride: manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd., product number is P910103;

[0064] Hexachlorocyclotriphosphazene;

[0065] Acid binding agent: triethylamine;

[0066] Solvent a: tetrahydrofuran;

[0067] Solvent b: a mixed solution of tetrahydrofuran and water, with tetrahydrofuran accounting for 20% by volume;

[0068] glucose;

[0069] Sodium hydroxide;

[0070] Polyamide 6 fabric: Manufacturer: Wujiang Fuhua Weaving Co., Ltd., weight: 112.8g / m 2 , the damage length is 30cm, and the limiting oxygen index is 20.1%;

[0071] (2) preparing a multifunctional modifier finishing liquid;

[0072] (2.1) After uniformly mixing polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and solvent a to obtain a reaction system a, the mixture is reacted at 55°C for 5 hours, and after post-treatment, a modified cyclotriphosphazene is obtained; wherein the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1:5, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6:1, and the amount ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:40 mL;

[0073] (2.2) preparing a reaction system b consisting of modified cyclotriphosphazene, solvent b, glucose and sodium hydroxide with a pH value of 11, and reacting at 75°C for 3 hours to obtain a multifunctional modifier finishing liquid (the multifunctional modifier finishing liquid can be purified to obtain a multifunctional modifier); wherein, in the reaction system b, the content of the modified cyclotriphosphazene is 40 g / L, and the content of the glucose is 80 g / L;

[0074] (3) Preparation of durable flame retardant polyamide 6 fabric;

[0075] The polyamide 6 fabric is added into the multifunctional modifier finishing liquid, reacted at 75°C for 2 hours, and then post-treated to obtain the durable flame retardant polyamide 6 fabric; wherein the bath ratio of the polyamide 6 fabric to the multifunctional modifier finishing liquid is 1:40.

[0076] The final durable flame-retardant polyamide 6 fabric has a limiting oxygen index of 30.1%, a damaged length of 11.3 cm, and no droplets are generated during the vertical burning test; the durable flame-retardant polyamide 6 fabric has an antibacterial rate of 99.9% against Escherichia coli and 99.9% against Staphylococcus aureus;

[0077] After 30 times of washing, the damaged length of the durable flame retardant polyamide 6 fabric was 14.4 cm, and no molten droplets were generated during the vertical burning test; after 30 times of washing, the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 98.1%, and the antibacterial rate against Staphylococcus aureus was 97.9%.

[0078] Example 3

[0079] A method for preparing a durable flame-retardant polyamide 6 fabric, the specific steps are as follows:

[0080] (1) Preparation of raw materials;

[0081] Polyhexamethylene biguanide hydrochloride: manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd., product number is P910103;

[0082] Hexachlorocyclotriphosphazene;

[0083] Acid binding agent: triethylamine;

[0084] Solvent a: tetrahydrofuran;

[0085] Solvent b: a mixed solution of tetrahydrofuran and water, with tetrahydrofuran accounting for 25% by volume;

[0086] glucose;

[0087] Sodium hydroxide;

[0088] Polyamide 6 fabric: Manufacturer: Wujiang Fuhua Weaving Co., Ltd., weight: 112.8g / m 2 , the damage length is 30cm, and the limiting oxygen index is 20.1%;

[0089] (2) preparing a multifunctional modifier finishing liquid;

[0090] (2.1) After uniformly mixing polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and solvent a to obtain a reaction system a, the mixture is reacted at 60°C for 4.5 hours, and after post-treatment, a modified cyclotriphosphazene is obtained; wherein the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1.3:5, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6.3:1, and the amount ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:45 mL;

[0091] (2.2) preparing a reaction system b consisting of modified cyclotriphosphazene, solvent b, glucose and sodium hydroxide with a pH value of 11.5, and reacting at 78°C for 2.8 hours to obtain a multifunctional modifier finishing liquid (the multifunctional modifier finishing liquid can be purified to obtain a multifunctional modifier); wherein, in the reaction system b, the content of modified cyclotriphosphazene is 45 g / L, and the content of glucose is 85 g / L;

[0092] (3) Preparation of durable flame retardant polyamide 6 fabric;

[0093] Add polyamide 6 fabric into the multifunctional modifier finishing solution, react at 78°C for 1.9 hours, and obtain durable flame retardant polyamide 6 fabric through post-treatment; wherein the bath ratio of polyamide 6 fabric to the multifunctional modifier finishing solution is 1:45.

