An antibacterial copolyamide and a method for its preparation

Abstract

This invention relates to an antibacterial copolyamide and its preparation method. The antibacterial copolyamide comprises a polyamide A structure formed by hexamethylenediamine and a dodecanoic acid, at least one polyamide B structure other than polyamide A, and an antibacterial agent C structure. The polyamide B structure is formed by at least one diacid b1 and at least one diamine b2, and / or by ring-opening of a lactam b3. The antibacterial agent C structure contains a quaternary phosphonium salt group and is formed by a quaternary phosphonium salt antibacterial agent containing a carboxylic acid group and the diamine b2. The melting point of the antibacterial copolyamide is 180℃~210℃. The antibacterial copolyamide of this invention exhibits good antibacterial stability, possesses highly efficient and long-lasting antibacterial effects, and does not affect the transparency of the polyamide itself.

Description

Technical Field

[0001] This invention belongs to the field of polyamide resin technology, specifically relating to an antibacterial polyamide and its preparation method. Background Technology

[0002] With rising living standards and health awareness, antibacterial nylon fabrics with "self-cleaning" properties are attracting increasing interest. These types of antibacterial fibers or fabrics can be used in many industries, including healthcare, hospitality, military, and sports. However, conventional antibacterial fibers or fabrics struggle to meet the requirements of these applications in practice. In many applications, reuse and washing cycles are quite common; unfortunately, it has been found that conventional nylon fabrics deteriorate during reuse or washing cycles, losing a significant proportion of their antibacterial properties. Ultimately, this prevents existing antibacterial nylon fibers from effectively meeting the actual application needs of the market and achieving large-scale production.

[0003] Chinese patent CN106633829A discloses an antibacterial nylon using attapulgite-nano silver composite inorganic powder as an antibacterial additive and its preparation method. While this antibacterial agent offers advantages such as high efficiency in small quantities, low cost, and simple process, it fails to consider the insufficient long-term stability of silver nanoparticle antibacterial agents, which are prone to aggregation and oxidative discoloration, thus affecting their long-term antibacterial activity. Chinese patent CN107541054A discloses an antibacterial nylon using a mixture of polyguanidine salt and sodium hydroxypyridinethione as an antibacterial agent and its preparation method. The antibacterial nylon material is obtained by melt-blending nylon with an antibacterial agent and dispersant, followed by extrusion granulation. However, the polyguanidine salt in this additive antibacterial agent has high water solubility, which can easily cause compatibility problems and yellowing with nylon materials under long-term use, potentially affecting the mechanical properties and chemical stability of the nylon material. Patent CN113502660A discloses a method for preparing modified polyamide fibers by polymerizing alkyl diguanidine salts and polyamides, and then spraying a finishing agent onto the fibers. This technology is complex, the antibacterial components are unevenly distributed and require large amounts, and post-treatment is necessary to ensure the antibacterial effect. Patent CN101942759A discloses a method for adding fibers to a solution containing silver nitrate to adsorb the silver nitrate in the solution, and then reducing the adsorbed fibers to obtain antibacterial fibers or fabrics with silver adhering to the surface. This method also cannot form a uniform and stable antibacterial coating, and the antibacterial time is limited, failing to achieve long-lasting antibacterial properties.

[0004] In summary, the main methods for achieving antibacterial function in nylon fibers are currently surface modification or blending modification techniques. However, neither of these techniques can solve the compatibility issues with the nylon bulk material or the problem of precipitation failure under long-term use conditions. Therefore, research on highly efficient and durable reactive antibacterial agents and long-lasting antibacterial polyamides is crucial. Summary of the Invention

[0005] Technical Problem: To overcome the above-mentioned technical defects, the present invention aims to disclose an antibacterial copolyamide and its preparation method. The invented antibacterial copolyamide has good antibacterial stability, possesses highly efficient and long-lasting antibacterial effects, and does not affect the transparency of the polyamide itself.

[0006] Technical solution: The antibacterial copolyamide of the present invention comprises a polyamide A structure formed by hexamethylenediamine and dodecanoic acid, at least one polyamide B structure other than polyamide A, and an antibacterial agent C structure;

[0007] The polyamide B structure is formed by at least one dicarboxylic acid b1 and at least one diamine b2, and / or by ring-opening of lactam b3;

[0008] The antibacterial agent C structure contains a quaternary phosphonium salt group and is formed by a quaternary phosphonium salt antibacterial agent containing a carboxylic acid group and a diamine b2.

