Preparation method for antimicrobial polyester and production method for antimicrobial fiber

Abstract

A preparation method for an antimicrobial polyester, an antimicrobial polyester obtained by the preparation method, a production method for an antimicrobial fiber, an antimicrobial fiber, and a use of the antimicrobial fiber in producing a medical surgical article. The present invention mainly aims at solving the defect that existing antimicrobial polyester fibers have poor wash durability and antimicrobial performance. The technical problem is well solved by means of the technical solution of the preparation method for an antimicrobial polyester, comprising: (i) performing an esterification reaction on a diol and a dibasic acid to obtain an esterified material I; (ii) mixing the esterified material I with a reactive antimicrobial component for a pre-polycondensation reaction to obtain a pre-polycondensation product; and (iii) performing a final polycondensation reaction on the pre-polycondensation product to obtain the antimicrobial polyester, wherein the reactive antimicrobial component is obtained by performing an esterification reaction on a substance as represented by formula 3 below and the diol. In the formula, Q is a quaternary ammonium group containing a long-chain hydrocarbon group, the number of carbon atoms in the long-chain hydrocarbon group is 6-20, and Ar is an aromatic ring.

Description

Preparation method of antibacterial polyester and production method of antibacterial fiber Technical Field

[0001] The present invention relates to a preparation method of antibacterial polyester, a production method of the antibacterial polyester and antibacterial fiber obtained by the preparation method, the antibacterial fiber, and application of the antibacterial fiber in the production of medical surgical products. Background Art

[0002] Polyester fiber is a high-volume, widely used synthetic fiber, widely used in home textiles, clothing, and industrial textiles. In 2022, my country's total polyester fiber production exceeded 50 million tons. Bacterial infections are a major threat to human health. The development of polyester fibers with antimicrobial properties is crucial because it can help prevent the spread of bacteria, reduce the risk of bacterial infections, reduce the use of antibiotics, and improve public health. Currently, antimicrobial polyester fibers are primarily produced by physically blending inorganic antimicrobial agents such as nanosilver and nanozinc oxide. However, the antimicrobial properties of these fibers are derived from the diffusion release of the antimicrobial agents, which are lost as the release of the agents is complete. This loss is particularly pronounced during daily washing, resulting in a lack of long-lasting antimicrobial efficacy. Furthermore, inorganic antimicrobial agents are highly biotoxic and can cause skin allergies when placed on textiles worn next to the human body, limiting their application. Currently, the most common method for large-scale commercial polyester fiber synthesis is the melt condensation polymerization of dicarboxylic acids and diols followed by melt spinning. Covalently binding organic ecological antimicrobial agents to the main chain of polyester through cocondensation can not only give polyester long-lasting antimicrobial properties, but also effectively reduce the biological toxicity of antimicrobial agents. This is the development direction of antimicrobial polyester fibers.

[0003] Summary of the Invention

[0004] One of the technical problems to be solved by the present invention is the defect that the existing antibacterial polyester fiber has poor washing resistance and antibacterial performance. A new preparation method of antibacterial polyester is provided. The antibacterial polyester fiber produced by using the antibacterial polyester has the advantages of good washing resistance and antibacterial performance.

[0005] In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

[0006] A method for preparing antibacterial polyester comprises the following steps:

[0007] (i) esterifying the diol with the dibasic acid to obtain an esterified material I;

[0008] (ii) mixing the esterified material I with the reactive antibacterial component to perform a pre-polycondensation reaction to obtain a pre-polycondensation product;

[0009] (iii) subjecting the pre-polycondensation product to a final polycondensation reaction to obtain an antibacterial polyester;

[0010] The reactive antibacterial component is obtained by esterification of the substance shown in Formula 3 with diol:

[0011] Q is a quaternary ammonium group containing a long-chain hydrocarbon group, the number of carbon atoms in the long-chain hydrocarbon group is 6 to 20, and Ar is an aromatic ring.

[0012] The key technical aspect of the present invention lies in the use of the reactive antimicrobial component in the preparation of the antimicrobial polyester. Once the reactive antimicrobial component is disclosed, those skilled in the art can utilize the reactive antimicrobial component in the preparation of the antimicrobial polyester by rationally selecting process conditions and achieving comparable technical results without inventive effort. However, compared to directly co-esterifying the components represented by Formula 3 in step (i), or esterifying in step (i) with the reactive antimicrobial component, we have found that the antimicrobial polyester obtained by adding the reactive antimicrobial component of the present invention in the pre-polycondensation reaction stage exhibits significantly superior antimicrobial efficacy to that obtained by adding the reactive antimicrobial component of the present invention in the esterification stage.

[0013] In the above technical solution, Ar is preferably a benzene ring or a naphthalene ring.

[0014] In the above technical solution, the diol in step (i) preferably includes at least one selected from the group consisting of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,4-cyclohexanedimethanol. For comparison purposes only, ethylene glycol is generally used in the embodiments of the present invention.

