Polyamide with antibacterial and antiviral functions and preparation method and application thereof

Abstract

The present application relates to a kind of polyamides with antibacterial and antiviral functions and its preparation method and application, the polyamide with antibacterial and antiviral functions is loaded cationic polymer guanidine salt antibacterial and antiviral polyamide;The loaded cationic polymer guanidine salt antibacterial and antiviral polyamide is by poly cation guanidine salt block and polyamide reaction monomer raw material mixing and by random copolymerization, or by poly cation polymer guanidine salt block and diacid end-capped polyamide block composition.Compared with prior art, the antibacterial and antiviral components in the polyamide prepared in the present application are not dissolved, uniformly dispersed, have good durability and good biocompatibility.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional polyamide materials, in particular to a polyamide with antibacterial and antiviral functions and a preparation method and application thereof. BACKGROUND

[0002] Globalization brings people increasingly prosperous life, but also faster and more unstable transmission of infectious diseases than ever before. The market demand for antibacterial properties of textile fabrics is also increasing, especially the safety in special environments is particularly important. Polyamide fibers are used frequently and widely in the textile field, but they have no antibacterial function and are easy to adsorb bacteria and other microorganisms, affecting human health. Therefore, it is urgent to study the polyamide with antibacterial function by adding a small amount of antibacterial agent.

[0003] At present, the antibacterial polyamide modified composite material usually faces two problems: one is that the organic antibacterial agent is adhered to the surface of the polyamide by finishing after loading, and the antibacterial durability is poor; the other is that the inorganic antibacterial agent has a small loading amount and a low effect, and the increase of the loading amount of the antibacterial agent will cause poor compatibility and difficult dispersion.

[0004] The patent application with the application number 202210625731.X discloses an antibacterial and antiviral polyamide 6 obtained by loading nano-copper on titanium dioxide and introducing polyamide 6 in situ polymerization; the patent with the application number 202110321834.2 uses zirconium hydrogen phosphate to load antibacterial nano-metal powder microspheres wrapped by organic polyfurfural alcohol, realizes high loading of nano-metal powder, and then adds polyamide polymerization reaction to obtain polyamide fibers with good antibacterial property; the patent application with the application number 201510867078.8 discloses a preparation method of antibacterial polyamide fibers loaded with nano-copper oxide by mesoporous zirconium phosphate. In the scheme, the mesoporous zirconium phosphate loaded with copper oxide gel precursor and polyamide reaction monomer are polymerized to obtain mesoporous zirconium phosphate loaded with nano-copper oxide antibacterial polyamide by melt blending or in-situ copolymerization. However, the nano-metal oxide used in the method is easy to cause toxicity to human cells during the falling-off process from the matrix, and pollutes the environment when leaking; in addition, the whiteness value of the fabric formed by the antibacterial polyamide fibers decreases obviously. SUMMARY

[0005] The present application relates to the technical field of functional polyamide materials, in particular to a polyamide with antibacterial and antiviral functions and a preparation method and application thereof.

[0006] The purpose of the present application is achieved by the following technical solutions:

[0007] The first aspect of the present application provides a polyamide with antibacterial and antiviral functions, which is a cationic polymer guanidine salt loaded antibacterial and antiviral polyamide.

[0008] The cationic polymer guanidine salt loaded antibacterial and antiviral polyamide is formed by mixing a poly cationic guanidine salt block and a polyamide reaction monomer and through random copolymerization, or is composed of a poly cationic polymer guanidine salt block and a diacid terminated polyamide block.

[0009] Further, the poly cationic guanidine salt block is selected from one of the following structural formulas:

[0010]

[0011] wherein m is the number of methylene groups, m = 2-10; n is the polymerization degree of the poly cationic polymer guanidine salt block, n = 4-50.

[0012] Further, the polyamide reaction monomer is selected from at least one of caprolactam, a linear dibasic acid with 4-10 carbon atoms, and a linear dibasic amine with 3-12 carbon atoms.

[0013] Further, the diacid terminated polyamide block is selected from one of the following structural formulas:

[0014]

[0015] wherein M is 2-10 methylene groups, n1 is the polymerization degree of the diacid terminated polycaprolactam, n1 = 2-20, m1 is 3-12, m2 is 4-10; n2 is the polymerization degree of the diacid terminated polyamide, n2 = 1-20.

