Silver ion antibacterial copolyester and preparation method thereof

Abstract

The invention provides silver ion antibacterial copolyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. According to the silver ion antibacterial copolyester, isophthalic acid containing sulfonic acid silver ion groups is used as a comonomer to be bonded to a polyethylene glycol terephthalate molecular main chain, and silver ions with efficient antibacterial performance are loaded to a polyester molecular chain through ionic bonds, so that the silver ions are dispersed in a polyester matrix. The preparation method of the silver ion antibacterial copolyester comprises the following steps: preparing 5-sulfoisophthalic acid silver; preparing slurry from 5-sulfoisophthalic acid silver, terephthalic acid and ethylene glycol; carrying out esterification reaction on the slurry to obtain a silver-containing polyester oligomer; carrying out a pre-polycondensation reaction and a final polycondensation reaction on the silver-containing polyester oligomer to obtain a silver ion antibacterial copolyester melt; and carrying out post-treatment on the silver ion antibacterial copolyester melt to obtain the silver ion antibacterial copolyester chip. The antibacterial efficiency of silver ions can be improved, and polyester products are endowed with excellent antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly to a silver ion antibacterial copolyester and a preparation method thereof. Background Art

[0002] Polyester has good fiber-forming properties, mechanical properties, wear resistance, creep resistance, low water absorption, electrical insulation and other properties, and is widely used in fibers, packaging bottles, films, engineering plastics, etc. It is the second largest class of synthetic polymers after polyolefins. With the improvement of people's living standards and the enhancement of people's awareness of health and environment, the market demand for antibacterial polyester fibers, films and plastic products has increased rapidly. In the prior art, the antibacterial efficiency of polyester is relatively low. Summary of the Invention

[0003] In view of this, the present invention provides a silver ion antibacterial copolyester and a preparation method thereof, which can disperse silver ions with high antibacterial performance in the polyester matrix, improve the antibacterial efficiency of silver ions, endow polyester products with excellent antibacterial properties, and thus be more suitable for practical use.

[0004] In order to achieve the first above-mentioned purpose, the technical solution of the silver ion antibacterial copolyester provided by the present invention is as follows:

[0005] The present invention provides a silver ion antibacterial copolyester, in which isophthalic acid containing a sulfonic acid silver ion group is used as a comonomer and bonded to the main chain of polyethylene terephthalate molecules, and silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, so that the silver ions are dispersed in the polyester matrix.

[0006] The silver ion antibacterial copolyester provided by the present invention can also be further realized by the following technical measures.

[0007] Preferably, the dispersion mode of the silver ions in the polyester matrix is atomic-level uniform dispersion.

[0008] Preferably, the silver ion antibacterial copolyester product has antibacterial properties.

[0009] Preferably, the filaments of the silver ion antibacterial copolyester spun in a specification of 75D / 36F have a bacteriostatic rate of not less than 95% against Staphylococcus aureus, not less than 91% against Escherichia coli, and not less than 80% against Candida albicans after being washed 50 times.

[0010] In order to achieve the second above-mentioned purpose, the technical solution of the preparation method of the silver ion antibacterial copolyester provided by the present invention is as follows:

[0011] The preparation method of the silver ion antibacterial copolyester provided by the present invention includes the following steps:

[0012] Silver isophthalate-5-sulfonate was prepared;

[0013] The silver isophthalate-5-sulfonate, terephthalic acid, and ethylene glycol were formulated into a slurry. Among them, the addition amount of the silver isophthalate-5-sulfonate was 80 ppm - 1000 ppm of the mass of the silver ion antibacterial copolyester produced in real time, the addition amount of the ethylene glycol was 33.9% - 64.6% of the mass of the silver ion antibacterial copolyester produced in real time, and the molar ratio of glycol to the acid of silver isophthalate-5-sulfonate and terephthalic acid was 1.05 - 2.0;

[0014] The slurry was subjected to an esterification reaction to obtain a silver-containing polyester oligomer;

[0015] The silver-containing polyester oligomer was subjected to a pre-polycondensation reaction and a final polycondensation reaction to obtain a silver ion antibacterial copolyester melt;

[0016] The silver ion antibacterial copolyester melt was post-treated to obtain silver ion antibacterial copolyester chips.