[0015] In the above technical solution, the dibasic acid in step (i) preferably comprises at least one selected from the group consisting of terephthalic acid, succinic acid, adipic acid, isophthalic acid, and furandicarboxylic acid. For comparison purposes only, terephthalic acid is generally used in the embodiments of the present invention.

[0016] In the above technical solution, in step (i), the molar ratio of diol to dibasic acid is preferably 1.1 to 1.5, for example but not limited to 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.

[0017] In the above technical solution, the esterification rate of the esterification reaction in step (i) is preferably 95% to 99%, for example but not limited to 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.

[0018] In order to achieve the above-mentioned esterification rate, those skilled in the art can reasonably select the esterification temperature and esterification time according to the actual conditions such as the operating conditions allowed by the reaction equipment. As a general rule, the higher the esterification temperature and the longer the esterification time, the more conducive to improving the esterification rate.

[0019] By way of non-limiting example only, the esterification temperature in step (i) may be selected from 150 to 250° C., with more specific non-limiting examples being 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., and the like. Within this temperature range, while continuously separating the water produced by the esterification reaction, even without a catalyst as in the embodiments of the present invention, the desired esterification rate can typically be achieved with an esterification reaction time of 0.5 to 2 hours. Of course, an esterification catalyst may also be used in the esterification reaction, which results in a faster esterification reaction rate.

[0020] The esterification reaction in step (i) can be carried out under the autogenous pressure of the reaction, or it can be carried out under a pressure higher than the autogenous pressure by filling the reaction system with an inert gas, such as nitrogen. Since the esterification reaction in step (i) is a liquid phase reaction, the pressure has no significant effect on the progress of the esterification reaction.

[0021] In the above technical solution, in step (ii), the mass ratio of the reactive antimicrobial component (calculated in terms of N content) to the esterified material I (calculated in terms of the dibasic acid required for its preparation) is preferably t:100, where t is greater than 0 and less than 4. For example, but not limited to, t is 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, and the like.

[0022] In the above technical solution, in step (ii), the pressure is preferably 400-600 Pa, for example but not limited to 410 Pa, 420 Pa, 430 Pa, 440 Pa, 450 Pa, 460 Pa, 470 Pa, 480 Pa, 490 Pa, 500 Pa, 510 Pa, 520 Pa, 530 Pa, 540 Pa, 550 Pa and the like.

[0023] In the above technical solution, in step (ii), the preferred reaction temperature is 255-265°C, for example but not limited to 256°C, 257°C, 258°C, 259°C, 260°C, 261°C, 262°C, 263°C, 264°C, etc.

[0024] In the above technical solution, in step (ii), the reaction time is preferably 30 to 60 minutes, for example but not limited to 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc.

[0025] In the above technical solution, in step (iii), the reaction pressure is preferably below 100 Pa, for example but not limited to 5 Pa, 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50 Pa, 60 Pa, 70 Pa, 80 Pa, 90 Pa, etc.

[0026] In the above technical solution, in step (iii), the reaction temperature is preferably 270-285°C, for example but not limited to 271°C, 272°C, 273°C, 274°C, 275°C, 276°C, 277°C, 278°C, 279°C, 280°C, 281°C, 282°C, 283°C, 284°C and the like.

[0027] Those skilled in the art will appreciate that reducing the reaction pressure and increasing the reaction temperature in step (iii) are both beneficial for promoting the final polycondensation reaction and for increasing the intrinsic viscosity of the final polycondensation product. Once the reaction pressure and reaction temperature in step (iii) are determined, the intrinsic viscosity in step (iii) tends to increase with increasing reaction time. In the above technical solution, step (iii) is preferably carried out until the intrinsic viscosity is 0.60-0.75 dl / g. For comparison purposes only, the intrinsic viscosity in both the embodiment and the comparative example is 0.68 dl / g.

[0028] In the above technical solution, in step (iii), under the above reaction temperature and reaction pressure, the reaction time is generally 1.5 to 3.0 hours to achieve the above required intrinsic viscosity range.

[0029] In the above technical solution, the method for synthesizing the reactive antibacterial component comprises the following steps:

[0030] (1) subjecting compound 1 and compound 2 to an ion exchange reaction in a solvent to obtain an intermediate product 3;

[0031] Compound 1 conforms to the structure shown in Formula 1:

[0032] Q + X - , formula 1,

[0033] Compound 2 conforms to the structure shown in Formula 2:

[0034] Intermediate product 3 conforms to the structure shown in formula 3;

[0035] X is Cl or Br; M is an alkali metal;

[0036] (2) The intermediate product 3 undergoes esterification reaction with diol to obtain a reactive antibacterial component.

[0037] In the above technical solution, the solvent described in step (1) is preferably water.

[0038] The ion exchange reaction equation in step (1) is expressed as follows:

[0039] When water is used as the solvent for the ion exchange reaction, the intermediate product 3 is precipitated in the reaction system, which is very convenient to separate from the reaction system.

