In-situ polymerization silver antibacterial black polyester and preparation method thereof

Abstract

The invention discloses in-situ polymerization silver antibacterial black polyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. In the polyester, 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 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 first slurry from terephthalic acid and ethylene glycol, and carrying out esterification reaction to obtain a polyester oligomer; mixing the black polyester oligomer with ethylene glycol slurry of carbon black to obtain a black polyester oligomer; and carrying out in-situ prepolymerization reaction, in-situ final polymerization reaction and post-treatment on the black polyester oligomer and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate to obtain the in-situ polymerization silver antibacterial black polyester chip. The antibacterial efficiency of silver ions can be improved, and a fiber product is endowed with excellent antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly to in-situ polymerization silver antibacterial black polyester and a preparation method thereof. Background Art

[0002] Processing the dope-dyed fiber into textiles can omit the dyeing process, which has a prominent effect of reducing emissions and carbon; it is estimated that, compared with the traditional post-spinning dyed polyester fiber, each ton of dope-dyed polyester fiber processed into textiles can reduce wastewater emissions by 32 tons and carbon dioxide emissions by 1.2 tons. Benefiting from industrial upgrading and the drive of energy conservation and emission reduction policies, the output of dope-dyed fibers has increased rapidly in recent years and has become the main variety of differential polyester fibers, among which the proportion of black fibers exceeds 80%. With the improvement of people's living standards and the enhancement of people's awareness of health and the environment, the market demand for antibacterial fibers has increased rapidly. Thus, developing in-situ polymerization antibacterial black polyester fibers can further expand the application fields of dope-dyed fibers. Summary of the Invention

[0003] In view of this, the present invention provides an in-situ polymerization silver antibacterial black polyester and a preparation method thereof, which can achieve atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing its fiber products with excellent antibacterial properties, making it more suitable for practical use.

[0004] In order to achieve the above first object, the technical solution of the in-situ polymerization silver antibacterial black polyester provided by the present invention is as follows:

[0005] The present invention provides an in-situ polymerization silver antibacterial black polyester, in which diethylene glycol isophthalate containing a sulfonic acid 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 in-situ polymerization silver antibacterial black polyester provided by the present invention can also be further realized by the following technical measures.

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

[0008] Preferably, in the in-situ polymerization silver antibacterial black polyester, the primary particle size of carbon black is 16 nm - 28 nm, and the mass percentage content of the added carbon black is 0.5% - 3.0%.

[0009] Preferably, the fiber products spun from the in-situ polymerization black polyester have antibacterial properties.

[0010] Preferably, after being washed 50 times, the filaments with a specification of 75D / 36F spun from the in-situ polymerized silver antibacterial black polyester have a bacteriostatic rate of more than 99% against Staphylococcus aureus, more than 99% against Escherichia coli, and not less than 80% against Candida albicans.

[0011] To achieve the above second object, the technical solution of the preparation method of the in-situ polymerized silver antibacterial black polyester provided by the present invention is as follows:

[0012] The preparation method of the in-situ polymerized silver antibacterial black polyester provided by the present invention includes the following steps:

[0013] Prepare dimethyl 5-sulfoisophthalate silver;

[0014] Dissolve the dimethyl 5-sulfoisophthalate silver in ethylene glycol, and through transesterification reaction, obtain an ethylene glycol solution of diethylene glycol 5-sulfoisophthalate silver. Among them, in the ethylene glycol solution of diethylene glycol 5-sulfoisophthalate silver, the mass percentage content of diethylene glycol 5-sulfoisophthalate silver is 1%-10%;

[0015] Prepare a first slurry with terephthalic acid and ethylene glycol, where the molar ratio of ethylene glycol to terephthalic acid is 1.05-2.0;

[0016] The first slurry undergoes an esterification reaction to obtain a polyester oligomer;

[0017] Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. Among them, in the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5%-15%; the addition amount of carbon black is 0.5%-3.0% of the mass output of the in-situ polymerized silver antibacterial black polyester produced in real time;

[0018] The black polyester oligomer and the ethylene glycol solution of diethylene glycol 5-sulfoisophthalate silver undergo in-situ pre-polymerization reaction, in-situ final polymerization reaction, filtration, cooling and solidification, and pelletizing to obtain the in-situ polymerized silver antibacterial black polyester chips. Among them, the addition amount of diethylene glycol 5-sulfoisophthalate silver is 80 ppm-800 ppm of the mass output of the in-situ polymerized silver antibacterial black polyester produced in real time.

