Silver antibacterial polyester and preparation method thereof

Abstract

The invention discloses silver antibacterial polyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. In the polyester, diethylene glycol isophthalate containing a sulfonic acid silver ion group 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 comprises the following steps: preparing dimethyl isophthalate-5-silver sulfonate; dissolving the silver diethylene glycol isophthalate-5-sulfonate in ethylene glycol, and carrying out ester exchange reaction to obtain an ethylene glycol solution of the silver diethylene glycol isophthalate-5-sulfonate; preparing terephthalic acid and ethylene glycol into slurry; carrying out esterification reaction on the slurry to obtain a polyester oligomer; the preparation method comprises the following steps: mixing a polyester oligomer and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate, and then carrying out pre-copolymerization reaction, final copolymerization reaction and post-treatment to obtain the silver antibacterial polyester chip. The polyester product can be endowed with excellent antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly relates to a silver antibacterial polyester 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 antibacterial polyester 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 performance, and thus be more suitable for practical use.

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

[0005] The present invention provides a silver antibacterial polyester, in which dimethyl isophthalate-5-sulfonate containing a silver ion group is bonded to the main chain of polyethylene terephthalate molecules as a comonomer, 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 antibacterial polyester provided by the present invention can also be further realized by the following technical measures.

[0007] Preferably, the silver ions are dispersed in the polyester matrix in an atomic-level uniform dispersion manner.

[0008] Preferably, the filament with a specification of 75D / 36F spun from the silver antibacterial polyester has a bacteriostatic rate of not less than 96% against Staphylococcus aureus, not less than 93% against Escherichia coli, and not less than 82% against Candida albicans after being washed 50 times.

[0009] In order to achieve the second above-mentioned purpose, the technical solution of the preparation method of the silver antibacterial polyester provided by the present invention is as follows:

[0010] The preparation method of the silver antibacterial polyester provided by the present invention includes the following steps:

[0011] Prepare dimethyl isophthalate-5-sulfonate silver;

[0012] Dissolve the silver dimethyl isophthalate-5-sulfonate in ethylene glycol, and obtain an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate through transesterification reaction. Among them, the mass percentage of the silver dimethyl isophthalate-5-sulfonate dissolved in ethylene glycol is 0.9%-8.5%;

[0013] Prepare a slurry from terephthalic acid and ethylene glycol. Among them, in the slurry, the molar ratio of glycol to acid between terephthalic acid and ethylene glycol is 1.05-2.0;

[0014] Perform an esterification reaction on the slurry to obtain a polyester oligomer;

[0015] After mixing the polyester oligomer and the ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate, through pre-copolymerization reaction, final copolymerization reaction and post-treatment, obtain silver antibacterial polyester chips.

[0016] The preparation method of the silver antibacterial polyester provided by the present invention can also be further realized by adopting the following technical measures.

[0017] Preferably, the preparation of the silver dimethyl isophthalate-5-sulfonate specifically includes the following steps:

[0018] Add an alkaline silver salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid, and obtain silver dimethyl isophthalate-5-sulfonate through acid-base neutralization reaction, recrystallization, filtration and drying. Among them,

[0019] The alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate;

[0020] The addition amount of the alkaline silver salt is 42.2%-50.3% of the mass of the dimethyl isophthalate-5-sulfonic acid;

[0021] The mass percentage of dimethyl isophthalate-5-sulfonic acid in the aqueous solution of dimethyl isophthalate-5-sulfonic acid is 10%-30%;

[0022] The reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

[0023] Preferably, in the step of dissolving the silver dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate through transesterification reaction, the reaction temperature of the transesterification reaction is 160°C-190°C.

[0024] Preferably, in the step of dissolving the silver dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate through transesterification reaction, the reaction temperature of the transesterification reaction is 160°C-190°C.

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

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

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

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

[0029] Preferably, in the step of mixing the polyester oligomer and an ethylene glycol solution of silver 5-sulfoisophthalate diglycol ester, and then subjecting the mixture to a prepolymerization reaction, a final copolymerization reaction, and post-treatment to obtain silver antibacterial polyester chips,

[0030] the addition amount of the polyester oligomer is 102.1% - 134.3% of the mass of the silver antibacterial polyester produced in real time;

[0031] the addition amount of silver 5-sulfoisophthalate diglycol ester is 100 ppm - 1200 ppm of the mass of the silver antibacterial polyester produced in real time

[0032] the reaction temperature of the prepolymerization reaction is 270°C - 290°C;

[0033] the reaction pressure of the prepolymerization reaction is 2 kPa - 4 kPa;

[0034] the intrinsic viscosity of the silver antibacterial polyester prepolymer prepared by the prepolymerization reaction is 0.15 dL / g - 0.30 dL / g.