[0017] The preparation method of the silver ion antibacterial copolyester provided by the present invention can also be further realized by the following technical measures.

[0018] Preferably, in the step of post-treating the silver ion antibacterial copolyester melt to obtain silver ion antibacterial copolyester chips, the post-treatment includes filtration, cooling and solidification, and pelletizing.

[0019] Preferably, the preparation of silver isophthalate-5-sulfonate specifically includes the following steps:

[0020] An alkaline silver salt was added to an aqueous solution of isophthalic acid-5-sulfonic acid, and after an acid-base neutralization reaction, recrystallization, filtration, and drying, the silver isophthalate-5-sulfonate was obtained. Among them,

[0021] The alkaline silver salt was selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate;

[0022] The addition amount of the alkaline silver salt was 47.1% - 56.0% of the mass of the isophthalic acid-5-sulfonic acid;

[0023] The mass percentage content of isophthalic acid-5-sulfonic acid in the aqueous solution of isophthalic acid-5-sulfonic acid was 10% - 30%;

[0024] The temperature of the acid-base neutralization reaction was 50°C - 90°C.

[0025] Preferably, in the step of subjecting the slurry to an esterification reaction to obtain a silver-containing polyester oligomer,

[0026] The reaction temperature of the esterification reaction was 250°C - 270°C;

[0027] The reaction pressure of the esterification reaction is 100 kPa - 210 kPa;

[0028] The esterification rate of the silver-containing polyester oligomer is 90% - 97%.

[0029] Preferably, during the step of subjecting the silver-containing polyester oligomer to a prepolycondensation reaction,

[0030] The reaction temperature of the prepolycondensation reaction is 270 °C - 290 °C;

[0031] The reaction pressure of the prepolycondensation reaction is 2 kPa - 4 kPa;

[0032] The intrinsic viscosity of the silver ion antibacterial copolyester prepolymer prepared by the prepolycondensation reaction is 0.15 dL / g - 0.30 dL / g.

[0033] Preferably, during the step of subjecting the silver ion antibacterial copolyester prepolymer to a final polycondensation reaction,

[0034] The reaction temperature of the final polycondensation reaction is 275 °C - 290 °C;

[0035] The reaction pressure of the final polycondensation reaction is 100 Pa - 300 Pa;

[0036] The intrinsic viscosity of the silver ion antibacterial copolyester melt prepared by the final polycondensation reaction is 0.60 dL / g - 0.75 dL / g.

[0037] The silver ion antibacterial copolyester prepared by the method for preparing silver ion antibacterial copolyester provided by the present invention has isophthalic acid containing a sulfonic acid silver ion group as a comonomer bonded to the main chain of the polyethylene terephthalate molecule, and silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing the polyester product with excellent antibacterial performance. Description of the Drawings

[0038] By reading the following detailed description of the preferred embodiments, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present invention. Moreover, throughout the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0039] Attached Figure 1 is a process flow chart of the method for preparing silver ion antibacterial copolyester provided by the embodiment of the present invention;

[0040] Attached Figure 2Schematic diagram of the material change relationship during the preparation process of the silver ion antibacterial copolyester provided by the embodiments of the present invention. Detailed implementation manners

[0041] In view of this, the present invention provides a silver ion antibacterial copolyester and a preparation method thereof, which can disperse silver ions with high antibacterial performance in a polyester matrix, improve the antibacterial efficiency of silver ions, endow polyester products with excellent antibacterial performance, and thus be more suitable for practical use.

[0042] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, the following describes in detail a silver ion antibacterial copolyester and a preparation method thereof proposed according to the present invention, its specific implementation manners, structures, features and effects in conjunction with the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. In addition, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0043] The term "and / or" in this article is merely a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B is specifically understood as: it can include both A and B at the same time, A can exist alone, or B can exist alone, and it can have any of the above three situations.