[0040] As a non-limiting example of compound 1, for example but not limited to benzalkonium chloride, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, N-hexylpyridinium chloride, N-octylpyridinium chloride, N-decylpyridinium chloride, N-dodecylpyridinium chloride, N-tetradecylpyridinium chloride, N-hexadecylpyridinium chloride, N-octadecylpyridinium chloride, 1-hexadecyl-3-methyl bromide imidazole bromide, 1-octadecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole bromide, 1-octadecyl-3-methylimidazole bromide, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, didodecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, dihexadecyldimethylammonium chloride or dioctadecyldimethylammonium chloride.

[0041] In the above technical solution, the optional compound 1 conforms to the structure shown in formula 1a:

[0042] R1 is a long-chain hydrocarbon group, and the number of carbon atoms in R1 is 6 to 20;

[0043] R2 to R4 are short-chain hydrocarbon groups, and R2 to R4 are preferably independently C1 to C2 alkyl groups.

[0044] As a non-limiting example, for example, the number of carbon atoms in R1 is, but not limited to, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, etc. R1 can be an alkyl group, an alkenyl group, or an aryl group.

[0045] In the above technical solution, the preferred compound 2 conforms to the structure shown in Formula 2a:

[0046] For example only, compound 2 in the embodiments of the present invention is 5-sulfonic isophthalic acid alkali metal salt.

[0047] In the above technical solution, the ion exchange reaction is rapid and the reaction is completed thoroughly, similar to the exchange reaction of inorganic ions. Therefore, there is no particular limitation on the specific process conditions of the ion exchange reaction, and the process conditions commonly used in the art can be adopted. For example only, for example, compound 1 can be dissolved into an aqueous solution with a weight concentration of 1 to 10% (for example, but not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) and added to the reaction system. For another example, compound 2 can be dissolved into an aqueous solution with a weight concentration of 1 to 10% (for example, but not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) and added to the reaction system. There is no particular requirement for the reaction temperature, and room temperature is sufficient for smooth progress. There is no particular limitation on the reaction time. Since the ion exchange reaction reacts rapidly, extending the time for maintaining the reaction conditions within a certain range, that is, the apparent reaction time, is beneficial for the precipitated material obtained by the ion exchange reaction to obtain a better precipitate form, which is convenient for subsequent washing and separation. For example, the apparent reaction time can be 1.5 to 3 hours. The apparent reaction time is actually mainly the aging time of the ion exchange product in the reaction system, because the ion exchange reaction itself can be completed instantly.

[0048] In the above technical solution, the diol in step (2) preferably includes at least one selected from the group consisting of 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanedimethanol and a diol based on an OCH2CH2 unit; the diol based on an OCH2CH2 unit conforms to Formula 4:

[0049] Preferably, the number average molecular weight of the diol based on OCH2CH2 units is above the molecular weight of ethylene glycol and below 4000 g / mol, with m being the value required to meet the desired molecular weight.

[0050] For example, but not limited to, diols based on OCH2CH2 units include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 500, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 1500, polyethylene glycol 2000, polyethylene glycol 2500, polyethylene glycol 3000, polyethylene glycol 3500, polyethylene glycol 4000, etc. According to the naming convention of polyethylene glycol grades, the number after polyethylene glycol represents the number average molecular weight.

[0051] We found that when the diols used in step (2) are different, the antibacterial properties of the antibacterial polyester are greatly affected. When the diol used in step (2) is 1,4-cyclohexanedimethanol, the antibacterial performance is significantly better than when the diol used is ethylene glycol, 1,3-propylene glycol, 1,4-butanediol or polyethylene glycol.

[0052] We also found that when the diol used in step (2) is a mixed alcohol of ethylene glycol and 1,4-cyclohexanedimethanol, ethylene glycol and 1,4-cyclohexanedimethanol have a synergistic effect in improving the antibacterial properties of the antibacterial polyester. In this case, there is no particular restriction on the ratio of ethylene glycol to 1,4-cyclohexanedimethanol, and comparable synergistic effects can be achieved. For example only, the molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol is 0.1 to 10. More specifically, for non-limiting examples, the molar ratio is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc. More preferably, it is 0.2 to 5.

[0053] In the above technical solution, the molar ratio of diol to intermediate product 3 in step (2) is preferably greater than 1 and less than 2, more preferably 1.1 to 1.5, for example but not limited to 1.05, 1.1, 1.15, 1.20, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95 and the like.

[0054] In the above technical solution, the esterification reaction in step (2) is preferably carried out to an esterification rate of 95% to 99%, for example but not limited to 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.

[0055] In order to achieve the above-mentioned esterification rate, those skilled in the art can reasonably select the esterification temperature and esterification time according to the actual conditions such as the operating conditions allowed by the reaction equipment. As a general rule, the higher the esterification temperature and the longer the esterification time, the more conducive to improving the esterification rate.

[0056] As a non-limiting example only, the esterification temperature in step (2) can be selected from 150 to 250° C., with more specific non-limiting examples being 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., and the like. Within this temperature range, when the water produced by the esterification reaction is continuously separated, even when no catalyst is used as in the embodiment of the present invention, the desired esterification rate can generally be achieved with an esterification reaction time of 0.5 to 2 hours. Of course, an esterification catalyst can also be used in the esterification reaction, which results in a faster esterification reaction rate.