[0016] Further, the cationic polymer guanidine salt loaded antibacterial and antiviral polyamide has a number average molecular weight of 10,000-30,000, a relative viscosity of 1.5-3.0, a glass transition temperature of 20-65℃, and a melting point of 180-250℃.

[0017] The second aspect of the present application provides a preparation method of the polyamide with antibacterial and antiviral functions as described above, comprising the following steps:

[0018] Reaction A: mixing the cationic polymer guanidine salt, caprolactam, 6-aminohexanoic acid, and deionized water, and then performing hydrolysis ring opening, polycondensation, and polyaddition reactions to obtain a cationic polymer guanidine salt loaded random copolymer 6;

[0019] Or,

[0020] Reaction B: the cationic polymer guanidine salt and linear dibasic acid, linear dibasic amine, deionized water are mixed, and then subjected to polycondensation and polyaddition reaction to obtain random copolyamide PAXX loaded with cationic polymer guanidine salt.

[0021] Further, in reaction A, the temperature of the ring-opening reaction is 200-260 DEG C, the time is 1-5 h, the pressure is 0-0.3 MPa, and then the pressure is slowly reduced to normal pressure;

[0022] Or, to improve the molecular weight of the random copolyamide 6, the system is subjected to vacuum extraction to perform polycondensation reaction, and the random copolymer product is obtained, the polycondensation reaction temperature is 240-265 DEG C, the time is 1-6 h, and the vacuum degree of the polycondensation reaction system is 500-5000 Pa,

[0023] The addition amount of the 6-aminocaproic acid is 0.1-5% based on the mass of the caprolactam, and the content of deionized water is 1%-8%;

[0024] In reaction B, first, the temperature is kept at 170-280 DEG C for 1-5 h, the pressure is 0-2 MPa, and then the pressure is slowly reduced to normal pressure, the polycondensation reaction temperature is 220-285 DEG C, the time is 1-6 h, and the vacuum degree of the polycondensation reaction system is 500-5000 Pa;

[0025] The mass concentration of the linear dibasic acid, dibasic amine or linear dibasic amine dibasic acid salt in deionized water is 40%-70%.

[0026] The third aspect of the present application provides another method for preparing the above-mentioned polyamide with antibacterial and antiviral functions, comprising the following steps:

[0027] Reaction C: caprolactam, dibasic acid and deionized water are placed in a reaction container, and subjected to hydrolysis ring-opening and polycondensation reaction at a certain temperature and pressure to obtain a double-end carboxyl polyamide 6 prepolymer, and then the cationic polymer guanidine salt is further added through secondary feeding, and subjected to polycondensation reaction under vacuum extraction to obtain antibacterial and antiviral copolyamide 6 loaded with cationic polymer guanidine salt;

[0028] Or,

[0029] Reaction D: linear dibasic acid dibasic amine salt, dibasic acid and deionized water are placed in a reaction container, and subjected to polycondensation reaction to obtain a double-end carboxyl polyamide prepolymer, and then the cationic polymer guanidine salt is further added through secondary feeding, and subjected to polycondensation reaction to obtain antibacterial and antiviral block copolyamide PAXX loaded with cationic polymer guanidine salt.

[0030] Further, in reaction C, the temperature of the ring-opening and polycondensation reaction is 200-260 DEG C, the time is 1-5h, the pressure is 0-0.3MPa, then the pressure is slowly reduced to normal pressure, to obtain the double-end carboxyl polyamide 6 prepolymer, through secondary feeding, adding the antibacterial and antiviral agent, vacuumizing the system, to make the polycondensation reaction, the temperature of the polycondensation reaction is 240-265 DEG C, the time is 1-6h, the vacuum degree of the polycondensation reaction system is 500-5000Pa,

[0031] In the preparation process of the double-end carboxyl polyamide 6 prepolymer, the mass content of deionized water is 1%-8%, and the number average molecular weight of the double-end carboxyl polyamide 6 prepolymer is 1000-8000.

[0032] In reaction D, the temperature is increased to 180-280 DEG C, the temperature is kept constant for 1-5h, the pressure is 0-2MPa, then the pressure is slowly reduced to normal pressure, the polycondensation reaction temperature is 220-285 DEG C, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa.

