CN113150267B - Amino acid-based polymer with antiviral and antibacterial functions and preparation method thereof - Google Patents

Amino acid-based polymer with antiviral and antibacterial functions and preparation method thereof Download PDF

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CN113150267B
CN113150267B CN202110432119.6A CN202110432119A CN113150267B CN 113150267 B CN113150267 B CN 113150267B CN 202110432119 A CN202110432119 A CN 202110432119A CN 113150267 B CN113150267 B CN 113150267B
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amino acid
antiviral
antibacterial
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based polymer
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CN113150267A (en
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严永刚
邓光进
焦雪菲
刘朋镇
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Zhongding Kairui Technology Chengdu Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams

Abstract

The invention relates to an amino acid-based polymer with antiviral and antibacterial functions and a preparation method thereof, belonging to the field of antiviral and antibacterial polymers. The invention provides a preparation method of an antiviral and antibacterial amino acid-based polymer, which comprises the following steps: reacting aromatic acid anhydride with basic amino acid to obtain an amino acid polymerization unit with an aromatic formic acid structure; then reacting the amino acid polymerization unit with an aromatic formic acid structure with metal salt with antiviral and antibacterial effects to obtain an amino acid-aromatic formate polymerization unit; and finally, carrying out melt polymerization reaction on the amino acid-aromatic formate polymerization unit and the cyclic lactam to obtain the amino acid-based polymer with the antiviral and antibacterial functions. The obtained antiviral and antibacterial polymer enables metal ions to be firmly bonded on a polymer molecular chain through chemical bonds, so that the metal ions are uniformly distributed on the molecular chain, the same polymer molecular chain can contain various metal ions in a polymerization manner, the effect of killing viruses and bacteria is synergistically enhanced, and the effect of killing viruses and bacteria is as high as 99.9%.

Description

Amino acid-based polymer with antiviral and antibacterial functions and preparation method thereof
Technical Field
The invention relates to an amino acid-based polymer with antiviral and antibacterial functions and a preparation method thereof, belonging to the field of antiviral and antibacterial polymers.
Background
The virus can survive for a certain time in the air and can also be attached to the surfaces of various objects to survive for a certain period, the transmission path is diversified, the infection capacity is extremely strong, once the virus is infected, no effective drug treatment is available, the variation speed is fast, great threat is caused to the health of people, and a more efficient method and means are needed for the protection. The prevention is the most effective way to ensure the health without infection. Therefore, the research and preparation of materials and wearing articles capable of inhibiting or killing viruses and bacteria with high efficiency in large-scale use are one of the most effective ways to combat the viruses and bacteria.
However, the common antibiotics only kill six different pathogens, have specific selectivity for viruses and bacteria, have mutual inhibitory effect among different antibiotics, and have limited effect on the simultaneous occurrence of a plurality of viruses or bacteria. Thus, the use of antibiotics to inhibit and block the spread of viruses and bacteria is almost impossible to achieve.
In the course of the history of viral and bacterial fight, human has selected metal ions as one of the most effective means for killing viruses and bacteria. The metal ion disinfection mode is that the fungus cells can enrich metal ions, and the metal ions adsorbed on the surfaces of the fungi destroy the functions of cell membranes to enter the cells, so that certain cell components escape, interfere the cell metabolic process or interfere the action of various enzymes, so that the cells lose the due biological functions, and finally die. For example, silver is one of the earliest metals used to kill viruses and bacteria. In the book Ben Cao gang mu of China, there are also records of "psoriasis (powder) pressing five zang organs, calming the heart, arresting convulsion, removing pathogenic qi, and taking for a long time to lighten body and grow years". The authors of the "human and silver" study found that the Robode Beacon: the immunity of human body is greatly dependent on silver, and if the content of silver in the body is lower than the standard level (0.0001%), the possibility of disease is increased. Many heavy metal ions such as iron (Fe), manganese (Mn), zinc (Zn), lead (Pb), tin (Sn), mercury (Hg), copper (Cu), cadmium (Cd), etc. have strong bactericidal ability. However, these metal ions can be toxic and life threatening when used in excess of a certain amount. Some ions also have strong toxicity and cannot directly contact with human body, such as lead, cadmium, etc. On the other hand, metals generally have high specific gravity, cannot be used as wearing protective clothing alone, some metals are expensive, and the pure products cannot be used as the protective clothing.
Many manufacturers mix metal ions into plastic fabrics to improve the sterilization and antivirus effects of the fabrics, and clothes with anion and masks with copper ions are commonly contained on the surfaces of the fabrics on the market. The fabric is typically extruded with a metal salt compound incorporated therein in an amount that does not achieve the desired viral and bacterial kill objective. However, the fabric material obtained by the method has single metal ion type, can also generate the migration and aggregation of metal salt for a long time, has unstable performance, and causes the rapid loss of the metal ions on the surface of the fabric material due to water washing, limited use times and potential pollution to the environment.
Disclosure of Invention
Aiming at the defects, the invention provides an antiviral and antibacterial amino acid-based polymer, the obtained polymer is a lactam-amino acid polymer, metal ions are firmly bonded on a polymer molecular chain through chemical bonds and are uniformly distributed on the molecular chain, the same polymer molecular chain can contain various different metal ions in a polymerization manner, the effect of killing viruses and bacteria is strengthened in a synergistic manner, the virus and bacteria killing rate is up to 99.9%, the content of the polymer is not influenced by washing, and the virus killing and sterilizing effects of the metal ions can be exerted for a long time.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of an antiviral and antibacterial amino acid-based polymer, which comprises the following steps:
reacting aromatic acid anhydride with basic amino acid to obtain an amino acid polymerization unit with an aromatic formic acid structure;
then reacting the amino acid polymerization unit with an aromatic formic acid structure with metal salt with antiviral and antibacterial effects to obtain an amino acid-aromatic formate polymerization unit;
finally, the amino acid-aromatic formate polymerization unit and the lactam are subjected to melt polymerization reaction to prepare the polymer with the antiviral and antibacterial effects (namely, lactam-amino acid polymer).
