Gemini quaternary ammonium salt antibacterial agent and its preparation and application in the synthesis of antibacterial polyester

Abstract

The present invention discloses a gemini quaternary ammonium salt antibacterial agent, a preparation method thereof and application thereof in the synthesis of antibacterial polyester. The gemini quaternary ammonium salt antibacterial agent has the following structure: #imgabs0# wherein R1 is an alkyl group containing 1 to 12 carbon atoms, R2 is an alkylene group containing 4 to 18 carbon atoms, and Z ‑ is an organic metal salt Y + Z ‑ Anions in organic metal salts Y + Z ‑ The invention comprises at least one of sodium 5-sulfoisophthalate, sodium dimethyl 5-sulfoisophthalate, sodium 2-sulfoterephthalate, sodium 3-carboxybenzenesulfonate, sodium 2,5-dihydroxybenzenesulfonate, sodium N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, sodium hydroquinone sulfate, potassium hydroquinone sulfate, and calcium hydroquinone sulfate. The gemini quaternary ammonium salt antibacterial agent is synthesized by quaternizing imidazoles with long carbon chains and then obtaining the product by ion exchange in the aqueous phase.

Description

Technical Field

[0001] The invention relates to the field of antibacterial materials, and in particular to a gemini quaternary ammonium salt antibacterial agent, a preparation method thereof and application thereof in the synthesis of antibacterial polyester. Background Art

[0002] At present, bacterial infection is becoming the second leading cause of death in the world after ischemic heart disease. How to reduce bacterial infection has become a public health safety issue that needs to be solved urgently by global health prevention and control departments. Gemini quaternary ammonium salt antibacterial agents are a class of compounds with two quaternary ammonium salt hydrophilic groups and two hydrophobic long carbon chain segments. Gemini quaternary ammonium salts have high heat resistance and high efficiency, stability and broad-spectrum antibacterial activity.

[0003] In the industry, large-scale synthesis of polyester is generally achieved by adding metal catalysts (such as germanium, antimony, titanium, etc.) and continuously extracting reaction byproducts under high temperature conditions to obtain high molecular weight polyester. However, heavy metal elements in metal catalysts may cause great harm to human health and the natural environment. The patent specification with publication number CN110790906A discloses a technical solution for synthesizing high molecular weight aliphatic polyesters with properties equivalent to commercial polyester materials using diols and an excess molar ratio of cyclic dicarboxylic acids or anhydrides as raw materials, avoiding a series of problems caused by the introduction of catalysts.

[0004] Blending antimicrobial agents with polyester materials is a common method for synthesizing antimicrobial polyesters at this stage. However, the high temperature conditions required for synthesizing antimicrobial modified polyesters will inactivate most antimicrobial agents, and the antimicrobial performance of blended antimicrobial polyesters is poor in durability, and the antimicrobial performance of the material decreases significantly after repeated use. Therefore, introducing antimicrobial agents into polyester segments through copolymerization and other methods is the best way to synthesize antimicrobial polyester materials. This method can give polyester materials efficient antimicrobial properties in situ.

[0005] The patent specification with publication number CN117756720A discloses an antibacterial polyester obtained by reacting raw materials including polyols, polyacids and polymerizable quaternary ammonium salt antibacterial agents, wherein the antibacterial activity of the polymerizable quaternary ammonium salt antibacterial agent is derived from imidazole quaternary ammonium salt. The patented technology introduces a quaternary ammonium salt component with a long-chain alkyl group into the polyester main chain to prepare and synthesize a high molecular weight antibacterial copolyester. The results of mechanical property tests and antibacterial activity tests show that the introduction of the quaternary ammonium salt component gives the copolyester excellent anti-Gram-negative and anti-Gram-positive bacteria activity. Summary of the invention

[0006] The invention provides a gemini quaternary ammonium salt antibacterial agent, a preparation method thereof and application of the gemini quaternary ammonium salt antibacterial agent in the synthesis of antibacterial polyester.