[0035] Preferably, in the step of subjecting the silver antibacterial polyester prepolymer to a final copolymerization reaction,

[0036] the reaction temperature of the final copolymerization reaction is 275°C - 290°C;

[0037] the reaction pressure of the final copolymerization reaction is 100 Pa - 300 Pa;

[0038] the intrinsic viscosity of the silver antibacterial polyester melt prepared by the final copolymerization reaction is 0.60 dL / g - 0.75 dL / g.

[0039] The silver antibacterial polyester prepared by the preparation method of the silver antibacterial polyester provided by the present invention is obtained by bonding 5-sulfoisophthalate diglycol ester containing a silver sulfonate ion group as a comonomer to the main chain of polyethylene terephthalate molecules, and loading silver ions with high antibacterial performance onto the polyester molecular chain through ionic bonds, realizing the 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. Brief Description of the Drawings

[0040] 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:

[0041] FIG Figure 1 is a flowchart of the steps of the method for preparing the silver antibacterial copolyester provided by the embodiment of the present invention;

[0042] FIG Figure 2 is a schematic diagram of the relationship of material changes during the steps of the method for preparing the silver antibacterial copolyester provided by the embodiment of the present invention. Detailed Embodiments

[0043] In view of this, the present invention provides a silver antibacterial polyester and a method for preparing the same, which can achieve the dispersion of silver ions with high antibacterial performance in the polyester matrix, improve the antibacterial efficiency of silver ions, and endow the polyester products with excellent antibacterial performance, thus being more suitable for practical use.

[0044] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, the following provides a detailed description of a silver antibacterial polyester and a method for preparing the same according to the present invention, including its specific embodiments, structures, features, and effects, with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "embodiment" does not necessarily refer to the same embodiment. In addition, the specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0045] As used herein, the term "and / or" is merely a description of the associated relationship between 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 one of the above three situations.

[0046] Silver antibacterial polyester

[0047] The embodiment of the present invention provides a silver antibacterial polyester, in which diethylene glycol isophthalate containing a sulfonic acid silver ion group is bonded as a comonomer 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, so that the silver ions are dispersed in the polyester matrix.

[0048] The silver antibacterial polyester provided by the embodiment of the present invention is to use dimethyl isophthalate-5-sulfonic acid silver containing a sulfonic acid silver ion group as a comonomer and bond it to the main chain of the polyethylene terephthalate molecule. The silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, realizing the 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 performance.

[0049] Among them, the way of silver ion dispersion in the polyester matrix is atomic-level uniform dispersion.

[0050] Among them, for the filaments with a specification of 75D / 36F spun from the silver antibacterial polyester, the antibacterial rates against Staphylococcus aureus are not less than 96%, against Escherichia coli are not less than 93%, and against Candida albicans are not less than 82% after being washed 50 times.

[0051] Preparation method of silver antibacterial polyester

[0052] See Appendix Figure 1 and Appendix Figure 2 , the preparation method of the silver antibacterial polyester provided by the embodiment of the present invention includes the following steps:

[0053] Step S1: Prepare dimethyl isophthalate-5-sulfonic acid silver;

[0054] Step S2: Dissolve dimethyl isophthalate-5-sulfonic acid silver in ethylene glycol, and obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver through transesterification reaction. Among them, the mass percentage content of dimethyl isophthalate-5-sulfonic acid silver dissolved in ethylene glycol is 0.9%-8.5%;

[0055] Step S3: Prepare a slurry of terephthalic acid and ethylene glycol. Among them, in the slurry, the molar ratio of glycol to acid between terephthalic acid and ethylene glycol is 1.05-2.0;

[0056] Step S4: Carry out an esterification reaction on the slurry to obtain a polyester oligomer;

[0057] Step S5: After mixing the polyester oligomer and the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver, through pre-copolymerization reaction, final copolymerization reaction and post-treatment, obtain silver antibacterial polyester chips.