Further, the molar ratio of the aromatic acid anhydride to the basic amino acid is 0.5-1.5: 1 (preferably 0.8 to 1.2).
Further, the basic amino acid is selected from lysine, histidine or arginine.
Further, the aromatic acid anhydride is selected from phthalic anhydride, 1, 8-naphthalic anhydride, 2, 3-naphthalic anhydride, biphenyldicarboxylic anhydride, 3', 4' -biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic anhydride, pyromellitic dianhydride, and 3,4,9, 10-perylenetetracarboxylic dianhydride.
Further, an amino acid polymerization unit with an aromatic formic acid structure obtained by reacting aromatic acid anhydride and basic amino acid is shown as a formula I:
Figure GDA0003937696540000021
in formula I, ar is derived from an aromatic structure corresponding to one of the following compounds:
Figure GDA0003937696540000031
further, the molar ratio of the amino acid polymer unit having an aromatic formic acid structure to the metal salt is 0.5 to 1.5:1 (preferably 0.8 to 1.2.
Further, the metal salt (MX) having antiviral and antibacterial effects is selected from the group consisting of: silver nitrate (AgNO) 3 ) Copper carbonate (CuCO) 3 ) Copper sulfate (CuSO) 4 ) Copper chloride (CuCl) 2 ) Silver carbonate (Ag) 2 CO 3 ) Silver acetate (AgOOCCH) 3 ) Zinc carbonate (ZnCO) 3 ) Zinc sulfate (ZnSO) 4 ) Zinc chloride (ZnCl) 2 ) Nickel carbonate (NiCO) 3 ) Nickel sulfate (NiSO) 4 ) Nickel chloride (NiCl) 2 ) Cobalt carbonate (CoCO) 3 ) Cobalt sulfate (CoSO) 4 ) Cobalt nickel chloride (CoCl) 2 ) Ferrous sulfate (FeSO) 4 ) Ferrous chloride (FeCl) 2 ) Manganese sulfate (MnSO) 4 ) Or manganese chloride (MnCl) 2 ) And the like.
Further, the molar ratio of the polymerized units of the cyclic lactam and the amino acid-aromatic formate is 80 to 99.9:0.1 to 20.
Further, the cyclic lactam is selected from at least one of the following: delta-valerolactam
Figure GDA0003937696540000032
Figure GDA0003937696540000033
Gamma-butyrolactams, processes for their preparation and their use,
Figure GDA0003937696540000034
Epsilon-caprolactam,
Figure GDA0003937696540000035
Omega-heptanesA lactam,
Figure GDA0003937696540000036
Caprylolactam or
Figure GDA0003937696540000037
Omega-laurolactam.
Further, the method for reacting the aromatic acid anhydride with the basic amino acid to obtain the amino acid polymerization unit with the aromatic formic acid structure comprises the following steps: under the protection of inert gas, aromatic acid anhydride and basic amino acid react in polar aprotic solvent at 0-200 ℃ for 1-8 hours, and after the reaction is finished, the amino acid polymerization unit with the aromatic formic acid structure is obtained by washing and drying.
Further, the polar aprotic solvent is selected from: n, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide (HMPA), N-Dimethylformamide (DMF), N-methylcaprolactam (NMC), N-vinylpyrrolidone (NVP), 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea (TMU), dimethyl sulfoxide (DMSO), or sulfolane (TMES); the dosage of the solvent is 1mol of amino acid: 500 to 2000ml of solvent, preferably 1mol amino acid: 1000-1500 ml.
Preferably, the reaction temperature is 20-150 ℃, and the reaction time is 2-6 hours.
Further, washing with deionized water, wherein the water consumption for washing is 1mol of amino acid: 600 to 1500ml of water, preferably 1mol of amino acid: 800-1200 ml (water).
Further, the method for preparing the amino acid-aromatic formate polymerization unit by reacting the amino acid polymerization unit with the aromatic formic acid structure with the metal salt with the antiviral and antibacterial effects comprises the following steps: adding an amino acid polymerization unit with an aromatic formic acid structure into deionized water under stirring, then adding metal salt with antiviral and antibacterial effects, and stirring and reacting for 2-8 hours at 0-95 ℃ under the protection of inert gas; and after the reaction is finished, filtering, washing and drying to obtain the amino acid-aromatic formate polymerization unit.
Preferably, the reaction temperature is 20-80 ℃, and the reaction time is 3-4 hours.
Further, the amount of deionized water added was 1mol of the amino acid polymerization unit having an aromatic formic acid structure: 500-2000 ml of water, preferably 1 mol.
Further, the method for preparing the polymer with antiviral and antibacterial effects by carrying out melt polymerization reaction on the amino acid-aromatic formate polymerization unit and the cyclic lactam comprises the following steps: adding the cyclic lactam and amino acid-aromatic formate polymerization unit into deionized water to dissolve most of the cyclic lactam to form a uniform solution or suspension with the amino acid-aromatic formate polymerization unit; gradually heating to 180-210 ℃ under the protection of inert gas, and then preserving heat at 210 ℃ for 1-5 hours; then gradually heating to 215-250 ℃, and keeping the temperature for 0.5-3.5 hours in the temperature range; and finally, cooling to room temperature to obtain the ionic bond polyamino acid with antiviral and antibacterial functions, namely the antiviral and antibacterial amino acid-based polymer.