[0007] A gemini quaternary ammonium salt antibacterial agent having the following structure:

[0008]

[0009] Wherein, R1 is an alkyl group containing 1 to 12 carbon atoms (the alkyl group includes a straight chain alkyl group, a branched chain alkyl group, a cyclic alkyl group, etc.), R2 is an alkylene group containing 4 to 18 carbon atoms (the alkylene group refers to the alkyl group that has lost one hydrogen, including a straight chain alkylene group, a branched chain alkylene group, a cyclic alkylene group, etc.), Z - is an organic metal salt Y + Z - The anion in the organic metal salt Y + Z - The invention comprises at least one of sodium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, sodium 2-sulfoterephthalate, sodium 3-carboxybenzenesulfonate, sodium 2,5-dihydroxybenzenesulfonate, sodium N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, sodium hydroquinone sulfate, potassium hydroquinone sulfate and calcium hydroquinone sulfate.

[0010] The invention first synthesizes a novel polymerizable gemini quaternary ammonium salt antibacterial agent by quaternizing imidazoles with long carbon chains, and then obtains the antibacterial agent by ion exchange in an aqueous phase. Under catalyst-free conditions, diols, dicarboxylic acids and / or dibasic acid anhydrides and the polymerizable gemini quaternary ammonium salt antibacterial agent are subjected to an esterification stage and a polycondensation stage, and then a quaternary ammonium salt component with a long-chain alkyl group is introduced into a polyester main chain to prepare a synthetic high-molecular-weight antibacterial copolyester. The antibacterial activity test results show that the introduction of the quaternary ammonium salt component gives the copolyester excellent anti-Gram-negative and anti-Gram-positive bacteria activities.

[0011] The structural formula of the gemini quaternary ammonium salt antibacterial agent contains two or more hydroxyl groups and / or carboxyl groups, which endow the gemini quaternary ammonium salt with polymerizability and high heat resistance; the imidazole quaternary ammonium salt endows the gemini quaternary ammonium salt with antibacterial activity.

[0012] The present invention also provides a method for preparing the gemini quaternary ammonium salt antibacterial agent, comprising the steps of:

[0013] (1) Add the first solvent X is a halogen atom (such as fluorine, chlorine, bromine, iodine, etc.), the temperature is raised to 80-100°C for reaction, the solvent is removed after the reaction is completed, the obtained crude product is washed and dried to obtain an intermediate product;

[0014] (2) Adding organic metal salt Y to the second solvent + Z - and the intermediate product, heating to 50-80° C. for reaction, washing and drying the reaction product to obtain the gemini quaternary ammonium salt antibacterial agent.

[0015] In step (1), the first solvent may include toluene.

[0016] In step (1), The molar ratio can be 2.01 to 2.50:1.

[0017] In step (1), the reaction can be carried out under condensation reflux conditions.

[0018] In step (1), the reaction time may be 6 to 10 hours.

[0019] In step (1), the washing agent used in the washing may include ethyl acetate.

[0020] In step (1), the drying may be vacuum drying.

[0021] In step (1), the drying temperature can be 45 to 55° C. and the drying time can be 10 to 24 hours.

[0022] In step (2), the second solvent may include deionized water.

[0023] In step (2), the organic metal salt Y + Z - The molar ratio to the intermediate product may be 2.05 to 2.50:1.

[0024] In step (2), the reaction may be carried out under continuous stirring.

[0025] In step (2), the reaction time may be 4 to 8 hours.

[0026] In step (2), the detergent used for washing may include deionized water.

[0027] In step (2), the drying may be vacuum drying.

[0028] In step (2), the drying temperature can be 75 to 85° C. and the drying time can be 10 to 24 hours.

[0029] The invention also provides application of the gemini quaternary ammonium salt antibacterial agent in synthesizing antibacterial polyester.

[0030] As a general inventive concept, the present invention also provides an antibacterial polyester obtained by reacting raw materials including polyols, polyacids and the gemini quaternary ammonium salt antibacterial agent.