[0094] The final durable flame-retardant polyamide 6 fabric has a limiting oxygen index of 31%, a damaged length of 10.2 cm, and no droplets are generated during the vertical burning test; the antibacterial rate of the durable flame-retardant polyamide 6 fabric against Escherichia coli is 99.9%, and the antibacterial rate against Staphylococcus aureus is 99.9%;

[0095] After 30 times of washing, the damaged length of the durable flame retardant polyamide 6 fabric was 13.9 cm, and no molten droplets were generated during the vertical burning test; after 30 times of washing, the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 97.2%, and the antibacterial rate against Staphylococcus aureus was 97.0%.

[0096] Example 4

[0097] A method for preparing a durable flame-retardant polyamide 6 fabric, the specific steps are as follows:

[0098] (1) Preparation of raw materials;

[0099] Polyhexamethylene biguanide hydrochloride: manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd., product number is P910103;

[0100] Hexachlorocyclotriphosphazene;

[0101] Acid binding agent: triethylamine;

[0102] Solvent a: tetrahydrofuran;

[0103] Solvent b: a mixed solution of tetrahydrofuran and water, with tetrahydrofuran accounting for 25% by volume;

[0104] glucose;

[0105] Sodium hydroxide;

[0106] Polyamide 6 fabric: Manufacturer: Wujiang Fuhua Weaving Co., Ltd., weight: 112.8g / m2 , the damage length is 30cm, and the limiting oxygen index is 20.1%;

[0107] (2) preparing a multifunctional modifier finishing liquid;

[0108] (2.1) After uniformly mixing polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and solvent a to obtain a reaction system a, the mixture is reacted at 60°C for 4.5 hours, and after post-treatment, a modified cyclotriphosphazene is obtained; wherein the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1.7:5, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6.8:1, and the amount ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:45 mL;

[0109] (2.2) preparing a reaction system b consisting of modified cyclotriphosphazene, solvent b, glucose and sodium hydroxide with a pH value of 11.5, and reacting at 83°C for 2.3h to obtain a multifunctional modifier finishing liquid (the multifunctional modifier finishing liquid can be purified to obtain a multifunctional modifier); wherein, in the reaction system b, the content of modified cyclotriphosphazene is 55g / L, and the content of glucose is 95g / L;

[0110] (3) Preparation of durable flame retardant polyamide 6 fabric;

[0111] Add polyamide 6 fabric into a multifunctional modifier finishing solution, react at 83°C for 1.6 hours, and obtain durable flame retardant polyamide 6 fabric through post-treatment; wherein the bath ratio of polyamide 6 fabric to the multifunctional modifier finishing solution is 1:45.

[0112] The final durable flame-retardant polyamide 6 fabric has a limiting oxygen index of 33.4%, a damaged length of 9.2 cm, and no droplets are generated during the vertical burning test; the antibacterial rate of the durable flame-retardant polyamide 6 fabric against Escherichia coli is 99.9%, and the antibacterial rate against Staphylococcus aureus is 99.9%;

[0113] After 30 times of washing, the damaged length of the durable flame retardant polyamide 6 fabric was 13 cm, and no molten droplets were generated during the vertical burning test; after 30 times of washing, the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 99.3%, and the antibacterial rate against Staphylococcus aureus was 99.1%.

[0114] Example 5

[0115] A method for preparing a durable flame-retardant polyamide 6 fabric, the specific steps are as follows:

[0116] (1) Preparation of raw materials;

[0117] Polyhexamethylene biguanide hydrochloride: manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd., product number is P910103;

[0118] Hexachlorocyclotriphosphazene;

[0119] Acid binding agent: triethylamine;

[0120] Solvent a: tetrahydrofuran;

[0121] Solvent b: a mixed solution of tetrahydrofuran and water, with tetrahydrofuran accounting for 20% by volume;

[0122] glucose;

[0123] Sodium hydroxide;

[0124] Polyamide 6 fabric: Manufacturer: Wujiang Fuhua Weaving Co., Ltd., weight: 112.8g / m 2 , the damage length is 30cm, and the limiting oxygen index is 20.1%;

[0125] (2) preparing a multifunctional modifier finishing liquid;

[0126] (2.1) After uniformly mixing polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and solvent a to obtain a reaction system a, the mixture is reacted at 55°C for 5 hours, and after post-treatment, a modified cyclotriphosphazene is obtained; wherein the mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 2:5, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 7:1, and the amount ratio of hexachlorocyclotriphosphazene to solvent a is 1 g:50 mL;