[0033] The mass concentration of the linear diamine dibasic acid salt in deionized water is 40%-70%, and the number average molecular weight of the double-end carboxyl polyamide PAXX prepolymer is 1000-8000.

[0034] The fourth aspect of the present application provides a kind of application of polyamide with antibacterial and antiviral function, the polyamide is applied in the preparation process of antibacterial and antiviral fiber, and specifically includes:

[0035] Antibacterial and antiviral random copolyamide resin or antibacterial and antiviral block copolyamide resin is obtained by pre-crystallization, drying, spinning and drawing to obtain antibacterial and antiviral fiber.

[0036] The breaking strength of the obtained fiber is 1.5-8 cN / dtex, and the breaking elongation is 10%-60%, and the antiviral activity rate of the fiber to influenza A H1N1 virus is greater than or equal to 90%.

[0037] The technical solution has the following technical advantages:

[0038] (1) In the present application, the cationic polymer guanidine salt is polymerized in-situ in the polyamide 6 matrix to realize the intrinsic antibacterial and antiviral copolymer, and the preparation method is simple and easy to operate.

[0039] (2) The antibacterial and antiviral copolyamide 6 of the present application has no skin irritation and is not easy to cause bacterial resistance, and is suitable for wide use.

[0040] (3) The present application can obtain antibacterial and antiviral copolyamide 6 with high addition amount, and the washing resistance is significantly superior.

[0041] (4) The prepared antibacterial and antiviral fiber can effectively inhibit bacteria and viruses, and the antibacterial and antiviral additives are not leached, green and environmentally friendly, and have a wide application prospect. DETAILED DESCRIPTION

[0042] The polyamide in the application is prepared by mixing raw materials of poly-cationic polymer guanidine salt blocks and polyamide reaction monomers through random copolymerization, or is composed of poly-cationic polymer guanidine salt blocks and diacid-terminated polyamide blocks, and the mass ratio of the poly-cationic polymer guanidine salt to the polyamide is 0.1%-8%.

[0043] The structural formula of the poly-cationic polymer guanidine salt block is as follows:

[0044]

[0045] In the formula, m is the number of methylene groups, m=2-10; n is the polymerization degree of the poly-cationic polymer guanidine salt block, n=4-50.

[0046] The polyamide reaction monomer can be at least one of caprolactam, a linear dibasic acid with 4-10 carbon atoms, and a linear dibasic amine with 3-12 carbon atoms.

[0047] The structural formula of the diacid-terminated polyamide block is as follows:

[0048] Or

[0049] In the formula, M can be 2-10 methylene groups, n1 is the polymerization degree of the diacid-terminated polyamide, n1=2-20, m1 is 3-12, m2 is 4-10, and n2 is the polymerization degree of the diacid-terminated polyamide, n2=1-20.

[0050] As a preferred technical solution:

[0051] The number-average molecular weight of the polyamide loaded with the poly-cationic polymer guanidine salt is 10,000-30,000, and the relative viscosity is 1.5-3.0; the glass transition temperature of the antibacterial and antiviral polyamide is 20-65℃, and the melting point is 180-250℃.

[0052] The application further provides two preparation methods of the polyamide loaded with the poly-cationic polymer guanidine salt.

[0053] The cationic polymer guanidine salt and caprolactam, 6-aminocaproic acid, deionized water are mixed in a certain proportion, and then hydrolysis ring opening, polycondensation, and polyaddition reactions are carried out at a certain temperature and pressure to obtain the cationic polymer guanidine salt-loaded antibacterial and antiviral random copolyamide 6; or the cationic polymer guanidine salt and linear dibasic acid, linear diamine, deionized water are mixed in a certain proportion, and then polycondensation and polyaddition reactions are carried out at a certain temperature and pressure to obtain the cationic polymer guanidine salt-loaded antibacterial and antiviral random copolyamide PAXX.