[0031] The present invention further provides a method for preparing the antibacterial polyester, comprising:

[0032] Esterification stage: in the absence of a catalyst, using diol, the gemini quaternary ammonium salt antibacterial agent and cyclic dicarboxylic acid and / or the corresponding anhydride as raw materials, an esterification reaction is carried out to obtain a carboxyl-terminated prepolymer;

[0033] Condensation polymerization stage: under reduced pressure, the reaction temperature is controlled not to be lower than the boiling point of the anhydride corresponding to the cyclic dicarboxylic acid, and the anhydride corresponding to the cyclic dicarboxylic acid is removed from the carboxyl-terminated prepolymer to obtain the antibacterial polyester.

[0034] In the preparation method of the antibacterial polyester, the diol may include at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, phenyl glycol, catechol, resorcinol, hydroquinone, 1,3-adamantanediol, and 1,1-cyclopropanediol.

[0035] In the preparation method of the antibacterial polyester, the cyclic dicarboxylic acid may include at least one of succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, maleic acid, phthalic acid, glutaric acid, 2-ketoglutaric acid, 1,3-acetonedicarboxylic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, and 3,3-tetramethyleneglutaric acid.

[0036] In the preparation method of the antibacterial polyester, the acid anhydride may include succinic anhydride, 2-methylsuccinic anhydride, 2-phenylsuccinic anhydride, 2-benzylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,3-diphenylsuccinic anhydride, 1,2-cyclosuccinic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, maleic anhydride, phthalic anhydride, maleic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, maleic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, 2,2,3,3-tetramethyls At least one of anhydride, 2-ketoglutaric anhydride, 1,3-acetone dicarboxylic anhydride, 2-methylglutaric anhydride, 3-methylglutaric anhydride, 3-phenylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl-3-methylglutaric anhydride, 3,3-tetramethyleneglutaric anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3-pyrazine dicarboxylic anhydride, and 2,3-pyridine dicarboxylic anhydride.

[0037] In the method for preparing the antibacterial polyester, the molar ratio of the diol to the cyclic dicarboxylic acid and / or the corresponding anhydride can be 1:1.05-2.

[0038] In the preparation method of the antibacterial polyester, based on the amount of the diol as 100%, the total addition amount of the gemini quaternary ammonium salt antibacterial agent can be 0.2 mol% to 5 mol%, for example, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, etc.

[0039] In the method for preparing the antibacterial polyester, the esterification stage can be carried out in an inert atmosphere, which can be a rare gas atmosphere and / or a nitrogen atmosphere.

[0040] In the method for preparing the antibacterial polyester, the temperature of the esterification reaction in the esterification stage can be 160 to 240° C., and the time can be 8 to 16 hours.

[0041] In the method for preparing the antibacterial polyester, the reaction temperature in the polycondensation stage can be 240-280° C., the reaction pressure is preferably lower than 100 Pa, and the reaction time can be 8-24 hours.

[0042] The invention provides a gemini quaternary ammonium salt antibacterial agent which can be used for polyester polycondensation and a preparation method thereof. The gemini quaternary ammonium salt antibacterial agent is applied to synthesize antibacterial copolyester under catalyst-free conditions to obtain an antibacterial copolyester material having a molecular weight equivalent to that of commercial polyester.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] Firstly, the highly heat-resistant gemini quaternary ammonium salt antibacterial agent synthesized by the present invention has high antibacterial activity and high yield, and can be extended to large-scale preparation.

[0045] In addition, after the synthetic high heat-resistant gemini quaternary ammonium salt antibacterial agent of the present invention is introduced into the antibacterial copolyester chain segment, the polyester material is endowed with broad-spectrum antibacterial activity, and the addition of the antibacterial agent will not affect the material properties, and the antibacterial copolyester material can be directly used without post-modification treatment.