[0044] Silver ion antibacterial copolyester

[0045] The embodiments of the present invention provide a silver ion antibacterial copolyester. Terephthalic acid containing a sulfonic acid silver ion group is used as a comonomer and bonded to the main chain of polyethylene terephthalate molecules. Silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, enabling the dispersion of silver ions in the polyester matrix.

[0046] The silver ion antibacterial copolyester provided by the embodiments of the present invention uses terephthalic acid containing a sulfonic acid silver ion group as a comonomer and bonds it to the main chain of polyethylene terephthalate molecules. Silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, achieving atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing polyester products with excellent antibacterial performance.

[0047] Among them, the dispersion mode of silver ions in the polyester matrix is atomic-level uniform dispersion.

[0048] Among them, the silver ion antibacterial copolyester product has antibacterial performance.

[0049] Among them, the filament with a specification of 75D / 36F spun from the silver ion antibacterial copolyester has a bacteriostatic rate of not less than 95% against Staphylococcus aureus, not less than 91% against Escherichia coli, and not less than 80% against Candida albicans after being washed 50 times.

[0050] Preparation method of silver ion antibacterial copolyester

[0051] See Appendix Figure 1 and Appendix Figure 2 For the preparation method of the silver ion antibacterial copolyester provided by the embodiment of the present invention, it includes the following steps:

[0052] Step S1: Prepare silver 5-sulfoisophthalate.

[0053] Step S2: Prepare a slurry with silver 5-sulfoisophthalate, terephthalic acid, and ethylene glycol. Among them, the addition amount of silver 5-sulfoisophthalate is 80 ppm - 1000 ppm of the mass of the silver ion antibacterial copolyester produced in real time, the addition amount of the ethylene glycol is 33.9% - 64.6% of the mass of the silver ion antibacterial copolyester produced in real time, and the molar ratio of glycol to the sum of 5-sulfoisophthalic acid and terephthalic acid is 1.05 - 2.0.

[0054] Step S3: Perform an esterification reaction on the slurry to obtain a silver-containing polyester oligomer.

[0055] Step S4: Subject the silver-containing polyester oligomer to a pre-polycondensation reaction and a final polycondensation reaction to obtain a silver ion antibacterial copolyester melt.

[0056] Step S5: Subject the silver ion antibacterial copolyester melt to post-treatment to obtain silver ion antibacterial copolyester chips.

[0057] The silver ion antibacterial copolyester prepared by the preparation method of the silver ion antibacterial copolyester provided by the embodiment of the present invention is obtained by bonding isophthalic acid containing a sulfonic acid silver ion group as a comonomer to the main chain of the polyethylene terephthalate molecule, and loading silver ions with high antibacterial performance onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing the polyester products with excellent antibacterial properties.

[0058] Among them, in the step of subjecting the silver ion antibacterial copolyester melt to post-treatment to obtain silver ion antibacterial copolyester chips, the post-treatment includes filtration, cooling and solidification, and pelletizing.

[0059] Among them, the specific steps for preparing silver 5-sulfoisophthalate include the following steps:

[0060] An alkaline silver salt is added to an aqueous solution of isophthalic acid-5-sulfonic acid. Through an acid-base neutralization reaction, recrystallization, filtration, and drying, silver isophthalate-5-sulfonate is obtained. Among them, the alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate; the addition amount of the alkaline silver salt is 47.1%-56.0% of the mass of isophthalic acid-5-sulfonic acid; the mass percentage content of isophthalic acid-5-sulfonic acid in the aqueous solution of isophthalic acid-5-sulfonic acid is 10%-30%; the temperature of the acid-base neutralization reaction is 50°C-90°C.

[0061] Among them, in the step of subjecting the slurry to an esterification reaction to obtain a silver-containing polyester oligomer, the reaction temperature of the esterification reaction is 250°C-270°C; the reaction pressure of the esterification reaction is 100 kPa-210 kPa, and the esterification rate of the silver-containing polyester oligomer is 90%-97%.

[0062] Among them, in the step of subjecting the silver-containing polyester oligomer to a prepolycondensation reaction, the reaction temperature of the prepolycondensation reaction is 270°C-290°C; the reaction pressure of the prepolycondensation reaction is 2 kPa-4 kPa; the intrinsic viscosity of the silver ion antibacterial copolyester prepolymer prepared by the prepolycondensation reaction is 0.15 dL / g-0.30 dL / g.