[0009] The polyamide A structure accounts for 70% to 95% of the mass of the antibacterial copolyamide;

[0010] The polyamide B structure accounts for 4% to 29% of the mass of the antibacterial copolyamide;

[0011] The antibacterial agent C structure accounts for 0.2% to 1% of the mass of the antibacterial copolyamide;

[0012] The melting point of the antibacterial copolyamide is 180℃~210℃.

[0013] The dicarboxylic acid b1 includes aromatic dicarboxylic acids, preferably one or more of terephthalic acid, terephthalic acid, terephthalic propionic acid, isophthalic acid, isophthalic acid, phthalic acid, and phthalic acid.

[0014] The diamine b2 comprises, independently, a C2 to C14 diamine, preferably one or more of pentanediamine, hexanediamine, octanediamine, decanediamine, and 1,12-diaminododecane.

[0015] The lactam b3 includes one or more of butyrolactam, valproic acid lactam, caprolactam, octyl lactam, lauryl lactam, N-methylcaprolactam, N-vinylcaprolactam, and 4-tert-butylcaprolactam.

[0016] The aforementioned quaternary phosphonium salt antibacterial agents containing carboxylic acid groups include tributylcarboxymethyl phosphorus chloride and / or 2-(carboxyethyl)triphenylphosphine bromide.

[0017] The preparation method of the antibacterial copolyamide of the present invention is as follows:

[0018] The process is carried out in the presence of a protective gas. A solution containing polyamide A salt, a solution containing polyamide B salt and / or lactam b3, and a solution containing antibacterial agent C salt are mixed to form a mixed solution, and the mixed solution is polymerized to form an antibacterial copolyamide.

[0019] The solution containing polyamide A salt is formed by dissolving hexamethylenediamine and dodecanoic acid in a solvent to form a salt solution;

[0020] The solution containing polyamide B salt is formed by dissolving at least one dicarboxylic acid b1, at least one diamine b2, and / or lactam b3 in a solvent to form a salt solution.

[0021] The solution of the antibacterial agent C salt is formed by dissolving a quaternary phosphonium salt antibacterial agent containing a carboxylic acid group and a diamine b2 in a solvent to form a salt solution containing the antibacterial agent C salt.

[0022] The protective gas includes one or more of nitrogen, carbon dioxide, argon, and helium, and does not participate in the polymerization reaction; the polymerization temperature is 150℃~280℃, and the pressure is 0~2.0MPa.

[0023] The solvent mentioned includes water.

[0024] The temperatures of the polyamide A salt solution, the polyamide B salt solution, and the antibacterial agent C salt solution are controlled at 50℃ to 80℃, and the mass percentages are controlled at 20% to 60%, respectively.

[0025] Beneficial Effects: Compared to polyamides using conventional additive antibacterial agents or metal ion antibacterial agents, the antibacterial copolyamide of this invention exhibits better antibacterial stability, provides highly efficient and long-lasting antibacterial effects, and does not affect the transparency of the polyamide itself. The specific antibacterial agent C containing quaternary phosphonium salt is used as one of the structures of the polyamide, which not only plays an antibacterial role but also has certain catalytic and end-capping effects, and can regulate the molecular weight of the polyamide. Combined with the introduction of the polyamide B structure, it disrupts the regularity of polyamide A to a certain extent. While ensuring that the main polyamide A structure still maintains relatively complete regularity, it effectively slows down the crystallinity of the polyamide A structure, further enhancing the antibacterial effect. Detailed Implementation

[0026] The antibacterial copolyamide of the present invention comprises a polyamide A structure formed by hexamethylenediamine and dodecanoic acid, at least one polyamide B structure other than polyamide A, and an antibacterial agent C structure;

[0027] The polyamide B structure is formed by at least one dicarboxylic acid b1 and at least one diamine b2, and / or by ring-opening of lactam b3;

[0028] The diamine b1 includes C2 to C14 diamines, preferably one or more of pentanediamine, hexanediamine, octanediamine, decanediamine, and 1,12-diaminododecane;

[0029] The dicarboxylic acid b2 includes aromatic dicarboxylic acids, preferably including one or more of terephthalic acid, terephthalic acid, terephthalic propionic acid, isophthalic acid, isophthalic acid, phthalic acid, and phthalic acid.