[0057] The esterification reaction in step (2) can be carried out under the autogenous pressure of the reaction, or it can be carried out under a pressure higher than the autogenous pressure by filling the reaction system with an inert gas, such as nitrogen. Since the esterification reaction in step (2) is a liquid phase reaction, the pressure has no significant effect on the progress of the esterification reaction.

[0058] Those skilled in the art know that since the above-mentioned step (2) and the above-mentioned step (i) belong to esterification reaction, esterification is easy to carry out, and a catalyst can be added or not. However, in the prepolymerization and final polymerization of step (ii) and step (iii), as the molecular chain increases, the mobility of the reactive group is limited, and a polymerization catalyst is usually required. The polymerization catalyst can be added in the esterification stage of step (2) and / or step (i), and enter the polycondensation stage of step (ii) and then step (iii) together with the esterification product. It can also be added in the prepolymerization of step (ii) and / or the final polymerization stage of step (iii), and comparable technical effects can be achieved without having to pay creative labor. In order to facilitate the dispersion of the catalyst in step (ii) and step (iii) and to play a more uniform catalytic effect, it is preferably added in the esterification stage of step (2) and / or step (i). For comparison only, the polymerization catalysts in the embodiments of the present invention are all added in step (i).

[0059] Regarding polymerization catalysts, those known to those skilled in the art, such as, but not limited to, antimony-based polymerization catalysts (such as, but not limited to, antimony trioxide, antimony acetate, and antimony glycolate), titanium-based polymerization catalysts, and the like, are not limited thereto and can all achieve comparable technical effects. For comparison purposes only, the polymerization catalysts used in the examples are all antimony-based catalysts, and the amount of the antimony-based catalyst used, expressed as antimony and measured by weight, is 100 to 300 ppmw (such as, but not limited to, 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200 ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.) relative to the terephthalic acid added in step (i). For comparison purposes only, the antimony-based polymerization catalysts used in the examples are all antimony glycolate.

[0060] Regarding the concept of esterification rate in the above steps (2) and (i), those skilled in the art will appreciate that the esterification rate is used to monitor the degree of completion of the esterification reaction. The esterification rate is defined as the ratio of the number of moles of carboxyl groups that generate ester groups to the number of moles of carboxyl groups in the feedstock. The esterification rate can be controlled by metering and collecting the amount of water generated and distilled during the esterification reaction. The esterification rate is measured by comparing the weight of the water actually generated during the esterification reaction with the weight of the water generated assuming that the carboxyl groups in the feedstock are completely esterified. Specifically, it is calculated according to the following formula:

[0061] Esterification rate (%) = (weight of water actually produced by esterification reaction / weight of water produced by assuming that the carboxyl groups in the reaction raw materials are completely esterified) × 100%.

[0062] The second technical problem to be solved by the present invention is to provide an antibacterial polyester.

[0063] To solve the second of the above technical problems, the technical solution of the present invention is as follows:

[0064] An antibacterial polyester is obtained by the preparation method described in any one of the technical solutions to the above technical problems.

[0065] The third technical problem to be solved by the present invention is to provide a method for producing antibacterial fiber.

[0066] To solve the third of the above technical problems, the technical solution of the present invention is as follows:

[0067] A method for producing antibacterial fiber comprises the following steps:

[0068] (a) blending spinning-grade PET polyester with the antibacterial polyester described in the technical solution of the second technical problem above, and melt spinning to obtain spun fibers;

[0069] (b) Hot drawing of the as-spun fibers.

[0070] The key to the present invention lies in the selection of the antimicrobial component (or, more accurately, the antimicrobial polyester). The specific production process for the antimicrobial fiber is not particularly limited. Those skilled in the art can reasonably select and adjust commonly used processes and conditions to achieve comparable technical results. The processes and conditions described below are provided for non-limiting purposes only.

[0071] For example, but not limited to, the mass ratio of the antimicrobial polyester (calculated by N content) to the spinning-grade PET polyester in step (a) is q:100, where q is greater than 0 and less than 0.2. More specific non-limiting examples include q of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, and the like, and more preferably 0.02 to 0.15. For comparison purposes only, q is generally 0.04 in the embodiments.

[0072] For example, but not limited to, the intrinsic viscosity of the spinning-grade PET polyester in step (a) is 0.60-0.70 dl / g. As non-limiting examples, for example, but not limited to, the intrinsic viscosity of the spinning-grade PET polyester is 0.61 dl / g, 0.62 dl / g, 0.63 dl / g, 0.64 dl / g, 0.65 dl / g, 0.66 dl / g, 0.67 dl / g, 0.68 dl / g, 0.69 dl / g, etc. For comparison purposes only, the commercial spinning polyethylene terephthalate (hereinafter referred to as commercial spinning-grade PET) used in the specific embodiment of the present invention is SB500 type produced by Sinopec Yizheng Chemical Fiber Co., Ltd., with an intrinsic viscosity of 0.67 dl / g. The actual measured intrinsic viscosity is 0.68 dl / g.