[0063] Among them, in the step of subjecting the silver ion antibacterial copolyester prepolymer to a final polycondensation reaction, the reaction temperature of the final polycondensation reaction is 275°C-290°C; the reaction pressure of the final polycondensation reaction is 100 Pa-300 Pa; the intrinsic viscosity of the silver ion antibacterial copolyester melt prepared by the final polycondensation reaction is 0.60 dL / g-0.75 dL / g.

[0064] Example 1

[0065] (1) Silver oxide is added to an aqueous solution with a mass percentage content of isophthalic acid-5-sulfonic acid of 20%. After an acid-base neutralization reaction at 80°C, recrystallization, filtration, and drying are carried out to obtain silver isophthalate-5-sulfonate, where the addition amount of silver oxide is 47.1% of the weight of isophthalic acid-5-sulfonic acid.

[0066] (2) The silver isophthalate-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. Among them, the molar ratio of alcohol to acid in the slurry is 1.15, the addition amount of silver isophthalate-5-sulfonate is 160 ppm of the mass of the silver ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 37.2% of the mass of the silver ion antibacterial copolyester produced in real time.

[0067] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer; the esterification rate of the silver-containing polyester oligomer is 97%. The esterification reaction system consists of two esterification reactors in series. The reaction temperature of the first esterification reactor is 260°C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification reactor is 265°C and the reaction pressure is 120 kPa.

[0068] (4) Continuously convey the silver-containing polyester oligomer prepared in step (3) to a prepolycondensation system for prepolycondensation reaction to obtain a silver ion antibacterial copolyester prepolymer; the prepolycondensation reaction temperature is 280°C and the reaction pressure is 3 kPa. The intrinsic viscosity of the prepared silver ion antibacterial copolyester prepolymer is 0.25 dL / g.

[0069] (5) Continuously convey the silver ion antibacterial copolyester prepolymer prepared in step (4) to a final polycondensation system for final polycondensation reaction to obtain a silver ion antibacterial copolyester melt; the final polycondensation reaction temperature is 285°C and the reaction pressure is 200 Pa. The intrinsic viscosity of the prepared silver ion antibacterial copolyester melt is 0.69 dL / g.

[0070] (6) Filter the silver ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain silver ion antibacterial copolyester chips.

[0071] Example 2

[0072] (1) Add silver carbonate to an aqueous solution with a mass percentage of 10% of isophthalic acid-5-sulfonic acid. After carrying out an acid-base neutralization reaction at 50°C, recrystallize, filter and dry to obtain silver isophthalic acid-5-sulfonate, where the addition amount of silver carbonate is 56.0% of the weight of isophthalic acid-5-sulfonic acid.

[0073] (2) Prepare a slurry by mixing the silver isophthalic acid-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 2.0. The addition amount of silver isophthalic acid-5-sulfonate is 80 ppm of the real-time output mass of the silver ion antibacterial copolyester, and the addition amount of ethylene glycol is 64.6% of the real-time output mass of the silver ion antibacterial copolyester.

[0074] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer; the esterification rate of the silver-containing polyester oligomer is 90%. The reaction temperature of the esterification reactor is 250°C and the reaction pressure is 210 kPa.

[0075] (4) Continuously convey the silver-containing polyester oligomer prepared in step (3) to a prepolycondensation system for prepolycondensation reaction to obtain a silver ion antibacterial copolyester prepolymer; wherein the prepolycondensation reaction temperature is 290 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester prepolymer is 0.30 dL / g

[0076] (5) Continuously convey the silver ion antibacterial copolyester prepolymer prepared in step (4) to a final polycondensation system for final polycondensation reaction to obtain a silver ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 290 °C, the reaction pressure is 100 Pa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester melt is 0.75 dL / g

[0077] (6) Filter the silver ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain silver ion antibacterial copolyester chips.