[0127] (2.2) preparing a reaction system b consisting of modified cyclotriphosphazene, solvent b, glucose and sodium hydroxide with a pH value of 11, and reacting at 85°C for 2 hours to obtain a multifunctional modifier finishing liquid (the multifunctional modifier finishing liquid can be purified to obtain a multifunctional modifier); wherein, in the reaction system b, the content of the modified cyclotriphosphazene is 60 g / L, and the content of the glucose is 100 g / L;

[0128] (3) Preparation of durable flame retardant polyamide 6 fabric;

[0129] Add polyamide 6 fabric into a multifunctional modifier finishing solution, react at 85°C for 1.5 hours, and obtain durable flame retardant polyamide 6 fabric through post-treatment; wherein the bath ratio of polyamide 6 fabric to the multifunctional modifier finishing solution is 1:40.

[0130] The final durable flame-retardant polyamide 6 fabric has a limiting oxygen index of 33.8%, a damaged length of 8.9 cm, and no droplets are generated during the vertical burning test; the antibacterial rate of the durable flame-retardant polyamide 6 fabric against Escherichia coli is 99.9%, and the antibacterial rate against Staphylococcus aureus is 99.9%;

[0131] After 30 times of washing, the damaged length of the durable flame retardant polyamide 6 fabric was 12.8 cm, and no molten droplets were generated during the vertical burning test; after 30 times of washing, the antibacterial rate of the durable flame retardant polyamide 6 fabric against Escherichia coli was 99.8%, and the antibacterial rate against Staphylococcus aureus was 99.5%.

Claims

1. A method for preparing a multifunctional modifier finishing liquid, It is characterized in that Here are the steps: (1) using polyhexamethylene biguanide hydrochloride to coat and modify hexachlorocyclotriphosphazene to obtain modified cyclotriphosphazene; (2) preparing a reaction system b containing modified cyclotriphosphazene, solvent b, and glucose and having a pH value greater than 7, and reacting at 75 to 85° C. to obtain a multifunctional modifier finishing liquid; The specific process of step (1) is: after polyhexamethylene biguanide hydrochloride, hexachlorocyclotriphosphazene, an acid-binding agent, and a solvent a are uniformly mixed to obtain a reaction system a, the mixture is reacted at 55 to 65° C. for 4 to 5 hours, and post-treated to obtain a modified cyclotriphosphazene; The mass ratio of polyhexamethylene biguanide hydrochloride to hexachlorocyclotriphosphazene is 1-2:5, the molar ratio of the acid binding agent to hexachlorocyclotriphosphazene is 6-7:1, and the dosage ratio of hexachlorocyclotriphosphazene to solvent a is 1g:40-50mL.

2. A method for preparing a multifunctional modifier finishing liquid according to claim 1, It is characterized in that In step (2), in the reaction system b, the content of modified cyclotriphosphazene is 40-60 g / L, and the content of glucose is 80-100 g / L; the pH value of the reaction system b is 11-12; and the reaction time is 2-3 h.

3. A multifunctional modifier finishing liquid, It is characterized in that The method for preparing a multifunctional modifier finishing liquid as claimed in claim 1 or 2 is adopted to prepare the same.

4. A method for preparing a multifunctional modifier, It is characterized in that The multifunctional modifier finishing liquid as claimed in claim 3 is purified to obtain a multifunctional modifier.

5. A multifunctional modifier, It is characterized in that The multifunctional modifier is prepared by the preparation method of the multifunctional modifier as claimed in claim 4.

6. A method for preparing a durable flame retardant polyamide 6 fabric, It is characterized in that The polyamide 6 fabric is added into the multifunctional modifier finishing liquid as claimed in claim 3, reacted at 75-85° C., and post-treated to obtain the durable flame retardant polyamide 6 fabric.

7. A method for preparing a durable flame retardant polyamide 6 fabric according to claim 6, It is characterized in that The bath ratio of polyamide 6 fabric to the multifunctional modifier finishing solution is 1:40-50, and the reaction time is 1.5-2h.

8. A durable flame retardant polyamide 6 fabric, It is characterized in that The method for preparing a durable flame retardant polyamide 6 fabric as claimed in claim 6 or 7 is used to prepare the durable flame retardant polyamide 6 fabric; the limiting oxygen index of the durable flame retardant polyamide 6 fabric is not less than 30.1%, the damaged length is not more than 11.3 cm, no molten droplets are generated, the antibacterial rates against Escherichia coli and Staphylococcus aureus are both above 99.9%, the damaged length is still less than 14.4 cm after 30 times of washing, no molten droplets are generated, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are still above 97.0%.

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