[0073] For example, but not limited to, the above-mentioned melt spinning can be used to produce filaments or staples. The filaments can be FDY, POY, or DTY prepared by adding POY to a stretchable yarn. The specifications of the filaments can be 50 to 300D (for example, but not limited to 50D, 60D, 70D, 80D, 90D, 100D, 110D, 120D, 130D, 140D, 150D, 160D, 170D, 180D, 190D, and 200D); the length of the staples can be 38 to 76 mm, and the fineness can be 0.5 to 3.0D. Whether filaments or staples are produced, regardless of the above-mentioned specifications, or regardless of which process is used for production, are not the key to the present invention, and comparable technical effects can be achieved. For comparison purposes only, the FDY process is used to produce filaments in the specific embodiments of the present invention, and the specifications of the filaments are all 150D.

[0074] In the above technical solution, the drawing temperature in step (b) is preferably 120-160° C., for example but not limited to 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., and 160° C. For comparison purposes only, the drawing temperature in the specific embodiment of the present invention is 140° C.

[0075] In the above technical solution, the drafting ratio in step (b) is preferably 3.0 to 5.0, for example but not limited to 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5.0. For comparison purposes only, the drafting ratio in the specific embodiment of the present invention is 4.0.

[0076] The fourth technical problem to be solved by the present invention is to provide antibacterial fiber.

[0077] To solve the fourth technical problem above, the technical solution of the present invention is as follows:

[0078] An antibacterial fiber is obtained by the production method described in any one of the technical solutions of the third technical problem above.

[0079] The fifth technical problem to be solved by the present invention is to provide the application of antibacterial fibers.

[0080] To solve the fifth technical problem above, the technical solution of the present invention is as follows:

[0081] The application of the antibacterial fiber described in the technical solution to the fourth technical problem above in the production of medical surgical products, especially in antibacterial gauze and / or antibacterial bandages.

[0082] Because the antimicrobial fibers possess antimicrobial properties, those skilled in the art will appreciate that they can be used to produce medical gauze and bandages. Due to the antimicrobial properties of the fibers, wound infections can be prevented during use of gauze or bandages produced using these fibers. Regarding the use of gauze or bandages made from these fibers, those skilled in the art can reasonably select from known methods for producing gauze or bandages from these fibers, without requiring any inventive effort.

[0083] The intrinsic viscosity of the present invention is measured using Method A in Section 5.1.1 of GB / T 14190-2017 (Test method for fiber-grade polyester (PET) chips), and the solvent used is a mixture of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 50:50.

[0084] The nitrogen content in the specific embodiments of the present invention is determined by the Kjeldahl method.

[0085] The durability of the antimicrobial performance of antimicrobial polyester fibers was evaluated according to GBT 20944.3-2008 Evaluation of Antimicrobial Properties of Textiles - Part 3: Oscillation Method. Prior to testing, the fiber products were washed 50 times according to the method in 10.1.2 of the standard. The test bacteria used was Staphylococcus aureus (ATCC 6538). A higher inhibition rate after 50 washes indicates better antimicrobial performance and durability of the fiber product.

[0086] The present invention is described in detail below through specific embodiments. DETAILED DESCRIPTION

[0087] The antibacterial rates in the examples and comparative examples are all the antibacterial rates measured after washing 50 times by the above method. In this application document, ppmw means 1 / 1000000 parts by weight.

[0088] [Example 1]

[0089] 1. Synthesis of reactive antibacterial components

[0090] 1.1, the compound shown in formula 3 is obtained

[0091] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0092] 1.2. Obtaining reactive antimicrobial components

[0093] Ethylene glycol and the product of step 1.1 were mixed in a molar ratio of 1.3:1 as reaction raw materials, and esterification was carried out at 180°C, with the generated water being metered and collected until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.43% by weight.

[0094] 2. Preparation of antibacterial polyester

[0095] 2.1 Esterification

[0096] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0097] 2.2 Precondensation

[0098] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0099] 2.3 Final polycondensation

[0100] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.73% by weight.

[0101] 3. Antibacterial fiber production

[0102] 3.1 Melt Spinning

[0103] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0104] 3.2 Drafting

[0105] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0106] 4. Antibacterial polyester fiber test

[0107] After testing, the antibacterial rate was 89.1%.

[0108] [Comparative Example 1]

[0109] The main difference from Example 1 is that the compound of formula 3 is directly added during the esterification stage in the preparation of the antibacterial polyester, specifically:

[0110] 1. Obtain the compound shown in formula 3 (same as 1.1 in Example 1)

[0111] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0112] 2. Preparation of antibacterial polyester

[0113] 2.1 Esterification

[0114] Terephthalic acid, the product of step 1, antimony glycol and ethylene glycol were mixed (wherein the molar ratio of ethylene glycol to (the sum of the product of step 1 and terephthalic acid) was 1.2; the mass ratio of the product of step 1 to terephthalic acid, calculated as nitrogen, was 1.2:100; and the amount of antimony glycol used, calculated as antimony, was equivalent to 200 ppmw of the weight of terephthalic acid) as reaction raw materials. An esterification reaction was carried out at 200° C., and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0115] 2.2 Precondensation

[0116] The esterified material I in step 2.1 was polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 min.