[0058] The silver antibacterial polyester prepared by the preparation method of the silver antibacterial polyester provided by the embodiment of the present invention is to use diethylene glycol isophthalate-5-sulfonic acid silver containing a sulfonic acid silver ion group as a comonomer and bond it to the main chain of the polyethylene terephthalate molecule. The silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, realizing the 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 performance.

[0059] Among them, the preparation of silver dimethyl isophthalate-5-sulfonate specifically includes the following steps:

[0060] Adding an alkaline silver salt to an aqueous solution of dimethyl isophthalate-5-sulfonate, and after an acid-base neutralization reaction, recrystallizing, filtering, and drying to obtain silver dimethyl isophthalate-5-sulfonate, wherein 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 42.2%-50.3% of the mass of dimethyl isophthalate-5-sulfonate; the mass percentage content of dimethyl isophthalate-5-sulfonate in the aqueous solution of dimethyl isophthalate-5-sulfonate is 10%-30%; the reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

[0061] Among them, in the step process of obtaining silver antibacterial polyester chips by mixing a polyester oligomer and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate, followed by prepolymerization reaction, final copolymerization reaction, and post-treatment, the post-treatment includes filtration, cooling and solidification, and pelletizing.

[0062] Among them, in the step process of dissolving silver dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate through a transesterification reaction, the reaction temperature of the transesterification reaction is 160°C-190°C.

[0063] Among them, in the step process of subjecting the slurry to an esterification reaction to obtain a 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 polyester oligomer is 90%-97%;.

[0064] Among them, in the step process of obtaining silver antibacterial polyester chips by mixing a polyester oligomer and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate, followed by prepolymerization reaction, final copolymerization reaction, and post-treatment, the addition amount of the polyester oligomer is 102.1%-134.3% of the mass of the silver antibacterial polyester produced in real time, the addition amount of silver diethylene glycol isophthalate-5-sulfonate is 100 ppm-1200 ppm of the mass of the silver antibacterial polyester produced in real time, the reaction temperature of the prepolymerization reaction is 270°C-290°C; the reaction pressure of the prepolymerization reaction is 2 kPa-4 kPa; the intrinsic viscosity of the silver antibacterial polyester prepolymer prepared by the prepolymerization reaction is 0.15 dL / g-0.30 dL / g.

[0065] Among them, in the step process of subjecting the silver antibacterial polyester prepolymer to a final copolymerization reaction, the reaction temperature of the final copolymerization reaction is 275°C-290°C; the reaction pressure of the final copolymerization reaction is 100 Pa-300 Pa; the intrinsic viscosity of the silver antibacterial polyester melt prepared by the final copolymerization reaction is 0.60 dL / g-0.75 dL / g.

[0066] Example 1

[0067] (1) Silver oxide is added to an aqueous solution with a mass percentage of 20% of dimethyl isophthalate-5-sulfonic acid. After an acid-base neutralization reaction at 80 °C, recrystallization, filtration, and drying are carried out to obtain silver dimethyl isophthalate-5-sulfonate, where the addition amount of silver oxide is 42.2% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0068] (2) The silver dimethyl isophthalate-5-sulfonate prepared in step (1) is dissolved in ethylene glycol, and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate is prepared through a transesterification reaction. The mass percentage of silver dimethyl isophthalate-5-sulfonate dissolved in ethylene glycol is 0.9%, the transesterification reaction temperature is 180 °C, and the mass percentage of silver diethylene glycol isophthalate-5-sulfonate in the prepared ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate is 1%.

[0069] (3) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry is 1.15;

[0070] (4) The slurry configured in step (3) is continuously transported into an esterification system for an esterification reaction to obtain a polyester oligomer; the esterification rate of the polyester oligomer is 97%. The esterification reaction system consists of two esterification kettles connected in series. The reaction temperature of the first esterification kettle is 260 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification kettle is 265 °C and the reaction pressure is 120 kPa.

[0071] (5) The polyester oligomer prepared in step (4) is mixed evenly with the ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate prepared by online injection in step (2) in the oligomer pipeline and then continuously transported to a pre-polycondensation system for a pre-copolymerization reaction to obtain a silver antibacterial polyester prepolymer; the addition amount of the polyester oligomer is 105.4% of the mass of the silver antibacterial polyester produced in real time, the addition amount of silver diethylene glycol isophthalate-5-sulfonate is 200 ppm of the mass of the silver antibacterial polyester produced in real time, the pre-polycondensation reaction temperature is 280 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared silver antibacterial polyester prepolymer is 0.25 dL / g

[0072] (6) The silver antibacterial polyester prepolymer prepared in step (5) is continuously transported to a final polycondensation system for a final copolymerization reaction to obtain a silver antibacterial polyester melt; the final copolymerization reaction temperature is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the prepared silver antibacterial polyester melt is 0.67 dL / g

[0073] (7) Filter the silver antibacterial polyester melt obtained in step (6), then cool, solidify, and pelletize it to obtain silver antibacterial polyester chips.