[0030] The lactam b3 includes one or more of butyrolactam, valproic acid lactam, caprolactam, octyl lactam, lauryl lactam, N-methylcaprolactam, N-vinylcaprolactam, and 4-tert-butylcaprolactam;

[0031] The antibacterial agent C structure contains a quaternary phosphonium salt group and is formed by a quaternary phosphonium salt antibacterial agent containing a carboxylic acid group and a diamine b2;

[0032] The aforementioned quaternary phosphonium salt antibacterial agents containing carboxylic acid groups include tributylcarboxymethyl phosphorus chloride and / or 2-(carboxyethyl)triphenylphosphine bromide;

[0033] The diamine b2 includes C2 to C14 diamines, preferably one or more of pentanediamine, hexanediamine, octanediamine, decanediamine, and 1,12-diaminododecane;

[0034] The antibacterial polyamide has a melting point (Tm) of 180℃ to 210℃, preferably 195℃ to 205℃;

[0035] In this invention, the polyamide B structure mainly disrupts the regularity of the polyamide A structure to a certain extent. While ensuring that the polyamide A structure still has relatively complete regularity, it effectively slows down the crystallinity of the polyamide A structure, which macroscopically manifests as a slight decrease in melting point and an increase in transparency.

[0036] The polyamide A structure accounts for 70% to 95% of the mass of the antibacterial copolyamide;

[0037] The polyamide B structure accounts for 4% to 29% of the mass of the antibacterial copolyamide;

[0038] The antibacterial agent C structure accounts for 0.2% to 1% of the mass of the antibacterial copolyamide.

[0039] The present invention discloses a method for preparing an antibacterial copolyamide, wherein a solution containing polyamide A salt, a solution containing polyamide B salt and / or lactam b3 and a solution containing antibacterial agent C salt are mixed to form a mixed solution, and the mixed solution is polymerized to form an antibacterial copolyamide;

[0040] The preparation method is carried out in the presence of a protective gas, and the polymerization temperature is 150℃~280℃, and the pressure is 0~2.0MPa;

[0041] Preferably, the solvent can be removed by evaporation and concentration.

[0042] In some embodiments of the present invention, the preparation method of the antibacterial copolyamide specifically includes the following steps:

[0043] In the presence of a protective gas, a solution containing polyamide A salt and a solution containing polyamide B salt and / or lactam b3 are mixed, and then polymerized and evaporated to concentrate the solution to a mass percentage of 70% to 80% under conditions of 120℃~160℃ and 0.2~0.3MPa.

[0044] Add a solution containing antibacterial agent C salt and continue mixing. Continue the polymerization reaction at a temperature of 160℃~180℃ and a pressure of 1.5~2.0MPa. Finally, reduce the pressure to room temperature to obtain antibacterial copolyamide.

[0045] Preferably, the protective gas does not participate in the polymerization reaction and includes one or more of nitrogen, carbon dioxide, argon, and helium;

[0046] In some embodiments of the present invention, the protective gas is nitrogen;

[0047] Furthermore, the solution containing polyamide A salt is formed by dissolving hexamethylenediamine and dodecanoic acid in a solvent to form a salt solution;

[0048] The solution containing polyamide B salt is formed by dissolving at least one dicarboxylic acid b1 and at least one diamine b2 in a solvent to form a salt solution;

[0049] In some embodiments of the present invention, the polyamide B salt includes one or more of hexamethylene terephthalate, hexamethylene diphenyl terephthalate, hexamethylene diphenyl terephthalate, and pentanediamine isophthalate.

[0050] The solution containing lactam b3 is obtained by dissolving lactam b3 in a solvent;

[0051] In some embodiments of the present invention, the lactam b3 includes one or more of caprolactam, N-methylcaprolactam, N-vinylcaprolactam, 4-tert-butylcaprolactam, and lauryl lactam;

[0052] The solution containing antibacterial agent C salt is formed by dissolving a quaternary phosphonium salt antibacterial agent containing a carboxylic acid group and a diamine b2 in a solvent to form a salt solution;

[0053] The solvent includes water, and further, the water is desalted.

[0054] In some embodiments of the present invention, the mass ratio of polyamide A salt, polyamide B salt and / or lactam b3, and antibacterial agent C salt is 71-94: 5-28.5: 0.2-1.5;

[0055] The temperatures of the polyamide A salt solution, the polyamide B salt solution and / or lactam b3 solution, and the antibacterial agent C salt solution are controlled at 50℃~80℃, and the mass percentage content is controlled at 20~60%, respectively.