[0117] 2.3 Final polycondensation

[0118] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.73% by weight.

[0119] 3. Antibacterial fiber production

[0120] 3.1 Melt Spinning

[0121] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0122] 3.2 Drafting

[0123] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0124] 4. Antibacterial polyester fiber test

[0125] After testing, the antibacterial rate was 76.8%.

[0126] [Comparative Example 2]

[0127] 1. Synthesis of reactive antibacterial components

[0128] Same as Example 1, specifically:

[0129] 1.1, the compound shown in formula 3 is obtained

[0130] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0131] 1.2. Obtaining reactive antimicrobial components

[0132] Ethylene glycol and the product of step 1.1 were mixed in a molar ratio of 1.3:1 as reaction raw materials, and esterification was carried out at 180°C, with the generated water being metered and collected until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.43% by weight.

[0133] 2. Preparation of antibacterial polyester

[0134] The main difference from Example 1 is that the product of step 1.2 is added during the esterification step in the preparation of the antibacterial polyester, specifically:

[0135] 2.1 Esterification

[0136] Terephthalic acid, the product of step 1.2, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, the mass ratio of the product of step 1.2 to terephthalic acid, calculated as nitrogen, was 1.2:100, and the amount of ethylene glycol antimony used, calculated as antimony, was equivalent to 200 ppmw of the weight of terephthalic acid) as reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0137] 2.2 Precondensation

[0138] The esterified material I in step 2.1 was polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 min.

[0139] 2.3 Final polycondensation

[0140] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.73% by weight.

[0141] 3. Antibacterial fiber production

[0142] 3.1 Melt Spinning

[0143] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0144] 3.2 Drafting

[0145] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0146] 4. Antibacterial polyester fiber test

[0147] After testing, the antibacterial rate was 82.9%.

[0148] [Example 2]

[0149] 1. Synthesis of reactive antibacterial components

[0150] 1.1, the compound shown in formula 3 is obtained

[0151] The same as step 1.1 of Example 1, specifically:

[0152] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0153] 1.2. Obtaining reactive antimicrobial components

[0154] The main difference from step 1.2 of Example 1 is that the diol is 1,4-butanediol, specifically:

[0155] 1,4-Butanediol and the product from step 1.1 were mixed in a molar ratio of 1.3:1 as the reaction raw materials. Esterification was carried out at 180°C, and the generated water was collected and metered until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.27% by weight.

[0156] 2. Preparation of antibacterial polyester

[0157] 2.1 Esterification

[0158] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0159] 2.2 Precondensation

[0160] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0161] 2.3 Final polycondensation

[0162] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content by weight of the antibacterial polyester was determined to be 0.72%.

[0163] 3. Antibacterial fiber production

[0164] 3.1 Melt Spinning

[0165] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0166] 3.2 Drafting

[0167] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0168] 4. Antibacterial polyester fiber test

[0169] After testing, the antibacterial rate was 87.6%.

[0170] [Example 3]

[0171] 1. Synthesis of reactive antibacterial components

[0172] 1.1, the compound shown in formula 3 is obtained

[0173] The same as step 1.1 of Example 1, specifically:

[0174] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0175] 1.2. Obtaining reactive antimicrobial components

[0176] The main difference from step 1.2 of Example 1 is that the diol is polyethylene glycol 400, specifically:

[0177] Polyethylene glycol 400 and the product from step 1.1 were mixed in a molar ratio of 1.3:1 as reaction raw materials. Esterification was carried out at 180°C, and the generated water was collected and metered until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 1.37% by weight.

[0178] 2. Preparation of antibacterial polyester

[0179] 2.1 Esterification

[0180] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0181] 2.2 Precondensation

[0182] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0183] 2.3 Final polycondensation

[0184] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.59% by weight.

[0185] 3. Antibacterial fiber production

[0186] 3.1 Melt Spinning

[0187] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0188] 3.2 Drafting

[0189] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0190] 4. Antibacterial polyester fiber test

[0191] After testing, the antibacterial rate was 90.9%.

[0192] [Example 4]

[0193] 1. Synthesis of reactive antibacterial components

[0194] 1.1, the compound shown in formula 3 is obtained

[0195] The same as step 1.1 of Example 1, specifically:

[0196] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0197] 1.2. Obtaining reactive antimicrobial components

[0198] The main difference from step 1.2 of Example 1 is that the diol is 1,4-cyclohexanedimethanol, specifically:

[0199] 1,4-Cyclohexanedimethanol and the product from step 1.1 were mixed in a molar ratio of 1.3:1 as reaction raw materials. Esterification was carried out at 180°C, and the generated water was collected and metered until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.03% by weight.