[0046] Finally, the antibacterial copolyester prepared and synthesized by the present invention has a dynamic chain structure connected by ion bonds. The introduction of the dynamic chain structure further improves the processing performance of the polyester material and increases the melt viscosity. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is the H NMR spectrum of the polymerizable gemini quaternary ammonium salt antibacterial agent synthesized in Example 1.

[0048] Figure 2 This is the thermogravimetric analysis diagram of the polymerizable gemini quaternary ammonium salt antibacterial agent synthesized in Example 1.

[0049] Figure 3 The viscosity-temperature curves of the antibacterial copolyester in Example 4 and the pure polyester in Comparative Example 1 are shown. DETAILED DESCRIPTION

[0050] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0051] The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturers.

[0052] Example 1

[0053] Preparation method of polymerizable gemini quaternary ammonium salt antibacterial agent:

[0054] (1) 1-Octyl imidazole (25 g), 1,12-dibromododecane (21 g) and toluene (50 mL) were added to a flask, the temperature was raised to 100°C, a condenser was connected, magnetic stirring was performed and condensation reflux was performed, the reaction was continued for 8 h, the toluene solvent was removed by rotary evaporation, the crude product was washed with ethyl acetate for several times, the supernatant was discarded after centrifugation, the product was collected, and vacuum dried at 50°C for 12 h, and the product was collected for use to obtain an intermediate product with a yield of 97.6%.

[0055] (2) The intermediate product (20 g), sodium 5-sulfonate of isophthalic acid (22 g) and deionized water (100 mL) were added to a flask, the temperature was raised to 80° C., and stirring was continued for 6 h. The crude product was washed with deionized water for multiple times, centrifuged and the supernatant was discarded, the product was collected, and vacuum dried at 80° C. for 12 h. The product was collected for use to obtain a polymerizable gemini quaternary ammonium salt antibacterial agent (see H NMR spectrum). Figure 1 ), the yield was 94.7%. The minimum inhibitory concentration (MIC) test showed that the MIC value of the antibacterial agent against Escherichia coli was 1.25 μg / ml, and the MIC value against Staphylococcus aureus was 1.25 μg / ml.

[0056] The gemini quaternary ammonium salt antibacterial agent of the present invention has two hydrophilic end quaternary ammonium salt ions, which strengthen the binding effect with the bacterial cell membrane, and the two long-chain alkyl groups have a more obvious effect on the bacterial hydrophilic group. These characteristics promote the dissolution and death of the bacterial cell structure and show a lower MIC value.

[0057] Figure 2 The results of thermogravimetric analysis of the polymerizable gemini quaternary ammonium salt antibacterial agent synthesized in this embodiment are shown. The 5% thermal weight loss temperature (T d,5％ ) reaches 340℃, showing high heat resistance and can be used in high temperature melt polycondensation conditions.

[0058] One-pot synthesis of antibacterial copolyesters without catalyst:

[0059] Esterification stage: Succinic acid (28.8 g), 1,4-butanediol (20.0 g) and the above-prepared polymerizable gemini quaternary ammonium antibacterial agent (1 mol%, based on 100% of the amount of diol) were added to a 250 mL three-necked flask, heated to 180°C, stirred for reaction, introduced argon, exhausted the air in the device, and took out the water and other small molecular products produced by esterification. After 8 hours of reaction, no water was produced in the system and the reaction was stopped to obtain a prepolymer of polybutylene succinate copolyester.

[0060] Condensation stage: stop passing argon, and connect the three-necked flask to a vacuum oil pump to evacuate the air. Gradually raise the temperature to 240°C, and the pressure in the three-necked flask is less than 100 Pa. Stir and carry out the polymerization reaction for 12 hours to obtain polybutylene succinate copolyester with a number average molecular weight of 43 kDa. The antibacterial test results show that the antibacterial rate of the synthesized polybutylene succinate copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0061] Embodiment 2-3

[0062] The synthesis process is the same as that of Example 1, except that 1-octylimidazole is replaced by 1-decylimidazole and 1-dodecylimidazole in equal molar amounts in sequence.