[0056] In some embodiments of the present invention, the temperature of the polyamide A salt solution is controlled at 50°C to 80°C, and the mass percentage is controlled at 50% to 60%; the temperature of the solution containing polyamide B salt and / or lactam b3 is controlled at 50°C to 80°C, and the mass percentage is controlled at 50% to 60%; the temperature of the antibacterial agent C salt solution is controlled at 50°C to 80°C, and the mass percentage is controlled at 20% to 30%.

[0057] Preferably, the polymerization reaction can be accelerated in the presence of a catalyst in the above steps, wherein the catalyst includes one or more of sodium hypophosphite, sodium phosphite, and potassium hypophosphite;

[0058] Preferably, additives known in the art may be added, including antioxidants, photothermal stabilizers, end-group modifiers, flame retardants, and high-temperature resistant additives;

[0059] The antioxidants mentioned are selected from hindered phenols, thioesters, phosphites, and aromatic amines.

[0060] The photothermal stabilizer is selected from hindered amines, benzotriazoles, or benzophenones.

[0061] The end-group regulator is selected from one or more of n-butylamine, n-pentylamine, n-hexylamine, benzylamine, phenethylamine, acetic acid, propionic acid, butyric acid, benzoic acid, and phenylacetic acid;

[0062] The heat-resistant agent is selected from organic copper, inorganic copper salts, and aromatic amine high-temperature resistant additives;

[0063] The flame retardant is selected from organophosphorus, organoaluminum, and melamine flame retardants.

[0064] The principles and features of this invention are described below with reference to specific examples. These examples are provided to facilitate a better understanding of the invention by those skilled in the art. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0065] Example 1

[0066] Antibacterial copolyamide 1 comprises 84% ​​by mass of polyamide A structure, 15.5% by mass of polyamide B structure, and 0.5% by mass of antibacterial agent C structure;

[0067] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0068] The polyamide B structure is formed through caprolactam ring-opening;

[0069] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0070] Example 2

[0071] Antibacterial copolyamide 2 comprises 75% polyamide A structure by mass, 24.7% polyamide B structure by mass, and 0.3% antibacterial agent C structure by mass.

[0072] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0073] The polyamide B structure is formed by hexamethylenediamine and terephthalic acid;

[0074] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0075] Example 3

[0076] The antibacterial copolyamide 3 comprises 86.2% by mass of polyamide A structure, 13% by mass of polyamide B structure, and 0.8% by mass of antibacterial agent C structure;

[0077] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0078] The polyamide B structure is formed by hexamethylenediamine and isophthalic acid;

[0079] The structure of antibacterial agent C is formed by 2-(carboxyethyl)triphenylphosphine bromide containing a carboxylic acid group and 1,12-diaminododecane.

[0080] Example 4

[0081] Antibacterial copolyamide 4 comprises 90% polyamide A structure, 9% polyamide B structure, and 1% antibacterial agent C structure by mass.

[0082] Among them, the polyamide A structure is formed by ring-opening caprolactam;

[0083] The polyamide B structure is formed by hexamethylenediamine and isophthalic acid;

[0084] The structure of antibacterial agent C is formed by combining 2-(carboxyethyl)triphenylphosphine bromide containing a carboxylic acid group and hexamethylenediamine.

[0085] Example 5

[0086] The antibacterial copolyamide 5 comprises 72.5% by mass of polyamide A structure, 27% by mass of polyamide B structure, and 0.5% by mass of antibacterial agent C structure;

[0087] Among them, the polyamide A structure is formed by ring-opening caprolactam;

[0088] The polyamide B structure is formed by hexamethylenediamine and terephthalic acid;

[0089] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0090] Example 6

[0091] Antibacterial copolyamide 6 comprises 75% polyamide A structure by mass, 24.7% polyamide B structure by mass, and 0.3% antibacterial agent C structure by mass.

[0092] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0093] The polyamide B structure is formed by hexamethylenediamine and adipic acid;

[0094] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0095] Example 7

[0096] Antibacterial copolyamide 7 comprises 84% ​​by mass of polyamide A structure, 15.5% by mass of polyamide B structure, and 0.5% by mass of antibacterial agent C structure;

[0097] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0098] The polyamide B structure is formed through caprolactam ring-opening;

[0099] The structure of antibacterial agent C is formed directly from dodecyl dimethylphenoxyethyl ammonium bromide.