Further, the antivirus and antibacterial amino acid-based polymer is melt spun and woven into various antivirus and antibacterial fabrics for use; wherein the melt spinning temperature is 160-260 ℃, preferably 180-220 ℃; the spinning winding speed is 2000-2500m/min, and the stretching ratio is 4-5 times.
The second technical problem to be solved by the present invention is to provide an antiviral and antibacterial amino acid-based polymer, which is prepared by the above preparation method.
Further, the structural formula of the antiviral and antibacterial amino acid-based polymer is shown as formula II:
Figure GDA0003937696540000061
in formula II, n 1 ≥100，n 2 ≥1；(n 1 The polymerization degree of the ring-opening lactam is more than 100, the mechanical strength can meet the use requirement, and n 2 By adding aromatic amino acid salt and ring-opening lactam to copolymerize, at least copolymerize, i.e. ring-opening lactam polymer with certain molecular weight and aromatic ammoniaCopolymerization of the base acid salt); m is metal with antiviral and antibacterial effects;
Figure GDA0003937696540000062
ar is derived from an aromatic structure corresponding to one of the following compounds:
phthalic anhydride
Figure GDA0003937696540000063
1, 8-naphthalic anhydride
Figure GDA0003937696540000064
2, 3-naphthalic anhydride
Figure GDA0003937696540000065
Biphenyl dicarboxylic anhydrides
Figure GDA0003937696540000066
3,3', 4' -Biphenyltetracarboxylic dianhydride
Figure GDA0003937696540000067
1,4,5, 8-Naphthalenetetracarboxylic anhydride
Figure GDA0003937696540000068
Pyromellitic dianhydride
Figure GDA0003937696540000071
Or 3,4,9, 10-perylene tetracarboxylic acid anhydride
Figure GDA0003937696540000072
The invention has the beneficial effects that:
the lactam-amino acid polymer obtained by the invention enables metal ions to be firmly bonded on a polymer molecular chain through chemical bonds, so that the metal ions are uniformly distributed on the molecular chain, the same polymer molecular chain can contain various different metal ions in a polymerization manner, the effect of killing viruses and bacteria is synergistically enhanced, the virus and bacteria killing rate is up to 99.9%, the content of the polymer is not influenced by washing, and the virus killing and sterilizing effects of the metal ions can be exerted for a long time.
Detailed Description
The first technical problem to be solved by the invention is to provide a preparation method of an antiviral and antibacterial amino acid-based polymer, which comprises the following steps:
reacting aromatic acid anhydride with basic amino acid to obtain an amino acid polymerization unit with an aromatic formic acid structure shown in a formula I; the amino acid polymerization unit with the aromatic formic acid structure contains a formic acid group with higher activity, so that the next reaction with metal salt can be carried out, and antiviral and antibacterial efficient metal ions are introduced into amino acid molecules;
Figure GDA0003937696540000073
then reacting the amino acid polymerization unit with an aromatic formic acid structure with metal salt with antiviral and antibacterial effects to obtain an amino acid-aromatic formate polymerization unit;
finally, the amino acid-aromatic formate polymerization unit and the cyclic lactam are subjected to melt polymerization reaction to prepare the polymer with the antiviral and antibacterial effects (namely, lactam-amino acid polymer); through the copolymerization reaction, the high-efficiency metal ions with antiviral and antibacterial functions are introduced into amino acid molecules and enter a polymer chain, so that the polymer is endowed with the high-efficiency antiviral and antibacterial functions.
Further, the antiviral and antibacterial amino acid-based polymer has an ionic polyamino acid with a side chain as a basic skeleton, which is represented by the formula (II):
Figure GDA0003937696540000081
wherein R is
Figure GDA0003937696540000082
M is silver (Ag), iron (Fe), nickel (Ni), manganese (Mn), zinc (Zn), lead (Pb), tin (Sn), mercury (Hg), copper (Cu), cadmium (Cd), etc.;
ar is derived from one of the following compounds:
phthalic anhydride
Figure GDA0003937696540000083
1, 8-naphthalic anhydride
Figure GDA0003937696540000084
2, 3-naphthalic anhydride
Figure GDA0003937696540000085
Biphenyl dicarboxylic anhydride
Figure GDA0003937696540000086
3,3', 4' -Biphenyltetracarboxylic dianhydride
Figure GDA0003937696540000087
1,4,5, 8-Naphthalenetetracarboxylic anhydride
Figure GDA0003937696540000088
Pyromellitic dianhydride
Figure GDA0003937696540000091
Or 3,4,9, 10-perylene tetracarboxylic acid anhydride
Figure GDA0003937696540000092
The polymers of the formula (II) can be exemplified by the following:
Figure GDA0003937696540000093
r is lysine, M is silver (Ag) or copper (Cu),
Figure GDA0003937696540000094
can be epsilon-caprolactam, and m =5.