[0063] After testing, the MIC value determination experiment of the polymerizable gemini quaternary ammonium salt antibacterial agent in Example 2 showed that the MIC value of the antibacterial agent against Escherichia coli was 1.25 micrograms / ml, and the MIC against Staphylococcus aureus was 1.25 micrograms / ml. The number average molecular weight of the polybutylene succinate copolyester product was 44kDa, and the antibacterial test results showed that the antibacterial rate of the synthesized polybutylene succinate copolyester product against Escherichia coli and Staphylococcus aureus was greater than 99.9%.

[0064] After testing, the MIC value determination experiment of the polymerizable gemini quaternary ammonium salt antibacterial agent in Example 3 showed that the MIC value of the antibacterial agent against Escherichia coli was 1.25 μg / ml, and the MIC against Staphylococcus aureus was 0.625 μg / ml. The number average molecular weight of the polybutylene succinate copolyester product was 43 kDa, and the antibacterial test results showed that the antibacterial rate of the synthesized polybutylene succinate copolyester product against Escherichia coli and Staphylococcus aureus was greater than 99.9%.

[0065] Embodiments 4 to 6

[0066] The synthesis process is the same as that of Example 1, except that 1,4-butanediol is replaced by equimolar amounts of ethylene glycol, 1,6-hexanediol, and 1,8-octanediol in sequence.

[0067] After testing, the number average molecular weight of the polyethylene succinate copolyester product in Example 4 is 51 kDa, and the antibacterial test results show that the antibacterial rate of the polyethylene succinate copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0068] After testing, the number average molecular weight of the poly(hexylene succinate) copolyester product in Example 5 is 41 kDa, and the antibacterial test results show that the antibacterial rate of the poly(hexylene succinate) copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0069] After testing, the number average molecular weight of the polyoctane succinate copolyester product in Example 6 is 43 kDa, and the antibacterial test results show that the antibacterial rate of the polyoctane succinate copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0070] Comparative Example 1

[0071] The synthesis process is the same as that of Example 1, except that 1,4-butanediol is replaced by ethylene glycol in an equal molar amount in sequence, and no gemini quaternary ammonium salt antibacterial agent is added to obtain polyethylene succinate.

[0072] Figure 3 The viscosity-temperature curves of the antibacterial copolyester obtained in Example 4 and the pure polyester in Comparative Example 1 are shown. In the entire measuring temperature range, the melt viscosity-temperature curve of Example 4 is higher than that of the pure polyester, indicating that Example 4 has a higher melt viscosity.

[0073] Embodiment 7-8

[0074] The synthesis process is the same as that of Example 1, except that 5-sodium sulfoisophthalate is replaced by equimolar amounts of 2-sodium sulfoterephthalate and sodium 2,5-dihydroxybenzenesulfonate in sequence.

[0075] After testing, the number average molecular weight of the polybutylene succinate copolyester product in Example 7 is 42 kDa, and the antibacterial test results show that the antibacterial rate of the polybutylene succinate copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0076] After testing, the number average molecular weight of the polybutylene succinate copolyester product in Example 8 is 41 kDa, and the antibacterial test results show that the antibacterial rate of the polybutylene succinate copolyester product against Escherichia coli and Staphylococcus aureus is greater than 99.9%.

[0077] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. An antibacterial polyester, characterized in that Obtained by reacting raw materials including diol, dicarboxylic acid and / or dibasic acid anhydride with a gemini quaternary ammonium salt antibacterial agent; The gemini quaternary ammonium salt antibacterial agent has the following structure: Wherein, R1 is an alkyl group containing 1 to 12 carbon atoms, R2 is an alkylene group containing 4 to 18 carbon atoms, and Z - is an organic metal salt Y + Z - The anion in the organic metal salt Y + Z - It is at least one of sodium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, sodium 2-sulfoterephthalate, sodium 2,5-dihydroxybenzenesulfonate, sodium N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, sodium hydroquinone sulfate, potassium hydroquinone sulfate, and calcium hydroquinone sulfate.