[0078] Example 3

[0079] (1) Add silver oxide to an aqueous solution with a mass percentage of 30% of isophthalic acid-5-sulfonic acid, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain silver isophthalate-5-sulfonate, wherein the addition amount of silver oxide is 47.1% of the weight of isophthalic acid-5-sulfonic acid

[0080] (2) Prepare a slurry by mixing the silver isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15, the addition amount of silver isophthalate-5-sulfonate is 320 ppm of the real-time output mass of the silver ion antibacterial copolyester, and the addition amount of ethylene glycol is 37.2% of the real-time output mass of the silver ion antibacterial copolyester.

[0081] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer; wherein the esterification rate of the silver-containing polyester oligomer is 97%, and the esterification reaction system consists of two esterification reactors in series. The reaction temperature of the first esterification reactor is 260 °C and the reaction pressure is 170 kPa, and the reaction temperature of the second esterification reactor is 265 °C and the reaction pressure is 120 kPa.

[0082] (4) Continuously convey the silver-containing polyester oligomer prepared in step (5) to a prepolycondensation system for prepolycondensation reaction to obtain a silver ion antibacterial copolyester prepolymer; wherein the prepolycondensation reaction temperature is 275 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester prepolymer is 0.23 dL / g

[0083] (5) Continuously convey the silver ion antibacterial copolyester prepolymer prepared in step (4) to the final polycondensation system for final polycondensation reaction to obtain a silver ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 280 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester melt is 0.65 dL / g

[0084] (6) Filter the silver ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain silver ion antibacterial copolyester chips

[0085] Example 4

[0086] (1) Add silver sulfide to an aqueous solution with a mass percentage of 10% of isophthalic acid-5-sulfonic acid, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain silver isophthalic acid-5-sulfonate, wherein the addition amount of silver sulfide is 50.3% of the weight of isophthalic acid-5-sulfonic acid

[0087] (2) Prepare a slurry by mixing the silver isophthalic acid-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.05, the addition amount of silver isophthalic acid-5-sulfonate is 640 ppm of the real-time output quality of the silver ion antibacterial copolyester, and the addition amount of ethylene glycol is 33.9% of the real-time output quality of the silver ion antibacterial copolyester

[0088] (3) Continuously convey the slurry prepared in step (2) to an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer; the esterification rate of the silver-containing polyester oligomer is 97%. The esterification reaction system consists of two esterification reactors in series. The reaction temperature of the first esterification reactor is 265 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification reactor is 270 °C and the reaction pressure is 100 kPa

[0089] (4) Continuously convey the black antibacterial polyester oligomer prepared in step (4) to a prepolycondensation system for prepolycondensation reaction to obtain a silver ion antibacterial copolyester prepolymer; wherein the prepolycondensation reaction temperature is 270 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester prepolymer is 0.17 dL / g

[0090] (5) Continuously convey the silver ion antibacterial copolyester prepolymer prepared in step (4) to the final polycondensation system for final polycondensation reaction to obtain a silver ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 275 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester melt is 0.62 dL / g

[0091] (6) Filter the silver ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain silver ion antibacterial copolyester chips

[0092] Example 5

[0093] (1) Silver oxide is added to an aqueous solution with a mass percentage of 30% of 5-sulfoisophthalic acid. After an acid-base neutralization reaction at 90 °C, recrystallization, filtration, and drying are carried out to obtain silver 5-sulfoisophthalate, where the addition amount of silver oxide is 47.1% of the weight of 5-sulfoisophthalic acid.

[0094] (2) Silver 5-sulfoisophthalate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 2.0. The addition amount of silver 5-sulfoisophthalate is 1000 ppm of the mass of the silver ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 64.6% of the mass of the silver ion antibacterial copolyester produced in real time.

[0095] (3) The slurry configured in step (2) is continuously fed into an esterification reactor for an esterification reaction to obtain a silver-containing polyester oligomer. The esterification rate of the silver-containing polyester oligomer is 90%. The reaction temperature of the esterification reactor is 250 °C, and the reaction pressure is 210 kPa.