[0054] In the preparation process of the cationic polymer guanidine salt-loaded antibacterial and antiviral random copolyamide 6, the ring opening reaction is carried out at a temperature of 200-260°C for 1-5h under a pressure of 0-0.3MPa; then the pressure is slowly reduced to normal pressure; in order to improve the molecular weight of the random copolyamide 6, the system is vacuumized to carry out polycondensation reaction to obtain a random copolymerization product; the polycondensation reaction is carried out at a temperature of 240-265°C for 1-6h under a vacuum degree of 500-5000Pa in the polycondensation reaction system. In the preparation process of the cationic polymer guanidine salt-loaded antibacterial and antiviral random copolyamide PAXX, the reaction is first carried out at a constant temperature of 170-280°C for 1-5h under a pressure of 0-2MPa; then the pressure is slowly reduced to normal pressure; the polycondensation reaction is carried out at a temperature of 220-285°C for 1-6h under a vacuum degree of 500-5000Pa in the polycondensation reaction system.

[0055] Two preparation methods of the cationic polymer guanidine salt-loaded antibacterial and antiviral polyamide are provided, and the second preparation method is as follows:

[0056] A certain proportion of caprolactam, dibasic acid, and deionized water are placed in a reaction container, and then hydrolysis ring opening and polycondensation reactions are carried out at a certain temperature and pressure to obtain a double-end carboxyl polyamide 6 prepolymer; a certain proportion of cationic polymer guanidine salt is added to the above reaction container through secondary feeding, and then polycondensation reaction is carried out under a certain temperature and vacuum condition to obtain the cationic polymer guanidine salt-loaded antibacterial and antiviral copolyamide 6. Or a certain proportion of linear dibasic acid, diamine salt, dibasic acid, and deionized water are placed in a reaction container, and then polycondensation reaction is carried out at a certain temperature and pressure to obtain a double-end carboxyl polyamide prepolymer; a certain proportion of cationic polymer guanidine salt is added to the above reaction container through secondary feeding, and then polycondensation reaction is carried out under a certain temperature and vacuum condition to obtain the cationic polymer guanidine salt-loaded antibacterial and antiviral block copolyamide PAXX.

[0057] In the preparation of the antibacterial and antiviral block copolymerized polyamide 6 loaded with cationic polymer guanidine salt, the temperature of the ring-opening and polycondensation reaction is 200-260℃, the time is 1-5h, and the pressure is 0-0.3MPa; then the pressure is slowly reduced to normal pressure to obtain a double-end carboxyl polyamide 6 prepolymer; through secondary feeding, the antibacterial and antiviral agent is added, the system is vacuumized, and the polycondensation reaction is carried out to obtain a polycation guanidine salt-polyamide 6 copolymer product; the temperature of the polycondensation reaction is 240-265℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa. In the preparation of the antibacterial and antiviral block copolymer PAXX loaded with cationic polymer guanidine salt, the temperature is increased to 180-280℃, the temperature is kept constant for 1-5h, the pressure is 0-2MPa; then the pressure is slowly reduced to normal pressure; the polycondensation reaction temperature is 220-285℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa.

[0058] In the preparation method of the antibacterial and antiviral random copolymer polyamide 6 as described above, the amount of 6-aminocaproic acid added is 0.1-5% based on the mass of caprolactam, and the content of deionized water is 1%-8%.

[0059] In the preparation method of the antibacterial and antiviral random copolymer PA6XX as described above, the concentration of the linear diamine dibasic acid salt is 40%-70%.

[0060] In the preparation method of the antibacterial and antiviral block copolymer polyamide 6 as described above, the content of deionized water in the preparation process of the double-end carboxyl polyamide 6 prepolymer is 1%-8%. The number average molecular weight of the double-end carboxyl polyamide 6 prepolymer is 1000-8000.

[0061] In the preparation method of the antibacterial and antiviral block copolymer PA6XX as described above, the mass concentration of the linear diamine dibasic acid salt in deionized water is 40%-70%. The number average molecular weight of the double-end carboxyl polyamide PAXX prepolymer is 1000-8000.

[0062] The application provides two kinds of fibers prepared from antibacterial and antiviral polyamides loaded with cationic polymer guanidine salt. The fibers are prepared from the antibacterial and antiviral random copolymer or antibacterial and antiviral block copolymer resin through pre-crystallization, drying, spinning and drawing. The breaking strength of the fibers is 1.5-8cN / dtex, and the breaking elongation is 10%-60%. The fibers have excellent antibacterial performance on Escherichia coli and Staphylococcus aureus, and have good antiviral effect, and the antiviral activity rate on influenza A H1N1 virus is ≥90%.

[0063] The present application will be described in detail below with specific examples, but is by no means limited to the present application. In the present technical solution, if the component model, material name, preparation process and other features are not explicitly stated, they are considered as common technical features disclosed in the prior art.