[0074] Example 2

[0075] (1) Add silver sulfide to an aqueous solution with a mass percentage of 10% of dimethyl isophthalate-5-sulfonic acid. After carrying out an acid-base neutralization reaction at 90 °C, recrystallize, filter, and dry to obtain dimethyl isophthalate-5-sulfonic acid silver, where the addition amount of silver sulfide is 45.2% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0076] (2) Dissolve the dimethyl isophthalate-5-sulfonic acid silver prepared in step (1) in ethylene glycol, and obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver through a transesterification reaction. Among them, the mass percentage of dimethyl isophthalate-5-sulfonic acid silver dissolved in ethylene glycol is 0.9%, the transesterification reaction temperature is 180 °C, and the mass percentage of diethylene glycol isophthalate-5-sulfonic acid silver in the prepared ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver is 1%.

[0077] (3) Prepare a slurry from terephthalic acid and ethylene glycol according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry is 2.0.

[0078] (4) Continuously transport the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer. Among them, the esterification rate of the polyester oligomer is 90%, the reaction temperature in the esterification reaction kettle is 250 °C, and the reaction pressure is 210 kPa.

[0079] (5) Mix the polyester oligomer prepared in step (4) with the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid prepared by online injection in step (2) evenly in the oligomer pipeline, and then continuously transport it to a prepolycondensation system for a prepolymerization reaction to obtain a silver antibacterial polyester prepolymer. Among them, the addition amount of the polyester oligomer is 134.3% of the mass of the silver antibacterial polyester produced in real time, the addition amount of diethylene glycol isophthalate-5-sulfonic acid silver is 100 ppm of the mass of the silver antibacterial polyester produced in real time. Among them, the prepolymerization reaction temperature is 290 °C, the reaction pressure is 2.0 kPa, and the intrinsic viscosity of the prepared silver antibacterial polyester prepolymer is 0.30 dL / g.

[0080] (6) Continuously transport the silver antibacterial polyester prepolymer prepared in step (5) to a final polycondensation system for a final copolymerization reaction to obtain a silver antibacterial polyester melt. Among them, the final copolymerization reaction temperature is 290 °C, the reaction pressure is 100 Pa, and the intrinsic viscosity of the prepared silver antibacterial polyester melt is 0.75 dL / g.

[0081] (7) Filter the silver antibacterial polyester melt prepared in step (6), then cool, solidify, pelletize and shape it to obtain silver antibacterial polyester chips.

[0082] Example 3

[0083] (1) Add silver oxide to an aqueous solution with a mass percentage of 20% of dimethyl isophthalate-5-sulfonic acid. After carrying out an acid-base neutralization reaction at 80 °C, recrystallize, filter and dry to obtain dimethyl isophthalate-5-sulfonic acid silver, where the addition amount of basic silver sulfate is 42.2% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0084] (2) Dissolve the dimethyl isophthalate-5-sulfonic acid silver prepared in step (1) in ethylene glycol, and prepare an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver through an ester exchange reaction. The mass percentage of dimethyl isophthalate-5-sulfonic acid silver dissolved in ethylene glycol is 4.3%, the ester exchange reaction temperature is 180 °C, and the mass percentage of diethylene glycol isophthalate-5-sulfonic acid silver in the prepared ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver is 5%.

[0085] (3) Prepare a slurry by mixing terephthalic acid and ethylene glycol according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry is 1.05;

[0086] (4) Continuously convey the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer; the esterification rate of the polyester oligomer is 97%. The esterification reaction system consists of two esterification kettles connected in series. The reaction temperature of the first esterification kettle is 265 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification kettle is 270 °C and the reaction pressure is 100 kPa.