The antiviral and antibacterial polymer can be prepared by the following steps:
1) Firstly, aromatic acid anhydride reacts with basic amino acid in a polar aprotic solvent to obtain an amino acid polymerization unit with an aromatic formic acid structure, wherein the reaction formula is as follows:
Figure GDA0003937696540000095
2) The amino acid-aromatic formate polymerization unit is prepared by reacting the amino acid polymerization unit with an aromatic formic acid structure with metal salt with antiviral and antibacterial effects, and the reaction formula is as follows:
Figure GDA0003937696540000101
3) The polymer with antiviral and antibacterial functions (lactam-amino acid polymer) is prepared by carrying out melt polymerization reaction on amino acid-aromatic formate polymerization units and cyclic lactam, and the reaction formula is as follows:
Figure GDA0003937696540000102
specifically, the preparation process of the antiviral and antibacterial polymer of the present invention is illustrated by lysine and phthalic anhydride as examples:
1) Lysine was reacted with phthalic anhydride under nitrogen in DMAc to form lysine benzamide phthalic acid, according to the following equation:
Figure GDA0003937696540000111
2) Adding lysine benzamide phthalic acid into water under stirring, adding silver nitrate or copper sulfate (sodium hydroxide to adjust the pH value), stirring and reacting for 2-8 hours under the protection of nitrogen, wherein the reaction temperature is 0-95 ℃ at room temperature; after the reaction is finished, filtering and washing the mixture for 4 times by deionized water, and carrying out vacuum drying for 5-15 hours at the temperature of 80 ℃ to obtain lysine benzamide silver o-benzoate or lysine benzamide copper o-benzoate; the reaction formula is as follows:
Figure GDA0003937696540000112
3) The polymerization reaction of the cyclic lactam and the polymerized unit of the amino acid-aromatic formate can prepare the ionic bond polyamino acid with the antiviral and antibacterial functions, and the reaction formula can be as follows:
Figure GDA0003937696540000121
Figure GDA0003937696540000131
the following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
148.11g of phthalic anhydride dried in vacuum at 80 ℃ and 146.19g of lysine are added into 1000ml of calcined calcium oxide dried DMAc in a 3L reactor with dry nitrogen protection, stirring and a thermometer, stirring is carried out for 2 hours, then the reaction solution is poured into normal-temperature deionized water, stirring and washing are carried out, after 4 times of repeated washing, washing is carried out for 2-3 times by absolute ethyl alcohol, and drying is carried out in a vacuum oven at 80 ℃ for 10 hours, thus obtaining lysine benzamide phthalic acid for later use.
The lysine benzamide phthalic acid is added into 1000ml of deionized water, stirred until the lysine benzamide phthalic acid is completely dissolved, 166.91g of silver acetate is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water, and dried in vacuum at 80 ℃ for 8 hours, and lysine benzamide silver (Ag) anthranilate is 400g for standby.
Weighing 1120.2g of epsilon-caprolactam and 4g of silver (Ag) lysine benzamide o-benzoate respectively, adding the weighed materials into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuing to heat to 210 ℃ after the dehydration is finished, performing prepolymerization for 1 hour in a molten state, continuing to heat to 220 ℃ for polymerization for 3 hours, finishing the reaction, cooling to room temperature, crushing the obtained polyamino acid into 100-mesh particles to obtain 1120g of poly epsilon-caprolactam-lysine benzamide o-benzoic acid silver polymer, crushing the poly epsilon-caprolactam-lysine benzamide o-benzoic acid silver polymer into 100-mesh particles, obtaining the antiviral and antibacterial poly epsilon-caprolactam-lysine benzamide o-benzoic acid silver polymer, and storing the antiviral and antibacterial poly epsilon-caprolactam-lysine benzamide o-benzoic acid silver polymer in a vacuum drier for later use.
And (3) carrying out melt spinning test on the poly-epsilon-caprolactam acid lysine benzamide silver anthranilate polymer particles, wherein the melt spinning temperature is 210-235 ℃, the spinning winding speed is 2000-2500m/min, and the stretching ratio is 4.5 times, and the strength and the antibacterial effect are tested.
The antibacterial effect test is carried out according to GB/T2951 and GB/T31402-2015 methods, and the test is carried out by adopting staphylococcus aureus and escherichia coli. The fiber strength is in accordance with the national standard of FZ/T54007-2019 nylon 6 stretch yarn. Cytotoxicity was as follows: GB/T16175-2008.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.5% and 99.8% respectively; (2) monofilament breaking strength (cN/dtex): 3.3; (3) cytotoxicity: no toxicity, grade 1.
Example 2
148.11g of phthalic anhydride and 146.19g of lysine which are dried in vacuum at 80 ℃ are added into a 3L reactor with dry nitrogen protection, stirring and a thermometer, 1000ml of calcined calcium oxide dried DMAc and stirred for 2 hours, then the reaction solution is poured into deionized water at normal temperature, stirred and washed, and after 4 times of stirring and washing, the reaction solution is washed for 2 to 3 times by absolute ethyl alcohol and dried for 10 hours at 80 ℃ in a vacuum oven, and lysine benzamide phthalic acid is obtained for standby.
The lysine benzamide phthalic acid is added into 1000ml of deionized water, stirred until the lysine benzamide phthalic acid is completely dissolved, 61.66g of copper carbonate (Cu) is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water and dried in vacuum at 80 ℃ for 8 hours, and 320g of lysine, benzamide and copper phthalate are reserved.