[0064] Example 1

[0065] Caprolactam (CPL, 160 g), polyhexamethylene guanidine hydrochloride (PHMG, 3.2 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml reaction kettle and replaced with nitrogen. The temperature was raised to 210°C and stirred for 1 h; then the temperature was raised to 260°C again and stirred for 2 h. Then the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the kettle was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6-PHMG2 was obtained.

[0066] The number average molecular weight of PA6-PHMG2 was 21000, the relative viscosity was 2.30 dL / g, and the melting point was 205°C.

[0067] After pre-crystallization, drying, spinning and drawing, PA6-PHMG2 fiber was obtained. The breaking strength of the PA6-PHMG2 fiber was 3.3 cN / dtex, and the breaking elongation was 30%. The antibacterial rate of the fiber against Escherichia coli and Staphylococcus aureus was 99%, and after 50 times of water washing, the antibacterial rate of the fiber against Escherichia coli and Staphylococcus aureus was 88%, and the antiviral activity rate of the fiber against influenza A H1N1 virus was 99%.

[0068] Comparative Example 1

[0069] Caprolactam (160 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml reaction kettle and replaced with nitrogen. The temperature was raised to 210°C and stirred for 1 h; then the temperature was raised to 260°C again and stirred for 2 h. Then the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the kettle was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6 was obtained.

[0070] The number average molecular weight of PA6 was 30000, the relative viscosity was 2.85 dL / g, and the melting point was 219°C.

[0071] After pre-crystallization, drying, spinning and drawing, PA6 fiber was obtained. The breaking strength of the PA6 fiber was 4.3 cN / dtex, and the breaking elongation was 35%. The obtained fiber had no antibacterial and antiviral effect.

[0072] Example 2

[0073] Caprolactam (CPL, 160 g), deionized water (8 g), adipic acid (3.2 g) were put into a 300 ml reactor, and replaced by nitrogen. The temperature was raised to 230 °C, and stirred for 2 h; then slowly released to atmospheric pressure within 1 h, to obtain adipic acid-terminated polyamide 6 prepolymer. By secondary feeding, polyhexamethylene guanidine hydrochloride (PHMG, 3.2 g) was added, stirred for 1 h, connected to a vacuum system, and the pressure in the reactor was reduced to 500 Pa within 1 h, and the stirring current reached 0.80 A, and the vacuum was removed, to obtain PA6-PHMG-2.

[0074] The number average molecular weight of PA66-PHMG2 was 25000, the relative viscosity was 2.76 dL / g, and the melting point was 255 °C.

[0075] After pre-crystallization, drying, spinning and drawing, PA66-PHMG2 fiber was obtained, and the breaking strength of PA66-PHMG2 fiber was 3.6 cN / dtex, and the breaking elongation was 30%. The antibacterial rate of the fiber against E. coli and Staphylococcus aureus was 96%, and the antiviral effect was 99%. After 50 times of water washing, the antibacterial rate of the fiber against E. coli and Staphylococcus aureus was 90%, and the antiviral activity rate against H1N1 influenza A virus was 99%.

[0076] Example 3

[0077] Caprolactam (CPL, 160 g), deionized water (8 g), adipic acid (3.2 g) were put into a 300 ml reactor, and replaced by nitrogen. The temperature was raised to 230 °C, and stirred for 2 h; then slowly released to atmospheric pressure within 1 h, to obtain adipic acid-terminated polyamide 6 prepolymer. By secondary feeding, polyhexamethylene guanidine hydrochloride (PHMG, 3.2 g) was added, stirred for 1 h, connected to a vacuum system, and the pressure in the reactor was reduced to 500 Pa within 1 h, and the stirring current reached 0.80 A, and the vacuum was removed, to obtain PA6-PHMG-2.

[0078] The number average molecular weight of PA66-PHMG2 was 25000, the relative viscosity was 2.76 dL / g, and the melting point was 255 °C.

[0079] After pre-crystallization, drying, spinning and drawing, PA66-PHMG2 fiber was obtained, and the breaking strength of PA66-PHMG2 fiber was 3.6 cN / dtex, and the breaking elongation was 30%. The antibacterial rate of the fiber against E. coli and Staphylococcus aureus was 96%, and the antiviral effect was 99%. After 50 times of water washing, the antibacterial rate of the fiber against E. coli and Staphylococcus aureus was 90%, and the antiviral activity rate against H1N1 influenza A virus was 99%.