2. The antimicrobial polyester according to claim 1, characterized in that The preparation method of the gemini quaternary ammonium salt antibacterial agent comprises the steps of: (1) Add the first solvent X is a halogen atom, the temperature is raised to 80-100°C for reaction, the solvent is removed after the reaction is completed, the obtained crude product is washed and dried to obtain an intermediate product; (2) Adding organic metal salt Y to the second solvent + Z - and the intermediate product, heating to 50-80° C. for reaction, washing and drying the reaction product to obtain the gemini quaternary ammonium salt antibacterial agent.

3. The antimicrobial polyester according to claim 2, characterized in that: In step (1): The first solvent includes toluene; The molar ratio is 2.01 to 2.50:1; The reaction is carried out under condensation reflux conditions; The reaction time is 6 to 10 hours; The washing agent used in the washing includes ethyl acetate; The drying is vacuum drying; The drying temperature is 45-55° C. and the drying time is 10-24 hours.

4. The antimicrobial polyester according to claim 2, characterized in that: In step (2): The second solvent includes deionized water; The organic metal salt Y + Z - The molar ratio of the intermediate product is 2.05 to 2.50:1; The reaction is carried out under continuous stirring; The reaction time is 4 to 8 hours; The washing agent used in the washing includes deionized water; The drying is vacuum drying; The drying temperature is 75-85° C. and the drying time is 10-24 hours.

5. The method for preparing the antibacterial polyester according to any one of claims 1 to 4, characterized in that: include: Esterification stage: in the absence of a catalyst, using diol, the gemini quaternary ammonium salt antibacterial agent and cyclic dicarboxylic acid and / or the corresponding anhydride as raw materials, an esterification reaction is carried out to obtain a carboxyl-terminated prepolymer; Condensation polymerization stage: under reduced pressure, the reaction temperature is controlled not to be lower than the boiling point of the anhydride corresponding to the cyclic dicarboxylic acid, and the anhydride corresponding to the cyclic dicarboxylic acid is removed from the carboxyl-terminated prepolymer to obtain the antibacterial polyester.

6. The method for preparing the antibacterial polyester according to claim 5, characterized in that: The diol includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, phenyl glycol, catechol, resorcinol, hydroquinone, 1,3-adamantanediol, and 1,1-cyclopropanediol; The cyclic dicarboxylic acid comprises at least one of succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, maleic acid, phthalic acid, glutaric acid, 2-ketoglutaric acid, 1,3-acetonedicarboxylic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, and 3,3-tetramethyleneglutaric acid; The acid anhydride includes succinic anhydride, 2-methylsuccinic anhydride, 2-phenylsuccinic anhydride, 2-benzylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,3-diphenylsuccinic anhydride, 1,2-cyclosuccinic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, maleic anhydride, 2-ketoglutaric anhydride, 1,3-acetone dicarboxylic anhydride, 2-methyl at least one of 1,2-dimethylglutaric anhydride, 3-methylglutaric anhydride, 3-phenylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl-3-methylglutaric anhydride, 3,3-tetramethyleneglutaric anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3-pyrazine dicarboxylic anhydride and 2,3-pyridine dicarboxylic anhydride; the molar ratio of the diol to the cyclic dicarboxylic acid and / or the corresponding anhydride is 1:1.05 to 2; Based on the amount of the diol as 100%, the total addition amount of the gemini quaternary ammonium salt antibacterial agent is 0.2 mol% to 5 mol%.

7. The method for preparing the antibacterial polyester according to claim 5, characterized in that: The esterification stage is carried out in an inert atmosphere; the inert atmosphere is a rare gas atmosphere and / or a nitrogen atmosphere; The temperature of the esterification reaction in the esterification stage is 160-240° C. and the time is 8-16 hours.

8. The method for preparing the antibacterial polyester according to claim 5, characterized in that: The reaction temperature of the polycondensation stage is 240-280° C., the reaction pressure is lower than 100 Pa, and the reaction time is 8-24 hours.

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