[0200] 2. Preparation of antibacterial polyester

[0201] 2.1 Esterification

[0202] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0203] 2.2 Precondensation

[0204] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0205] 2.3 Final polycondensation

[0206] The material obtained in step 2.2 was subjected to a polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.69% by weight.

[0207] 3. Antibacterial fiber production

[0208] 3.1 Melt Spinning

[0209] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0210] 3.2 Drafting

[0211] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0212] 4. Antibacterial polyester fiber test

[0213] After testing, the antibacterial rate was 95.3%.

[0214] [Example 5]

[0215] 1. Synthesis of reactive antibacterial components

[0216] 1.1, the compound shown in formula 3 is obtained

[0217] The same as step 1.1 of Example 1, specifically:

[0218] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0219] 1.2. Obtaining reactive antimicrobial components

[0220] The main difference from step 1.2 of Example 1 is that the diols are ethylene glycol and 1,4-cyclohexanedimethanol, specifically:

[0221] Ethylene glycol, 1,4-cyclohexanedimethanol, and the product from step 1.1 were mixed (the molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol being 1:1, and the molar ratio of the sum of ethylene glycol and 1,4-cyclohexanedimethanol to the product from step 1.1 being 1.3:1) as the reaction raw materials. Esterification was performed at 180°C, and the generated water was collected and metered until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.21% by weight.

[0222] 2. Preparation of antibacterial polyester

[0223] 2.1 Esterification

[0224] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0225] 2.2 Precondensation

[0226] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0227] 2.3 Final polycondensation

[0228] The material obtained in step 2.2 was subjected to a polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content in the antibacterial polyester was determined to be 0.71% by weight.

[0229] 3. Antibacterial fiber production

[0230] 3.1 Melt Spinning

[0231] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0232] 3.2 Drafting

[0233] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0234] 4. Antibacterial polyester fiber test

[0235] After testing, the antibacterial rate was 99.7%.

[0236] [Example 6]

[0237] 1. Synthesis of reactive antibacterial components

[0238] 1.1, the compound shown in formula 3 is obtained

[0239] The same as step 1.1 of Example 1, specifically:

[0240] With stirring, an aqueous solution of hexadecyltrimethylammonium chloride (5.6% by weight) was added to an equal weight of an aqueous solution of 5-sodium sulfoisophthalate (5.0% by weight). The mixture was stirred for 2 hours, allowed to stand for separation, and filtered. The filter cake was washed three times with water, each time using an equal volume of water to the filter cake. The filter cake was dried at 80°C for 5 hours to obtain the dry product of the compound represented by Formula 3. The nitrogen content of the product was determined to be 2.64% by weight.

[0241] 1.2. Obtaining reactive antimicrobial components

[0242] The main difference from step 1.2 of Example 1 is that the diols are ethylene glycol and 1,4-cyclohexanedimethanol, specifically:

[0243] Ethylene glycol, 1,4-cyclohexanedimethanol, and the product from step 1.1 were mixed (the molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol being 4:1, and the molar ratio of the sum of ethylene glycol and 1,4-cyclohexanedimethanol to the product from step 1.1 being 1.3:1) as the reaction raw materials. Esterification was carried out at 180°C, and the generated water was collected and metered until the esterification yield reached 97%, thereby obtaining a reactive antimicrobial component. The product had a nitrogen content of 2.34% by weight.

[0244] 2. Preparation of antibacterial polyester

[0245] 2.1 Esterification

[0246] Terephthalic acid, ethylene glycol antimony, and ethylene glycol were mixed (the molar ratio of ethylene glycol to terephthalic acid was 1.2, and the amount of ethylene glycol antimony used was equivalent to 200 ppmw of the weight of terephthalic acid in terms of antimony) as the reaction raw materials. An esterification reaction was carried out at 200° C. and the water generated by the esterification was measured and collected until the esterification yield reached 97%, thereby obtaining esterified material I.

[0247] 2.2 Precondensation

[0248] The product of step 1.2 is calculated based on the weight of nitrogen contained, and the esterification material I of step 2.1 is calculated based on the weight of terephthalic acid required for its preparation. The product of step 1.2 and the esterification material I of step 2.1 are mixed in a weight ratio of 1.2:100, and polycondensed at an absolute pressure of 500 Pa and 260° C. for 45 minutes.

[0249] 2.3 Final polycondensation

[0250] The material obtained in step 2.2 was subjected to polycondensation reaction at an absolute pressure of 50 Pa and 280° C. until the intrinsic viscosity reached 0.68 dl / g, thereby obtaining an antibacterial polyester. The nitrogen content by weight of the antibacterial polyester was determined to be 0.72%.

[0251] 3. Antibacterial fiber production

[0252] 3.1 Melt Spinning

[0253] The antibacterial polyester (calculated based on the N content) prepared in step 2.3 was blended with commercial spinning-grade PET at a weight ratio of 0.040:100 and melt-spun to obtain spun fibers at a melt-spinning temperature of 280°C.