Weighing 1120.2g of epsilon-caprolactam and 4g of lysine benzamide copper phthalate respectively, adding the weighed materials into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuing to heat to 210 ℃ after the dehydration is finished, performing prepolymerization in a molten state for 1 hour, continuing to heat to 220 ℃ for polymerization for 3 hours, finishing the reaction, cooling to room temperature, crushing the obtained polyamino acid into 100-mesh particles to obtain 1120g of poly-epsilon-caprolactam-lysine benzamide copper phthalate, crushing the polymer into 100-mesh particles to obtain the antiviral and antibacterial poly-epsilon-caprolactam-lysine benzamide copper phthalate polymer, and storing the antiviral and antibacterial poly-epsilon-caprolactam-lysine benzamide copper phthalate polymer in a vacuum drier for later use.
And (3) carrying out melt spinning test on the poly-epsilon-caprolactam-lysine benzamide copper phthalate polymer particles at the temperature of 210-230 ℃, at the winding speed of 2000-2500m/min and at the stretching ratio of 4.3 times, and testing the strength and the antibacterial effect.
The antibacterial effect test method comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.6% and 99.7%, respectively; (2) monofilament breaking strength (cN/dtex): 3.2; (3) cytotoxicity: no toxicity, grade 1.
Example 3
148.11g of phthalic anhydride and 146.19g of lysine which are dried in vacuum at 80 ℃ are added into a 3L reactor with dry nitrogen protection, stirring and a thermometer, 1000ml of calcined calcium oxide dried DMAc and stirred for 2 hours, then the reaction solution is poured into deionized water at normal temperature, stirred and washed, and after 4 times of stirring and washing, the reaction solution is washed for 2 to 3 times by absolute ethyl alcohol and dried for 10 hours at 80 ℃ in a vacuum oven, and lysine benzamide phthalic acid is obtained for standby.
The lysine benzamide phthalic acid is added into 1000ml of deionized water, stirred until the lysine benzamide phthalic acid is completely dissolved, then 63g of zinc carbonate (Zn) is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water and dried in vacuum at 80 ℃ for 8 hours, and 300g of zinc benzyl phthalate (Zn) as lysine benzamide is reserved.
Weighing 1120.2g of epsilon-caprolactam and 6g of lysine benzamide zinc o-benzoate (Zn) respectively, adding the weighed materials into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuing to heat to 210 ℃ after the dehydration is finished, prepolymerizing for 1 hour in a molten state, continuing to heat to 220 ℃ for polymerization for 3 hours, finishing the reaction, cooling to room temperature, crushing the obtained polyamino acid into particles of 100 meshes, crushing 1120g of poly epsilon-caprolactam-lysine benzamide zinc o-benzoate (Zn) polymer into particles of 100 meshes, obtaining the antiviral and antibacterial poly epsilon-caprolactam-lysine benzamide zinc o-phthalate polymer, and storing the antiviral and antibacterial poly epsilon-caprolactam-lysine benzamide zinc o-phthalate polymer in a vacuum drier for later use.
The poly-epsilon-caprolactam-lysine benzamide zinc phthalate polymer particles are taken to carry out melt spinning test, the melt spinning temperature is 210-235 ℃, and the spinning winding speed is 2000-2500m/min. The stretching ratio was 4.5 times, and the strength and the antibacterial effect were measured.
The method for testing the antibacterial effect comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 Chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.5% and 99.8% respectively; (2) monofilament breaking strength (cN/dtex): 3.5; (3) cytotoxicity: no toxicity, grade 1.
Example 4
148.11g of phthalic anhydride dried in vacuum at 80 ℃ and 146.19g of lysine are added into 1000ml of calcined calcium oxide dried DMAc in a 3L reactor with dry nitrogen protection, stirring and thermometer for 2 hours (294.3 g), then the reaction solution is poured into normal temperature deionized water, stirred and washed, after 4 times of repeated washing, the reaction solution is washed with absolute ethyl alcohol for 2-3 times, and dried in a vacuum oven at 80 ℃ for 10 hours to obtain lysine benzamide phthalic acid for later use.
The lazy amino acid benzamide phthalic acid is added into 1000ml deionized water, stirred until the lazy amino acid benzamide phthalic acid is completely dissolved, 166.91g of silver acetate is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water and dried in vacuum at 80 ℃ for 8 hours, and lysine benzamide silver (Ag) was used 400g.
Weighing 1259.1g of omega-enantholactam and 4g of lysine benzamide silver (Ag) phthalate respectively, adding into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, and heating to 180 ℃ for dehydration (whether dehydration treatment is finished can be judged by observing whether amino acid starts to melt or not). And after dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization for 3 hours, finishing the reaction, cooling to room temperature, crushing the obtained polymer into 100-mesh particles to obtain 1129g of poly omega-enantholactam-lysine benzamide silver anthranilate polymer powder, obtaining the antiviral and antibacterial ionic bond polyamino acid, and storing in a vacuum drier for later use.
The poly-omega-enantholactam lysine benzamide silver anthranilate polymer particles are taken to carry out melt spinning test, the melt spinning temperature is 215-240 ℃, and the spinning winding speed is 2000-2500m/min. The stretching ratio was 4.5 times, and the strength and the antibacterial effect were measured.
The method for testing the antibacterial effect comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.7% and 99.9% respectively; (2) monofilament breaking strength (cN/dtex): 3.8 of the total weight of the mixture; (3) cytotoxicity: no toxicity, grade 1.
Example 5
198.17g of 1, 8-naphthalic anhydride dried in vacuum at 80 ℃ and 146.19g of lysine are added into NMP dried by 1000ml of calcined calcium oxide in a 3L reactor with dry nitrogen protection, stirring and a thermometer, stirred for 2 hours, then the reaction solution is poured into deionized water at normal temperature, stirred and washed, after 4 times of repeated washing, washed with absolute ethyl alcohol for 2-3 times, and dried in a vacuum oven at 80 ℃ for 10 hours to obtain lysine naphthamide naphthoic acid for later use.