[0096] (4) The silver-containing polyester oligomer prepared in step (3) is continuously fed into a prepolycondensation system for a prepolycondensation reaction to obtain a silver ion antibacterial copolyester prepolymer. The prepolycondensation reaction temperature is 270 °C, the reaction pressure is 4 kPa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester prepolymer is 0.15 dL / g.

[0097] (5) The silver ion antibacterial copolyester prepolymer prepared in step (4) is continuously fed into a final polycondensation system for a final polycondensation reaction to obtain a silver ion antibacterial copolyester melt. The final polycondensation reaction temperature is 275 °C, the reaction pressure is 300 Pa, and the intrinsic viscosity of the prepared silver ion antibacterial copolyester melt is 0.60 dL / g.

[0098] (6) The silver ion antibacterial copolyester melt prepared in step (5) is filtered, cooled, solidified, and pelletized to obtain silver ion antibacterial copolyester chips.

[0099] Experimental example 1

[0100] (1) The silver ion antibacterial copolyester chips prepared in Examples 1 to 5 and the in-situ polymerized black polyester chips prepared in Comparative Example 1 are dried in a rotary drum with a vacuum degree less than 100 Pa and a drying temperature of 150 °C until the water content is less than 30 ppm.

[0101] (2) The dried slices prepared in step (1) are melt-spun on a melt spinning machine to prepare pre-oriented yarns with a specification of 120D / 36F, where the melt spinning temperature is 290 °C and the spinning speed is 3000 m / min.

[0102] (3) The pre-oriented yarns prepared in step (2) are drawn and processed on a flat drawing machine to prepare drawn yarns with a specification of 75D / 36F, where the draw ratio is 1.6 times, the drawing temperature is 80 °C, and the setting temperature is 130 °C

[0103] (4) The filaments with a specification of 75D / 36F prepared in step (3) are woven into a garter belt, then washed 50 times under test condition A1M in GB / T 12490-1990, and then the antibacterial rates of the garter belt against Staphylococcus aureus, Escherichia coli, and Candida albicans after 50 washes are tested according to GB / T 20944.3-2007. The test results are shown in Table 1

[0104] Table 1 Antibacterial performance test results of filaments with a specification of 75D / 36F spun from the in-situ polymerization silver antibacterial black polyester slices prepared in Examples 1-5 and the in-situ polymerization black polyester slices prepared in Comparative Example 1

[0105]

[0106] As can be seen from Table 1, for the filaments with a specification of 75D / 36F spun from the silver ion antibacterial copolyester slices prepared in Examples 1-5, after 50 washes with water, the antibacterial rate against Staphylococcus aureus is not less than 95%, the antibacterial rate against Escherichia coli is not less than 91%, and the antibacterial rate against Candida albicans is not less than 80%. According to the regulations of the national standard "GB / T20944.3-2007 Evaluation of antibacterial properties of textiles - Part 3: Oscillation method": when the antibacterial rate of Staphylococcus aureus and Escherichia coli ≥ 70% and the antibacterial rate of Candida albicans ≥ 60%, the textiles have antibacterial effects. This shows that the silver ion antibacterial copolyesters prepared in Examples 1-5 all have good antibacterial effects. For the filaments with a specification of 75D / 36F spun from the silver ion antibacterial copolyester slices prepared in Example 2, after 50 washes with water, the antibacterial rate against the fungus Candida albicans is 80%, the antibacterial rate against the bacterium Staphylococcus aureus is 95%, and the antibacterial rate against Escherichia coli is 91%. This further shows that the copolymer addition of 80 ppm of silver isophthalate-5-sulfonate relative to the weight of the silver ion antibacterial copolyester can endow the polyester products with excellent antibacterial properties.

[0107] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concepts. Therefore, the appended claims are intended to be construed as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0108] Obviously, those skilled in the art can make various modifications and variations to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims

1. A silver ion antibacterial copolyester, characterized in that, Isophthalic acid containing a sulfonic acid silver ion group is bonded as a comonomer to the main chain of polyethylene terephthalate molecules, and silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, enabling the dispersion of the silver ions in the polyester matrix.

2. The silver ion antibacterial copolyester according to claim 1, wherein The dispersion mode of the silver ions in the polyester matrix is atomic-level uniform dispersion.