[0087] (5) Mix the polyester oligomer prepared in step (4) with the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid prepared by online injection in step (2) evenly in the oligomer pipeline, and then continuously convey it to a prepolycondensation system for a prepolymerization reaction to obtain a silver antibacterial polyester prepolymer; the addition amount of the polyester oligomer is 102.1% of the mass of the silver antibacterial polyester produced in real time, and the addition amount of diethylene glycol isophthalate-5-sulfonic acid silver is 400 ppm of the mass of the silver antibacterial polyester produced in real time. The prepolymerization reaction temperature is 275 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the prepared silver antibacterial polyester prepolymer is 0.22 dL / g.

[0088] (6) Continuously convey the silver antibacterial polyester prepolymer prepared in step (5) to the final polycondensation system for final copolymerization reaction to obtain a silver antibacterial polyester melt; wherein the temperature of the final copolymerization reaction is 280 °C, the reaction pressure is 300 Pa, and the intrinsic viscosity of the prepared silver antibacterial polyester melt is 0.64 dL / g.

[0089] (7) Filter, cool, solidify and pelletize the silver antibacterial polyester melt prepared in step (6) to obtain silver antibacterial polyester chips.

[0090] Example 4

[0091] (1) Add silver oxide to an aqueous solution with a mass percentage of dimethyl isophthalate-5-sulfonic acid of 30%, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain dimethyl isophthalate-5-sulfonic acid silver, wherein the addition amount of silver oxide is 42.2% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0092] (2) Dissolve the dimethyl isophthalate-5-sulfonic acid silver prepared in step (1) in ethylene glycol, and prepare an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver through an ester exchange reaction. The mass percentage of dimethyl isophthalate-5-sulfonic acid silver dissolved in ethylene glycol is 8.5%, the temperature of the ester exchange reaction is 190 °C, and the mass percentage of diethylene glycol isophthalate-5-sulfonic acid silver in the prepared ethylene glycol solution of diethylene glycol isophthalate-5-sulfonic acid silver is 10%.

[0093] (3) Prepare a slurry from terephthalic acid and ethylene glycol according to a certain molar ratio, wherein the molar ratio of alcohol to acid in the slurry is 1.15;

[0094] (4) Continuously convey the slurry prepared in step (3) into an esterification system for esterification reaction to obtain a polyester oligomer; wherein the esterification rate of the polyester oligomer is 97%. The esterification reaction system consists of two esterification kettles connected in series. The reaction temperature of the first esterification kettle is 260 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification kettle is 265 °C and the reaction pressure is 120 kPa.

[0095] (5) The polyester oligomer prepared in step (4) is mixed uniformly with the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate prepared in step (2) by online injection in the oligomer pipeline and then continuously transported to the prepolycondensation system for prepolymerization reaction to obtain a silver antibacterial polyester prepolymer; the addition amount of the polyester oligomer is 105.2% of the real-time output quality of the silver antibacterial polyester, and the addition amount of silver 5-sulfoisophthalate diglycolate is 800 ppm of the real-time output quality of the silver antibacterial polyester. The prepolymerization reaction temperature is 270 °C and the reaction pressure is 4 kPa. The intrinsic viscosity of the prepared silver antibacterial polyester prepolymer is 0.15 dL / g.

[0096] (6) The silver antibacterial polyester prepolymer prepared in step (5) is continuously transported to the final polycondensation system for final polymerization reaction to obtain a silver antibacterial polyester melt; the final polymerization reaction temperature is 275 °C and the reaction pressure is 150 Pa. The intrinsic viscosity of the prepared silver antibacterial polyester melt is 0.62 dL / g.

[0097] (7) The silver antibacterial polyester melt prepared in step (6) is filtered, cooled, solidified and pelletized to obtain silver antibacterial polyester chips.

[0098] Example 5

[0099] (1) Silver carbonate is added to an aqueous solution with a mass percentage of dimethyl 5-sulfoisophthalate of 10%. After an acid-base neutralization reaction at 50 °C, recrystallization, filtration and drying are carried out to obtain silver 5-sulfoisophthalate dimethyl ester, and the addition amount of silver carbonate is 50.3% of the weight of dimethyl 5-sulfoisophthalate.

[0100] (2) The silver 5-sulfoisophthalate dimethyl ester prepared in step (1) is dissolved in ethylene glycol, and an ethylene glycol solution of silver 5-sulfoisophthalate diglycolate is prepared through a transesterification reaction. The mass percentage of silver 5-sulfoisophthalate dimethyl ester dissolved in ethylene glycol is 4.3%, the transesterification reaction temperature is 160 °C, and the mass percentage of silver 5-sulfoisophthalate diglycolate in the prepared ethylene glycol solution of silver 5-sulfoisophthalate diglycolate is 5%.