The lysine naphthalene formamide naphthoic acid is added into 1000ml deionized water, stirred until the lysine naphthalene formamide naphthoic acid is completely dissolved, 166.91g of silver acetate is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water and dried in vacuum at 80 ℃ for 8 hours, and lysine, naphthalene formamide, and silver naphthoate (Ag) are 450g for standby.
Respectively weighing 1120.2g of epsilon-caprolactam and 4.5g of lysine naphthalene formamide silver naphthoate (Ag), adding the weighed materials into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuously heating to 210 ℃ after the dehydration is finished, performing prepolymerization in a molten state for 1 hour, continuously heating to 220 ℃ for polymerization for 3 hours, completing the reaction, cooling to room temperature to obtain 1121g of poly epsilon-caprolactam-indolenine naphthalene formamide silver naphthoate polymer, crushing into 100-mesh particles to obtain the ionic bond polyamino acid with antiviral and antibacterial effects, and storing in a vacuum drier for later use.
Taking poly-epsilon-caprolactam-lysine naphthalene formamide silver naphthoate polymer particles to carry out melt spinning test, wherein the melt spinning temperature is 215-235 ℃, and the spinning winding speed is 2200-2500m/min. The stretching ratio is 4.2 times, and the strength and the antibacterial effect are measured.
The method for testing the antibacterial effect comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.5% and 99.8% respectively; (2) monofilament breaking strength (cN/dtex): 3.3; (3) cytotoxicity: no toxicity, grade 1.
Example 6
1120.2g of epsilon-caprolactam, 2g of lysine benzamide o-benzyl silver (Ag) obtained in example 1 and 2g of lysine benzamide copper (Cu) obtained in example 2 are respectively weighed, added into a 2500ml three-necked bottle, 500ml of distilled water is added, nitrogen is introduced for protection, stirring is carried out, the temperature is increased to 180 ℃ for dehydration, after dehydration is finished, the temperature is continuously increased to 210 ℃, prepolymerization is carried out for 1 hour in a molten state, then the temperature is continuously increased to 220 ℃ for polymerization for 3 hours, reaction is finished, cooling is carried out to room temperature, the obtained polyamino acid is crushed into 100-mesh particles, 1121g of poly epsilon-caprolactam-lysine benzamide o-benzyl copper phthalate polymer is obtained, the poly epsilon-caprolactam-lysine benzamide o-benzyl copper polymer is crushed into 100-mesh particles, the antiviral and antibacterial ionic bond polyamino acid is obtained, and the particles are stored in a vacuum drier for later use.
Taking poly-epsilon-caprolactam-lysine benzamide copper silver phthalate polymer particles to carry out melt spinning test, wherein the melt spinning temperature is 215-235 ℃, and the spinning winding speed is 2300-2400m/min; the stretching ratio was 4.3 times, and the strength and the antibacterial effect were measured.
The method for testing the antibacterial effect comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.9% and 99.9% respectively; (2) monofilament breaking strength (cN/dtex): 3.2; (3) cytotoxicity: no toxicity, grade 1.
Example 7
148.11g of phthalic anhydride dried in vacuum at 80 ℃ and 146.19g of lysine are added into 1000ml of calcined calcium oxide dried DMAc in a 3L reactor with dry nitrogen protection, stirring and a thermometer, stirring is carried out for 2 hours, then the reaction solution is poured into normal-temperature deionized water, stirring and washing are carried out, after 4 times of repeated washing, washing is carried out for 2-3 times by absolute ethyl alcohol, and drying is carried out in a vacuum oven at 80 ℃ for 10 hours, thus obtaining lysine benzamide phthalic acid for later use.
The lysine benzamide phthalic acid is added into 1000ml deionized water, stirred until the lysine benzamide phthalic acid is completely dissolved, 166.91g of silver acetate is added, and stirring is continued for two hours. The reaction solution was then added to 5000ml of deionized water, stirred for ten minutes, and filtered. Then washed 6 times with deionized water and dried in vacuum at 80 ℃ for 8 hours, and lysine benzamide silver o-benzoate (Ag) is 400g for standby.
Weighing 1120.2g of epsilon-caprolactam and 2g of lysine benzamide silver o-benzoate (Ag), adding the weighed materials into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuing to heat to 210 ℃ after the dehydration is finished, performing prepolymerization in a molten state for 1 hour, continuing to heat to 220 ℃ for polymerization for 3 hours, finishing the reaction, cooling to room temperature, crushing the obtained polymer acid into 100-mesh particles to obtain 1120g of poly-epsilon-caprolactam-lysine benzamide silver o-benzoate polymer, and storing the poly-epsilon-caprolactam-lysine benzamide silver o-benzoate polymer in a vacuum drier for later use.
And carrying out melt spinning test on the poly-epsilon-caprolactam-lysine benzamide silver anthranilate polymer particles, wherein the melt spinning temperature is 180-230 ℃, and the spinning winding speed is 2000-2500m/min. The stretching ratio was 4.5 times, and the strength and the antibacterial effect were measured.
The method for testing the antibacterial effect comprises the following steps: the detection is carried out according to the method GB/T31402-2015, and staphylococcus aureus and escherichia coli are adopted for testing. The fiber strength was as follows: FZ/T54007-2019 chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.5% and 99.8% respectively; (2) monofilament breaking strength (cN/dtex): 3.4; (3) cytotoxicity: no toxicity, grade 1.