[0080] Example 4

[0081] Caprolactam (CPL, 160 g), polyhexamethylene biguanide hydrochloride (PHMB, 3.2 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml autoclave, and nitrogen was replaced. The temperature was raised to 200 °C, and stirred for 2 h. The temperature was raised to 250 °C again, and stirred for 2 h. Then, the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the autoclave was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6-PHMB2 was obtained.

[0082] The number average molecular weight of PA6-PHMB2 was 17000, the relative viscosity was 2.56 dL / g, and the melting point was 200 °C.

[0083] After pre-crystallization, drying, spinning, and drawing, PA6-PHMG-2 fiber was obtained. The breaking strength of PA6-PHMG-2 fiber was 2.5 cN / dtex, and the breaking elongation was 40%. The antibacterial rate of the fiber against E. coli and S. aureus was >95%, and the antiviral activity rate against H1N1 influenza A virus was 95%. After being washed with water for 50 times, the antibacterial rate of the fiber against E. coli and S. aureus was >93%, and the antiviral activity rate against H1N1 influenza A virus was 90%.

[0084] Example 5

[0085] Caprolactam (CPL, 160 g), polyhexamethylene biguanide hydrochloride (PHMB, 3.2 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml autoclave, and nitrogen was replaced. The temperature was raised to 200 °C, and stirred for 2 h. The temperature was raised to 250 °C again, and stirred for 2 h. Then, the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the autoclave was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6-PHMB2 was obtained.

[0086] The number average molecular weight of PA6-PHMB2 was 17000, the relative viscosity was 2.56 dL / g, and the melting point was 200 °C.

[0087] After pre-crystallization, drying, spinning, and drawing, PA6-PHMG-2 fiber was obtained. The breaking strength of PA6-PHMG-2 fiber was 2.5 cN / dtex, and the breaking elongation was 40%. The antibacterial rate of the fiber against E. coli and S. aureus was >95%, and the antiviral activity rate against H1N1 influenza A virus was 95%. After being washed with water for 50 times, the antibacterial rate of the fiber against E. coli and S. aureus was >93%, and the antiviral activity rate against H1N1 influenza A virus was 90%.

[0088] Example 6

[0089] Caprolactam (CPL, 160 g), poly-p-xylylene guanidine hydrochloride (PPXDG, 3.2 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml autoclave, and nitrogen was replaced. The temperature was raised to 200 °C, and stirred for 2 h; then the temperature was raised to 260 °C again, and stirred for 2 h. Then the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the autoclave was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6-PPXDG2 was obtained.

[0090] The number average molecular weight of PA6-PPXDG2 was 18000, the relative viscosity was 2.45 dL / g, and the melting point was 220 °C.

[0091] PA6-PPXDG2 fibers were obtained after pre-crystallization, drying, spinning, and drawing of PA6-PPXDG2. The breaking strength of the PA6-PPXDG2 fibers was 3.0 cN / dtex, and the breaking elongation was 30%. The antibacterial rate of the fibers against Escherichia coli and Staphylococcus aureus was >95%, and the antiviral activity rate against influenza A H1N1 virus was 95%. After 50 times of water washing, the antibacterial rate of the fibers against Escherichia coli and Staphylococcus aureus was >93%, and the antiviral activity rate against influenza A H1N1 virus was 90%.

[0092] Example 7

[0093] Caprolactam (CPL, 160 g), poly-p-xylylene guanidine hydrochloride (PPXDG, 3.2 g), deionized water (8 g), and aminohexanoic acid (1.6 g) were put into a 300 ml autoclave, and nitrogen was replaced. The temperature was raised to 200 °C, and stirred for 2 h; then the temperature was raised to 260 °C again, and stirred for 2 h. Then the pressure was slowly released to normal pressure within 1 h. A vacuum system was connected, and the pressure in the autoclave was reduced to 500 Pa within 1 h. When the stirring current reached 0.80 A, the vacuum was removed, and PA6-PPXDG2 was obtained.

[0094] The number average molecular weight of PA6-PPXDG2 was 18000, the relative viscosity was 2.45 dL / g, and the melting point was 220 °C.