[0101] (3) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, and the molar ratio of alcohol to acid in the slurry is 2.0.

[0102] (4) The slurry configured in step (3) is continuously transported into an esterification system for esterification reaction to obtain a polyester oligomer; the esterification rate of the polyester oligomer is 90%, the reaction temperature of the esterification reaction kettle is 250 °C, and the reaction pressure is 210 kPa.

[0103] (5) The polyester oligomer prepared in step (4) is mixed uniformly with the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate prepared in step (2) by online injection in the oligomer pipeline and then continuously transported to the prepolycondensation system for prepolymerization reaction to obtain a silver antibacterial polyester prepolymer; the addition amount of the polyester oligomer is 133.6% of the mass of the silver antibacterial polyester produced in real time, and the addition amount of silver 5-sulfoisophthalate diglycolate is 1200 ppm of the mass of the silver antibacterial polyester produced in real time. The prepolymerization reaction temperature is 270 °C and the reaction pressure is 3.0 kPa. The intrinsic viscosity of the prepared silver antibacterial polyester prepolymer is 0.18 dL / g.

[0104] (6) The silver antibacterial polyester prepolymer prepared in step (5) is continuously transported to the final polycondensation system for final polymerization reaction to obtain a silver antibacterial polyester melt; the final polymerization reaction temperature is 275 °C and the reaction pressure is 300 Pa. The intrinsic viscosity of the prepared silver antibacterial polyester melt is 0.60 dL / g.

[0105] (7) The silver antibacterial polyester melt prepared in step (6) is filtered, cooled, solidified and pelletized to obtain silver antibacterial polyester chips.

[0106] Experimental example 1

[0107] (1) The silver antibacterial polyester chips prepared in Examples 1 to 5 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.

[0108] (2) The dried chips prepared in step 1 are melt-spun on a melt spinning machine to prepare a partially oriented yarn with a specification of 120 D / 36 F. The melt spinning temperature is 290 °C and the spinning speed is 3000 m / min.

[0109] (3) The partially oriented yarn prepared in step (2) is drawn and processed on a flat drawing machine to prepare a drawn yarn with a specification of 75 D / 36 F. The draw ratio is 1.6 times, the drawing temperature is 80 °C, and the setting temperature is 130 °C.

[0110] (4) The filaments with a specification of 75 D / 36 F prepared in step (3) are woven into a sock band, and then washed 50 times under test condition A1M in GB / T 12490-1990. Then, the antibacterial rates of the sock band against Staphylococcus aureus, Escherichia coli, and Candida albicans after washing 50 times are tested according to GB / T 20944.3-2007. The test results are shown in Table 1.

[0111] Table 1 Antibacterial performance test results of filaments with a specification of 75 D / 36 F spun from the silver antibacterial polyester chips prepared in Examples 1 to 5

[0112]

[0113]

[0114] As can be seen from Table 1, for the filaments with a specification of 75D / 36F spun from the silver antibacterial polyester chips prepared in Examples 1 to 5, after 50 times of water washing, the antibacterial rate against Staphylococcus aureus is not less than 96%, the antibacterial rate against Escherichia coli is not less than 93%, and the antibacterial rate against Candida albicans is not less than 82%. According to the national standard "GB / T 20944.3-2007 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 antibacterial polyesters prepared in Examples 1 to 5 all have good antibacterial effects. For the filaments with a specification of 75D / 36F spun from the silver antibacterial polyester chips prepared in Example 2, after 50 times of water washing, the antibacterial rate against the fungus Candida albicans is 82%, the antibacterial rate against the bacterium Staphylococcus aureus is 96%, and the antibacterial rate against Escherichia coli is 93%. This further shows that the copolymer addition of 100 ppm of silver 5-sulfoisophthalate diglycolate relative to the weight of the silver antibacterial polyester can endow the polyester products with excellent antibacterial properties.

[0115] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications once they know the basic creative concept. 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.

[0116] Obviously, those skilled in the art can make various changes and modifications 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 is also intended to include these modifications and variations.

Claims

1. A silver antibacterial polyester, characterized in that, Dimethyl isophthalate-5-sulfonate containing silver ion groups is bonded to the main chain of polyethylene terephthalate molecules as a comonomer, and silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, enabling the silver ions to be dispersed in the polyester matrix.