Example 8
The other steps are the same as example 1, and only differ: the dosage of the lysine benzamide silver benzoate (Ag) is 0.4g.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.2% and 99.5% respectively; (2) monofilament breaking strength (cN/dtex): 3.5; (3) cytotoxicity: no toxicity, grade 0.
Example 9
The other steps are the same as the embodiment 1, and only differ: the reaction with epsilon-caprolactam was carried out using 0.4g of silver (Ag) lysine benzamide anthranilate obtained in example 1, 1g of copper (Cu) lysine benzamide phthalate obtained in example 2, and 1g of zinc (Zn) lysine benzamide phthalate obtained in example 3, instead of the silver (Ag) lysine benzamide anthranilate in example 1.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.9% and 99.9% respectively; (2) monofilament breaking strength (cN/dtex): 3.5; (3) cytotoxicity: no toxicity, grade 0.
Example 10
Otherwise, the same as example 4, only differences are: the reaction was carried out using 0.4g of silver (Ag) lysine benzamide anthranilate obtained in example 1, 1g of copper (Cu) lysine benzamide phthalate obtained in example 2, and 1g of zinc (Zn) lysine benzamide phthalate obtained in example 3, instead of the silver (Ag) lysine benzamide anthranilate in example 4, with ω -heptanolactam.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 99.9% and 99.9% respectively; (2) monofilament breaking strength (cN/dtex): 3.9; (3) cytotoxicity: no toxicity, grade 0.
Comparative example 1
Weighing 1131g of epsilon-caprolactam, adding the epsilon-caprolactam into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, raising the temperature to 202 ℃ until all water is removed, continuously raising the temperature to 210 ℃, prepolymerizing in a molten state for 1 hour, continuously raising the temperature to 220 ℃ for polymerization for 4 hours to complete reaction, cooling to room temperature, and crushing the obtained polycaprolactam into particles with 100 meshes. Taking poly-epsilon-amino caproic acid lysine particles to carry out melt spinning test, wherein the melt spinning temperature is 210-230 ℃, and the spinning winding speed is 2000-2500m/min; the stretching ratio is 4.5 times; the strength and the antibacterial effect of the antibacterial agent are measured.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 45.9% and 39.9% respectively; it has poor antibacterial effect; (2) monofilament breaking strength (cN/dtex): 3.6; (3) cytotoxicity: no toxicity, grade 1.
Comparative example 2
1079g of epsilon-caprolactam and 75g of lysine are weighed and added into a 2500ml three-necked bottle, 500ml of distilled water is added, nitrogen is introduced for protection, the mixture is stirred and heated to 180 ℃ for dehydration, the water is completely dehydrated when the temperature is raised to 202 ℃, the temperature is continuously raised to 210 ℃, the mixture is subjected to prepolymerization for 1 hour in a molten state, then the mixture is continuously raised to 220 ℃ for polymerization for 4 hours, the reaction is completed, the mixture is cooled to room temperature, and the obtained polyamino acid is crushed into particles of 100 meshes. The poly epsilon-caprolactam-lysine particles are taken to carry out melt spinning test, the melt spinning temperature is 210-230 ℃, and the winding speed of the spinning is 2000-2500m/min. The stretching ratio was 4.5 times, and the strength and the antibacterial effect were measured.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 55.3% and 61.5%, respectively; the lysine has certain antibacterial effect, but the overall antibacterial effect of the polymer is poor; (2) monofilament breaking strength (cN/dtex): 3.3; (3) cytotoxicity: no toxicity, grade 1.
Comparative example 3
Weighing 50g of silver carbonate, and pressing
Figure GDA0003937696540000201
The small disks of (4) were tested for performance.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 100% and 100% respectively; (2) it cannot be used as a flexible material; (3) cytotoxicity: high toxicity, grade 5.
Comparative example 4
Respectively weighing 1271g of omega-enantholactam, adding the weighed omega-enantholactam into a 2500ml three-necked bottle, adding 500ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, continuing to heat to 210 ℃ after the dehydration is finished, performing prepolymerization in a molten state for 1 hour, continuing to heat to 220 ℃ for polymerization for 3 hours, finishing the reaction, cooling to room temperature, and crushing the obtained polyamino acid into 100-mesh particles.
The poly omega-enantholactam particles are taken to carry out melt spinning test, the melt spinning temperature is 215-240 ℃, and the winding speed of the spinning is 2000-2500m/min. The stretching ratio is 4.5 times, and the strength and the antibacterial effect are measured.
The method for testing the antibacterial effect comprises the following steps: the test is carried out according to the method of GB/T31402-2015 by adopting staphylococcus aureus and escherichia coli. The fiber strength was as follows: FZ/T54007-2019 Chinlon 6 stretch yarn national standard.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 45.5% and 49.6% respectively; the antibacterial effect is basically not achieved; (2) monofilament breaking strength (cN/dtex): 3.9; (3) cytotoxicity: no toxicity, grade 1.
Comparative example 5
Weighing 50g of copper carbonate and 50g of zinc carbonate, uniformly mixing and pressing
Figure GDA0003937696540000202
The small disks of (4) were tested for performance.
And (3) testing results: (1) The inhibition rates of staphylococcus aureus and escherichia coli are 100% and 100% respectively; (2) it cannot be used as a flexible material; (3) cytotoxicity: high toxicity, grade 5.