[0095] PA6-PPXDG2 fibers were obtained after pre-crystallization, drying, spinning, and drawing of PA6-PPXDG2. The breaking strength of the PA6-PPXDG2 fibers was 3.0 cN / dtex, and the breaking elongation was 30%. The antibacterial rate of the fibers against Escherichia coli and Staphylococcus aureus was >95%, and the antiviral activity rate against influenza A H1N1 virus was 95%. After 50 times of water washing, the antibacterial rate of the fibers against Escherichia coli and Staphylococcus aureus was >93%, and the antiviral activity rate against influenza A H1N1 virus was 90%.

[0096] The foregoing description of the embodiments has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the application to the precise form disclosed. Modifications and variations are possible in light of the above teachings or can be acquired from practice of the application. As well, the description is presented in the context of the preferred embodiments as a number of alternatives. It is not intended to limit the application to the precise form described.

Claims

1. A polyamide having an antibacterial and antiviral function, characterized in that, The polyamide with antibacterial and antiviral functions is a cationic polymer guanidine salt antibacterial and antiviral polyamide; The cationic polymer guanidine salt antibacterial and antiviral polyamide is obtained by mixing a poly cationic guanidine salt block and polyamide reaction monomers and through random copolymerization, or is composed of a poly cationic polymer guanidine salt block and a diacid-terminated polyamide block. The preparation method of the polyamide with antibacterial and antiviral functions comprises the following steps: Reaction A: mixing the cationic polymer guanidine salt, caprolactam, 6-aminocaproic acid and deionized water, and then performing hydrolytic ring-opening, polycondensation and polyaddition reactions to obtain the random copolyamide 6 loaded with the cationic polymer guanidine salt; Or, Reaction B: mixing the cationic polymer guanidine salt, linear dibasic acid, linear diamine or linear diamine dibasic acid salt and deionized water, and then performing polycondensation and polyaddition reactions to obtain the random copolyamide PAXX loaded with the cationic polymer guanidine salt. Reaction C: placing caprolactam, dibasic acid and deionized water in a reaction container, and performing hydrolytic ring-opening and polycondensation reactions under certain temperature and pressure to obtain a double-end carboxyl polyamide 6 prepolymer, further adding the cationic polymer guanidine salt through secondary feeding, and performing polycondensation under vacuum to obtain the antibacterial and antiviral copolyamide 6 loaded with the cationic polymer guanidine salt. Or, Reaction D: placing linear dibasic acid diamine salt, dibasic acid and deionized water in a reaction container, and performing polycondensation to obtain a double-end carboxyl polyamide prepolymer, further adding the cationic polymer guanidine salt through secondary feeding, and performing polycondensation to obtain the antibacterial and antiviral block copolyamide PAXX loaded with the cationic polymer guanidine salt.

2. The polyamide with antibacterial and antiviral functions according to claim 1, characterized in that, The poly cationic guanidine salt block is selected from one of the following structural formulas: wherein m is the number of methylene groups, m = 2-10; n is the polymerization degree of the poly cationic polymer guanidine salt block, n = 4-50.

3. The polyamide with antibacterial and antiviral functions according to claim 1, characterized in that, The polyamide reaction monomer is selected from at least one of caprolactam, linear dibasic acid with 4-10 carbon atoms and linear diamine with 3-12 carbon atoms.

4. The polyamide with antibacterial and antiviral functions according to claim 1, wherein, The diacid-terminated polyamide block is selected from one of the following structural formulas: wherein M is 2-10 methylene groups, n1 is the polymerization degree of the diacid-terminated polycaprolactam, n1 = 2-20, m1 is 3-12, m2 is 4-10; n2 is the polymerization degree of the diacid-terminated polyamide, n2 = 1-20.

5. The polyamide with antibacterial and antiviral functions according to claim 1, wherein, The number average molecular weight of the cationic polymer guanidine salt antibacterial and antiviral polyamide is 10000-30000, the relative viscosity is 1.5-3.0, the glass transition temperature is 20-65℃, and the melting point is 180-250℃.