[0254] 3.2 Drafting

[0255] The spun fibers obtained by melt spinning were subjected to hot drawing at a drawing ratio of 4.0 times and a drawing temperature of 140° C. FDY fibers were then spun to obtain FDY fibers having a specification of 150D.

[0256] 4. Antibacterial polyester fiber test

[0257] After testing, the antibacterial rate was 98.5%.

Claims

1. A method for preparing antibacterial polyester, comprising: (i) carrying out an esterification reaction between a diol and a dibasic acid to obtain an esterified material I; (ii) mixing the esterified material I with the reactive antibacterial component to carry out a pre-polycondensation reaction to obtain a pre-polycondensation product; (iii) subjecting the pre-polycondensation product to a final polycondensation reaction to obtain an antibacterial polyester; The reactive antibacterial component is obtained by esterification reaction of the substance shown in Formula 3 with diol: Q is a quaternary ammonium group containing a long-chain hydrocarbon group, the number of carbon atoms in the long-chain hydrocarbon group is 6 to 20, and Ar is an aromatic ring; The diol includes 1,4-cyclohexanedimethanol.

2. The preparation method according to claim 1, characterized in that: The diol is a mixed alcohol of ethylene glycol and 1,4-cyclohexanedimethanol.

3. The preparation method according to claim 2, characterized in that: The molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol is 0.1-10.

4. The preparation method according to claim 3, characterized in that: The molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol is 0.2-5.

5. The preparation method according to claim 1, characterized in that: Ar is a benzene ring or a naphthalene ring.

6. The preparation method according to claim 1, characterized in that: In step (i): the diol comprises at least one selected from the group consisting of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,4-cyclohexanedimethanol; and / or the dibasic acid comprises at least one selected from the group consisting of terephthalic acid, succinic acid, adipic acid, isophthalic acid and furandicarboxylic acid; and / or the molar ratio of the diol to the dibasic acid is 1.1 to 1.5; and / or the esterification reaction is carried out until the esterification rate is 95 to 99%; and / or the reaction temperature is 150 to 250°C.

7. The preparation method according to claim 1, characterized in that: In step (ii): the reaction pressure is 400-600 Pa; and / or the reaction temperature is 255-265° C.; and / or the reaction time is 30-60 minutes.

8. The preparation method according to claim 1, characterized in that: In step (iii): the reaction pressure is below 100 Pa; and / or the reaction temperature is 270-285° C.; and / or step (iii) is carried out until the intrinsic viscosity is 0.60-0.75 dL / g.

9. The preparation method according to claim 1, characterized in that: The synthesis method of the reactive antibacterial component comprises the following steps: (1) subjecting compound 1 to an ion exchange reaction with compound 2 in a solvent to obtain an intermediate product 3; Compound 1 conforms to the structure shown in Formula 1: Q + X - , Formula 1, Compound 2 conforms to the structure shown in Formula 2: Intermediate product 3 conforms to the structure shown in formula 3; X is Cl or Br; M is an alkali metal; (2) The intermediate product 3 undergoes an esterification reaction with diol to obtain a reactive antibacterial component.

10. The preparation method according to claim 9, characterized in that: The solvent described in step (1) is water.

11. The preparation method according to claim 9, characterized in that: Compound 1 conforms to the structure shown in formula 1a: R1 is a long-chain hydrocarbon group, and the number of carbon atoms in R1 is 6 to 20; R2 to R4 are short-chain hydrocarbon groups; And / or compound 2 conforms to the structure shown in formula 2a: and / or the molar ratio of diol to intermediate product 3 in step (2) is greater than 1 and less than 2; and / or the esterification reaction in step (2) is carried out until the esterification rate is 95-99%; And / or the esterification temperature in step (2) is 150-250°C.

12. The preparation method according to claim 11, characterized in that: R2-R4 are independently C1-C2 alkyl groups; and / or the molar ratio of the diol to the intermediate product 3 in step (2) is 1.1-1.

5.

13. An antibacterial polyester, characterized in that: The antibacterial polyester is an antibacterial polyester obtained by the preparation method according to any one of claims 1 to 12.

14. A method for producing an antibacterial fiber, comprising the following steps: (a) blending spinning-grade PET polyester with the antibacterial polyester described in claim 13, and melt spinning to obtain spun fibers; (b) Thermal drawing of the spun fibers.

15. The production method according to claim 14, characterized in that: The mass ratio of the antibacterial polyester in step (a) to the spinning-grade PET polyester is b:100, based on the N contained therein, and b is greater than 0 and less than 0.2; and / or the drawing temperature in step (b) is 120-160° C.; and / or the drawing multiple in step (b) is 3.0-5.

0.

16. An antibacterial fiber, characterized in that: The antibacterial fiber is an antibacterial fiber obtained by the production method according to claim 14 or 15.

17. Use of the antibacterial fiber according to claim 16 in the production of medical surgical products.

18. Use of the antibacterial fiber according to claim 16 in producing antibacterial gauze and / or antibacterial bandage.

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