Claims (18)

1. A preparation method of an antiviral and antibacterial amino acid-based polymer is characterized by comprising the following steps:
reacting aromatic acid anhydride with basic amino acid to obtain an amino acid polymerization unit with an aromatic formic acid structure;
then reacting the amino acid polymerization unit with an aromatic formic acid structure with metal salt with antiviral and antibacterial effects to obtain an amino acid-aromatic formate polymerization unit;
and finally, carrying out melt polymerization reaction on the amino acid-aromatic formate polymerization unit and the cyclic lactam to obtain the amino acid-based polymer with the antiviral and antibacterial functions.
2. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1, wherein the molar ratio of the aromatic acid anhydride to the basic amino acid is 0.5 to 1.5:1.
3. the method for preparing an antiviral-antibacterial amino acid-based polymer according to claim 1 or 2, wherein the basic amino acid is selected from lysine, histidine or arginine.
4. The method for preparing an antiviral and antibacterial amino acid based polymer according to claim 1 or 2, wherein said aromatic acid anhydride is selected from phthalic anhydride, 1, 8-naphthalic anhydride, 2, 3-naphthalic anhydride, biphenyldicarboxylic anhydride, 3', 4' -biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic anhydride, pyromellitic dianhydride, and 3,4,9, 10-perylenetetracarboxylic acid.
5. The method for preparing an antiviral-antibacterial amino acid-based polymer according to claim 1 or 2, wherein the molar ratio of the polymerized amino acid units having an aromatic formic acid structure to the metal salt is 0.5 to 1.5:1.
6. the method for preparing an antiviral-antibacterial amino acid-based polymer according to claim 1 or 2, wherein said metal salt having an antiviral-antibacterial effect is selected from the group consisting of: silver nitrate, copper carbonate, copper sulfate, copper chloride, silver carbonate, silver acetate, zinc carbonate, zinc sulfate, zinc chloride, nickel carbonate, nickel sulfate, nickel chloride, cobalt carbonate, cobalt sulfate, cobalt chloride, ferrous sulfate, ferrous chloride, manganese sulfate, or manganese chloride.
7. The method for preparing an antiviral-antibacterial amino acid-based polymer according to claim 1 or 2, wherein the molar ratio of the cyclic lactam to the polymerized units of the amino acid-aromatic formate is 80 to 99.9:0.1 to 20.
8. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1 or 2, wherein the cyclic lactam is at least one selected from the group consisting of: delta-valerolactam, gamma-butyrolactam, epsilon-caprolactam, omega-enantholactam, omega-caprylolactam or omega-laurolactam.
9. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1 or 2, wherein the method for reacting an aromatic acid anhydride with a basic amino acid to obtain an amino acid polymerized unit having an aromatic formic acid structure comprises: under the protection of inert gas, aromatic acid anhydride reacts with basic amino acid in polar aprotic solvent at 0-200 ℃ for 1-8 hours, and after the reaction is finished, the amino acid polymerization unit with the aromatic formic acid structure is obtained through washing and drying.
10. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 9, wherein the polar aprotic solvent is selected from the group consisting of: n, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, N-dimethylamide, N-methylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethylsulfoxide, or sulfolane; the solvent dosage is 1mol of amino acid: 500-2000 ml of solvent.
11. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 9, wherein the reaction temperature is 20 to 150 ℃ and the reaction time is 2 to 6 hours.
12. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 9, wherein the washing is performed using deionized water in an amount of 1mol of amino acid: 600-1500 ml of water.
13. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1 or 2, wherein the method for preparing the amino acid-aromatic formate polymerized unit by reacting the amino acid polymerized unit having an aromatic formic acid structure with the metal salt having an antiviral and antibacterial effect comprises: adding an amino acid polymerization unit with an aromatic formic acid structure into deionized water under stirring, then adding metal salt with antiviral and antibacterial effects, and stirring and reacting for 2-8 hours at 0-95 ℃ under the protection of inert gas; and after the reaction is finished, filtering, washing and drying to obtain the amino acid-aromatic formate polymerization unit.
14. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 13, wherein the reaction temperature is 20 to 80 ℃ and the reaction time is 3 to 4 hours.
15. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1 or 2, wherein deionized water is added in an amount of 1mol of the amino acid polymerization unit having an aromatic formic acid structure: 500-2000 ml of water.
16. The method for preparing an antiviral and antibacterial amino acid-based polymer according to claim 1 or 2, wherein said melt-polymerizing amino acid-aromatic formate polymerized units with cyclic lactam to obtain said antiviral and antibacterial polymer is: adding the cyclic lactam and amino acid-aromatic formate polymerization unit into deionized water to dissolve most of the cyclic lactam to form a uniform solution or suspension with the amino acid-aromatic formate polymerization unit; under the protection of inert gas, the temperature is gradually increased to 180-210 ℃, and then the temperature is kept at 210 ℃ for 1-5 hours; then gradually raising the temperature to 215-250 ℃, and keeping the temperature for 0.5-3.5 hours in the temperature interval; and finally, cooling to room temperature to obtain the ionic bond polyamino acid with antiviral and antibacterial functions, namely the antiviral and antibacterial amino acid-based polymer.
17. The method for preparing an antiviral-antibacterial amino acid-based polymer according to claim 1 or 2, wherein the antiviral-antibacterial amino acid-based polymer is used by melt spinning and knitting into various antiviral-antibacterial fabrics; wherein the melt spinning temperature is 160-260 ℃, the spinning winding speed is 2000-2500m/min, and the stretching multiple is 4-5 times.
18. An antiviral and antibacterial amino acid-based polymer, characterized in that it is obtained by the method according to any one of claims 1 to 17.
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