6. A method of producing the polyamide having an antibacterial and antiviral function according to any one of claims 1 to 5, characterized by, The preparation method comprises the following steps: Reaction A: mixing the cationic polymer guanidine salt, caprolactam, 6-aminocaproic acid and deionized water, and then performing hydrolytic ring-opening, polycondensation and polyaddition reactions to obtain the random copolyamide 6 loaded with the cationic polymer guanidine salt; Or, Reaction B: mixing the cationic polymer guanidine salt, linear dibasic acid, linear diamine or linear diamine dibasic acid salt and deionized water, and then performing polycondensation and polyaddition reactions to obtain the random copolyamide PAXX loaded with the cationic polymer guanidine salt.

7. The method for preparing a polyamide with antibacterial and antiviral functions according to claim 6, characterized in that, In reaction A, the temperature of the ring-opening reaction is 200-260℃, the time is 1-5h, the pressure is 0-0.3MPa, and then the pressure is slowly reduced to normal pressure; Or, to improve the molecular weight of the random copolyamide 6, the system is vacuumized to perform the polycondensation reaction, and the random copolymer product is obtained, the temperature of the polycondensation reaction is 240-265℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa, The mass content of the 6-aminocaproic acid is 0.1-5% and the content of the deionized water is 1%-8% based on the mass of the caprolactam; In reaction B, first, the temperature is kept at 170-280℃ for 1-5h, the pressure is 0-2MPa, and then the pressure is slowly reduced to normal pressure, the polycondensation reaction temperature is 220-285℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa; The mass concentration of the linear diacid, diamine or linear diacid salt of diamine in deionized water is 40%-70%.

8. A method of producing a polyamide having an antibacterial and antiviral function according to any one of claims 1 to 5, characterized by, The method comprises the following steps: Reaction C: caprolactam, diacid, and deionized water are placed in a reaction container, and a hydrolysis ring-opening and polycondensation reaction is performed at a certain temperature and pressure to obtain a double-end carboxyl polyamide 6 prepolymer, a cationic polymer guanidine salt is further added through secondary feeding, and a polycondensation reaction is performed under vacuum to obtain an antibacterial and antiviral copolyamide 6 loaded with a cationic polymer guanidine salt; Or, Reaction D: a linear diacid salt of diamine, diacid, and deionized water are placed in a reaction container, and a polycondensation reaction is performed to obtain a double-end carboxyl polyamide prepolymer, a cationic polymer guanidine salt is further added through secondary feeding, and a polycondensation reaction is performed to obtain an antibacterial and antiviral block copolyamide PAXX loaded with a cationic polymer guanidine salt.

9. The method for preparing a polyamide with antibacterial and antiviral functions according to claim 8, characterized in that, In reaction C, the temperature of the ring-opening and polycondensation reaction is 200-260℃, the time is 1-5h, the pressure is 0-0.3MPa, and then the pressure is slowly reduced to normal pressure to obtain a double-end carboxyl polyamide 6 prepolymer, a cationic polymer guanidine salt is further added through secondary feeding, and a polycondensation reaction is performed under vacuum to obtain a poly-cationic guanidine salt-polyamide 6 copolymer product, the temperature of the polycondensation reaction is 240-265℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa, In the preparation process of the double-end carboxyl polyamide 6 prepolymer, the mass content of the deionized water is 1%-8%, and the number average molecular weight of the double-end carboxyl polyamide 6 prepolymer is 1000-8000; In reaction D, the temperature is raised to 180-280℃, kept at 1-5h, the pressure is 0-2MPa, and then the pressure is slowly reduced to normal pressure, the polycondensation reaction temperature is 220-285℃, the time is 1-6h, and the vacuum degree of the polycondensation reaction system is 500-5000Pa, The mass concentration of the linear diacid salt of diamine in deionized water is 40%-70%, and the number average molecular weight of the double-end carboxyl polyamide PAXX prepolymer is 1000-8000.

10. Use of the polyamide according to any one of claims 1 to 5 having antibacterial and antiviral functions, characterized in that, The polyamide is applied in the preparation process of the antibacterial and antiviral fiber, specifically comprising: The antibacterial and antiviral fiber is obtained by pre-crystallization, drying, spinning and drawing of the antibacterial and antiviral random copolyamide resin or the antibacterial and antiviral block copolyamide resin. The fiber has a breaking strength of 1.5-8 cN / dtex, an elongation at break of 10%-60%, and an antiviral activity rate against influenza A H1N1 virus of ≥90%.

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