[0100] Example 8

[0101] Antibacterial copolyamide 8 comprises 84% ​​by mass of polyamide A structure, 15.5% by mass of polyamide B structure, and 0.5% by mass of antibacterial agent C structure;

[0102] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0103] The polyamide B structure is formed through caprolactam ring-opening;

[0104] The structure of antibacterial agent C is formed directly through tributylcarboxymethyl phosphorus chloride.

[0105] Example 9

[0106] Antibacterial copolyamide 9 comprises 94% polyamide A structure, 5% polyamide B structure, and 1% antibacterial agent C structure by mass.

[0107] Among them, the polyamide A structure is formed by ring-opening caprolactam;

[0108] The polyamide B structure is formed by hexamethylenediamine and isophthalic acid;

[0109] The structure of antibacterial agent C is formed by combining 2-(carboxyethyl)triphenylphosphine bromide containing a carboxylic acid group and hexamethylenediamine.

[0110] Example 10

[0111] Antibacterial copolyamide 10 comprises 71% polyamide A structure, 28.5% polyamide B structure, and 0.5% antibacterial agent C structure by mass.

[0112] Among them, the polyamide A structure is formed by ring-opening caprolactam;

[0113] The polyamide B structure is formed by hexamethylenediamine and terephthalic acid;

[0114] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0115] Example 11

[0116] Antibacterial copolyamide 11 comprises 75.2% by mass of polyamide A structure, 24.7% by mass of polyamide B structure, and 0.1% by mass of antibacterial agent C structure;

[0117] Among them, the polyamide A structure is formed by hexamethylenediamine and dodecanoic acid;

[0118] The polyamide B structure is formed by hexamethylenediamine and terephthalic acid;

[0119] The structure of antibacterial agent C is formed by tributylcarboxymethyl phosphorus chloride containing a carboxylic acid group and hexamethylenediamine.

[0120] Example 12

[0121] Antibacterial copolyamide 12 comprises 88.5% by mass of polyamide A structure, 9% by mass of polyamide B structure, and 1.5% by mass of antibacterial agent C structure;

[0122] Among them, the polyamide A structure is formed by ring-opening caprolactam;

[0123] The polyamide B structure is formed by hexamethylenediamine and isophthalic acid;

[0124] The structure of antibacterial agent C is formed by combining 2-(carboxyethyl)triphenylphosphine bromide containing a carboxylic acid group and hexamethylenediamine.

[0125] Comparative Example 1

[0126] The difference from Example 1 is that the polyamide A structure is formed by hexamethylenediamine and adipic acid, while everything else remains the same.

[0127] Comparative Example 2

[0128] The difference from Example 1 is that the polyamide A structure is formed by hexamethylenediamine and 1,10-sebacic acid, while the rest remains the same.

[0129] Comparative Example 3

[0130] The difference from Example 1 is that it does not contain the polyamide B structure, but everything else remains the same.

[0131] Comparative Example 4

[0132] The difference from Example 1 is that it does not contain the polyamide C structure, but everything else remains the same.

[0133] The preparation methods of the copolyamides in the above embodiments and comparative examples specifically include the following steps:

[0134] (1) Salt solution preparation steps

[0135] The polyamide A salt solution was prepared by dissolving the diamine and diamine in a solvent according to the above examples and comparative examples to form a salt solution. The solution temperature was controlled at 55°C and the mass percentage was controlled at 40%.

[0136] Solutions of polyamide B salt and / or lactam b3, wherein in the examples and comparative examples of polyamide B structure formed by diacid and diamine, the diacid and diamine of the above examples and comparative examples are dissolved in demineralized water to form a salt solution; wherein in the examples and comparative examples of polyamide b3 structure formed by lactam ring opening, the lactam of the above examples and comparative examples is dissolved in demineralized water to form a lactam solution, wherein comparative examples 3 and 4 do not add solutions containing polyamide B salt and / or lactam b3; the solution temperature is controlled at 55°C, and the mass percentage is controlled at 40% respectively.

[0137] The solution containing antibacterial agent C salt was dissolved in demineralized water to form a salt solution according to the above examples and comparative examples. In Examples 7 and 8, the antibacterial agent was directly dispersed in demineralized water. The solution temperature was controlled at 55°C and the mass percentage was controlled at 20%.

[0138] (2) Aggregation step

[0139] In the presence of nitrogen, a solution containing polyamide A salt and a solution containing polyamide B salt and / or lactam b3 are mixed, polymerized and evaporated to concentrate the solution to a mass percentage of 75% under conditions of 145°C and 0.25 MPa.