2. The silver antibacterial polyester according to claim 1, wherein The way the silver ions are dispersed in the polyester matrix is atomic-level uniform dispersion.

3. The silver antibacterial polyester according to claim 1, wherein The filaments of the silver antibacterial polyester with a specification of 75D / 36F, after being washed 50 times, have a bacteriostatic rate of not less than 96% against Staphylococcus aureus, not less than 93% against Escherichia coli, and not less than 82% against Candida albicans.

4. The preparation method of the silver antibacterial polyester according to any one of claims 1-3, characterized in that, It includes the following steps: Prepare dimethyl isophthalate-5-sulfonate silver. Dissolve the dimethyl isophthalate-5-sulfonate silver in ethylene glycol, and obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver through transesterification reaction. Among them, the mass percentage content of the dimethyl isophthalate-5-sulfonate silver dissolved in ethylene glycol is 0.9% - 8.5%. Prepare a slurry of terephthalic acid and ethylene glycol. Among them, in the slurry, the molar ratio of glycol to acid between terephthalic acid and ethylene glycol is 1.05 - 2.

0. The slurry undergoes an esterification reaction to obtain a polyester oligomer. After mixing the polyester oligomer and the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver, through pre-copolymerization reaction, final copolymerization reaction and post-treatment, silver antibacterial polyester chips are obtained.

5. The preparation method of the silver antibacterial polyester according to claim 4, characterized in that, The specific preparation of dimethyl isophthalate-5-sulfonate silver includes the following steps: Add an alkaline silver salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid, and after acid-base neutralization reaction, recrystallize, filter and dry to obtain dimethyl isophthalate-5-sulfonate silver. Among them, The alkaline silver salt is selected from one or a mixture of silver oxide, silver sulfide, silver carbonate; The addition amount of the alkaline silver salt is 42.2% - 50.3% of the mass of dimethyl isophthalate-5-sulfonic acid; The mass percentage content of dimethyl isophthalate-5-sulfonic acid in the aqueous solution of dimethyl isophthalate-5-sulfonic acid is 10% - 30%; The reaction temperature of the acid-base neutralization reaction is 50°C - 90°C.

6. The preparation method of the silver antibacterial polyester according to claim 4, wherein, In the step process of obtaining silver antibacterial polyester chips after mixing the polyester oligomer and the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver, through pre-copolymerization reaction, final copolymerization reaction and post-treatment, the post-treatment includes filtration, cooling and solidification, and pelletizing.

7. The preparation method of the silver antibacterial polyester according to claim 4, characterized in that, In the step process of dissolving the dimethyl isophthalate-5-sulfonate silver in ethylene glycol and obtaining an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver through transesterification reaction, the reaction temperature of the transesterification reaction is 160°C - 190°C.

8. The preparation method of the silver antibacterial polyester according to claim 4, characterized in that, In the step process of the slurry undergoing an esterification reaction to obtain a 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; The esterification rate of the polyester oligomer is 90% - 97%.

9. The preparation method of the silver antibacterial polyester according to claim 4, characterized in that In the step process of obtaining the silver antibacterial polyester chips after mixing the polyester oligomer and the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate, followed by prepolymerization reaction, final copolymerization reaction and post-treatment, The addition amount of the polyester oligomer is 102.1%-134.3% of the mass of the silver antibacterial polyester produced in real time; The addition amount of the silver 5-sulfoisophthalate diglycolate is 100 ppm - 1200 ppm of the mass of the silver antibacterial polyester produced in real time; The reaction temperature of the prepolymerization reaction is 270°C - 290°C; The reaction pressure of the prepolymerization reaction is 2 kPa - 4 kPa; The intrinsic viscosity of the silver antibacterial polyester prepolymer prepared by the prepolymerization reaction is 0.15 dL / g - 0.30 dL / g.

10. The preparation method of the silver antibacterial polyester according to claim 9, characterized in that, In the step process of carrying out the final copolymerization reaction on the silver antibacterial polyester prepolymer, The reaction temperature of the final copolymerization reaction is 275°C - 290°C; The reaction pressure of the final copolymerization reaction is 100 Pa - 300 Pa; The intrinsic viscosity of the silver antibacterial polyester melt prepared by the final copolymerization reaction is 0.60 dL / g - 0.75 dL / g.

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