3. The silver ion antibacterial copolyester according to claim 1, wherein The silver ion antibacterial copolyester product has antibacterial performance.

4. The silver ion antibacterial copolyester according to claim 1, characterized in that, For the filaments with a specification of 75D / 36F spun from the silver ion antibacterial copolyester, after being washed 50 times, the antibacterial rate against Staphylococcus aureus is not less than 95%, the antibacterial rate against Escherichia coli is not less than 91%, and the antibacterial rate against Candida albicans is not less than 80%.

5. The preparation method of the silver ion antibacterial copolyester according to any one of claims 1-4, characterized in that, Including the following steps: Prepare isophthalic acid-5-sulfonic acid silver. The isophthalic acid-5-sulfonic acid silver, terephthalic acid, and ethylene glycol are formulated into a slurry. Among them, the addition amount of the isophthalic acid-5-sulfonic acid silver is 80 ppm - 1000 ppm of the mass of the silver ion antibacterial copolyester produced in real time, the addition amount of the ethylene glycol is 33.9% - 64.6% of the mass of the silver ion antibacterial copolyester produced in real time, and the molar ratio of the ethylene glycol to the isophthalic acid-5-sulfonic acid silver and terephthalic acid is 1.05 - 2.

0. The slurry undergoes an esterification reaction to obtain a silver-containing polyester oligomer. The silver-containing polyester oligomer undergoes a pre-polycondensation reaction and a final polycondensation reaction to obtain a silver ion antibacterial copolyester melt. The silver ion antibacterial copolyester melt undergoes post-treatment to obtain silver ion antibacterial copolyester chips.

6. The preparation method of the silver ion antibacterial copolyester according to claim 5, characterized in that, During the step of obtaining the silver ion antibacterial copolyester chips by post-treating the silver ion antibacterial copolyester melt, the post-treatment includes filtration, cooling and solidification, and pelletizing.

7. The preparation method of the silver ion antibacterial copolyester according to claim 5, characterized in that, The preparation of the isophthalic acid-5-sulfonic acid silver specifically includes the following steps: Adding an alkaline silver salt to an aqueous solution of isophthalic acid-5-sulfonic acid, and through an acid-base neutralization reaction, recrystallization, filtration, and drying, the isophthalic acid-5-sulfonic acid silver is obtained. Among them, The alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate; The addition amount of the alkaline silver salt is 47.1% - 56.0% of the mass of the isophthalic acid-5-sulfonic acid; The mass percentage content of isophthalic acid-5-sulfonic acid in the aqueous solution of isophthalic acid-5-sulfonic acid is 10% - 30%; The temperature of the acid-base neutralization reaction is 50°C - 90°C.

8. The preparation method of the silver ion antibacterial copolyester according to claim 5, characterized in that, During the step of obtaining the silver-containing polyester oligomer by the slurry undergoing an esterification reaction, The reaction temperature of the esterification reaction is 250°C - 270°C; The reaction pressure of the esterification reaction is 100 kPa - 210 kPa; The esterification rate of the silver-containing polyester oligomer is 90% - 97%.

9. The preparation method of the silver ion antibacterial copolyester according to claim 5, characterized in that, During the step of the silver-containing polyester oligomer undergoing a pre-polycondensation reaction, The reaction temperature of the pre-polycondensation reaction is 270°C - 290°C; The reaction pressure of the pre-polycondensation reaction is 2 kPa - 4 kPa; The intrinsic viscosity of the silver ion antibacterial copolyester prepolymer prepared by the pre-polycondensation reaction is 0.15 dL / g - 0.30 dL / g.

10. The preparation method of the silver ion antibacterial copolyester according to claim 9, characterized in that, During the step of the silver ion antibacterial copolyester prepolymer undergoing a final polycondensation reaction, The reaction temperature of the final polycondensation reaction is 275°C - 290°C; The reaction pressure of the final polycondensation reaction is 100 Pa - 300 Pa; The intrinsic viscosity of the silver ion antibacterial copolyester melt prepared by the final polycondensation reaction is 0.60 dL / g - 0.75 dL / g.

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