[0140] A solution containing antibacterial agent C salt was added and mixed further. The polymerization reaction continued at a temperature of 170°C and a pressure of 1.6 MPa. Finally, the pressure was reduced to room temperature to obtain the copolyamide.

[0141] Polyamides were prepared according to the above examples and comparative examples. The performance of the polyamide samples was tested, and the test methods and standards for each performance parameter are as follows:

[0142] 1. Melting point: ASTM D3418.

[0143] 2. Viscosity: ISO 307.

[0144] 3. Mechanical properties: Tensile strength is tested according to standard ISO527, and impact strength of simply supported beam is tested according to standard ISO 179.

[0145] 4. Antibacterial properties: Referring to QB / T 2591-2003A "Test methods and antibacterial effects of antibacterial plastics", the antibacterial rate was tested using Escherichia coli ATCC 25922 after 24 hours; the antibacterial rate was tested after the sample was placed under conditions of 85% relative humidity and 85℃ for 500 hours.

[0146] The performance test results are as follows:

[0147]

[0148]

Claims

1. An antibacterial copolyamide, characterized in that... The polyamide A structure comprises hexamethylenediamine and dodecanoic acid, at least one polyamide B structure other than polyamide A, and an antibacterial agent C structure. The polyamide B structure is formed by at least one diacid b1 and at least one diamine b2, and / or by ring-opening of lactam b3; the diacid b1 includes aromatic diacids; The antibacterial agent C structure contains quaternary... Salt groups, through quaternary structures containing carboxylic acid groups Salt antibacterial agent and diamine B2 are formed; The polyamide A structure accounts for 70% to 95% of the mass of the antibacterial copolyamide; The polyamide B structure accounts for 4% to 29% of the mass of the antibacterial copolyamide; The antibacterial agent C structure accounts for 0.2% to 1% of the mass of the antibacterial copolyamide; The melting point of the antibacterial copolyamide is 180℃~210℃.

2. The antibacterial copolyamide according to claim 1, characterized in that... The aromatic dicarboxylic acid includes one or more of terephthalic acid, terephthalic acid, terephthalic propionic acid, isophthalic acid, isophthalic acid, phthalic acid, and phthalic acid.

3. The antibacterial copolyamide according to claim 1, characterized in that... The diamine b2 mentioned above independently includes diamines of C2 to C14.

4. The antibacterial copolyamide according to claim 3, characterized in that... The C2-C14 diamines include one or more of pentanediamine, hexanediamine, octanediamine, decanediamine, and 1,12-diaminododecane.

5. The antibacterial copolyamide according to claim 1, characterized in that... The lactam b3 includes one or more of butyrolactam, valproic acid lactam, caprolactam, octyl lactam, lauryl lactam, N-methylcaprolactam, N-vinylcaprolactam, and 4-tert-butylcaprolactam.

6. An antibacterial copolyamide according to claim 1, characterized in that... The aforementioned quaternary ammonium carbonate containing carboxylic acid groups Salt antibacterial agents include tributylcarboxymethyl phosphorus chloride and / or 2-(carboxyethyl)triphenylphosphine bromide.

7. A method for preparing an antibacterial copolyamide as described in claim 1 or 2, characterized in that, The preparation method is as follows: The process is carried out in the presence of a protective gas. A solution containing polyamide A salt, a solution containing polyamide B salt and / or lactam b3, and a solution containing antibacterial agent C salt are mixed to form a mixed solution, and the mixed solution is polymerized to form an antibacterial copolyamide.

8. The method for preparing an antibacterial copolyamide according to claim 7, characterized in that, The solution containing polyamide A salt is formed by dissolving hexamethylenediamine and dodecanoic acid in a solvent to form a salt solution; The solution containing polyamide B salt is formed by dissolving at least one dicarboxylic acid b1, at least one diamine b2, and / or lactam b3 in a solvent to form a salt solution. The solution of the antibacterial agent C salt is prepared by passing the antibacterial agent C salt through a quaternary ammonium salt containing a carboxylic acid group. Salt antibacterial agent and diamine B2 are dissolved in solvent to form salt solution.

9. The method for preparing an antibacterial copolyamide according to claim 7, characterized in that, The protective gas includes one or more of nitrogen, carbon dioxide, argon, and helium, and does not participate in the polymerization reaction; the polymerization temperature is 150℃~280℃, and the pressure is 0~2.0MPa.

10. The method for preparing an antibacterial copolyamide according to claim 8, characterized in that, The solvent mentioned includes water.

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