[0019] The preparation method of the in-situ polymerized silver antibacterial black polyester provided by the present invention can also be further realized by adopting the following technical measures.

[0020] Preferably, the preparation of dimethyl 5-sulfoisophthalate silver specifically includes the following steps:

[0021] An alkaline silver salt is added to an aqueous solution of dimethyl isophthalate-5-sulfonate, and through an acid-base neutralization reaction, recrystallization, filtration, and drying, silver dimethyl isophthalate-5-sulfonate is obtained. Among them,

[0022] the alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate;

[0023] the addition amount of the alkaline silver salt is 42.2%-50.3% of the mass of dimethyl isophthalate-5-sulfonate;

[0024] in the aqueous solution of dimethyl isophthalate-5-sulfonate, the mass percentage content of dimethyl isophthalate-5-sulfonate is 10%-30%;

[0025] the temperature of the acid-base neutralization reaction is 50°C-90°C.

[0026] Preferably, the temperature of the transesterification reaction is 160°C-190°C.

[0027] Preferably, in the step of obtaining a polyester oligomer through the esterification reaction of the first slurry,

[0028] the temperature of the esterification reaction is 250°C-270°C;

[0029] the pressure of the esterification reaction is 100 kPa-210 kPa;

[0030] the esterification rate of the polyester oligomer is 90%-97%.

[0032] Preferably, in the step of carrying out an in-situ pre-polymerization reaction on the black polyester oligomer and an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate,

[0033] the temperature of the in-situ pre-polymerization reaction is 270°C-290°C;

[0034] the pressure of the in-situ pre-polymerization reaction is 2 kPa-4 kPa;

[0035] the intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester prepolymer prepared by the in-situ pre-polymerization reaction is 0.15 dL / g-0.30 dL / g.

[0036] Preferably, in the step of carrying out an in-situ final polymerization reaction on the in-situ polymerized silver antibacterial black polyester prepolymer,

[0037] the temperature of the in-situ final polymerization reaction is 275°C-290°C;

[0038] the pressure of the in-situ final polymerization reaction is 100 Pa-300 Pa;

[0039] The intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester melt prepared by the in-situ terminal polymerization reaction is 0.58 dL / g - 0.72 dL / g.

[0040] The in-situ polymerized silver antibacterial black polyester prepared by the preparation method provided by the present invention is obtained by bonding diethylene glycol isophthalate containing a sulfonic acid silver ion group as a comonomer to the main chain of a 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 its fiber products with excellent antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] By reading the detailed description of the preferred embodiments below, 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:

[0042] Attached Figure 1 is a process flow chart of the preparation method of the in-situ polymerized silver antibacterial black polyester provided by the embodiment of the present invention;

[0043] Attached Figure 2 is a schematic diagram of the material change relationship during the process of the preparation method of the in-situ polymerized silver antibacterial black polyester provided by the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] In view of this, the present invention provides an in-situ polymerized silver antibacterial black polyester and a preparation method thereof, which can achieve the atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing its fiber products with excellent antibacterial properties, and thus being more suitable for practical use.

[0045] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following combines the drawings and preferred embodiments to detail the specific embodiments, structures, features and effects of an in-situ polymerized silver antibacterial black polyester and a preparation method thereof proposed according to the present invention. In the following description, different "one embodiment" or "embodiment" do 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.

[0046] In this text, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B is specifically understood as follows: it can include both A and B simultaneously, A can exist alone, or B can exist alone, and it can possess any one of the above three situations.

[0047] In-situ polymerized silver antibacterial black polyester

[0048] The present invention provides an in-situ polymerized silver antibacterial black polyester. Diethylene glycol isophthalate containing a silver sulfonate 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 silver ions to be dispersed in the polyester matrix.

[0049] The in-situ polymerized silver antibacterial black polyester provided by the present invention bonds diethylene glycol isophthalate containing a silver sulfonate ion group as a comonomer to the main chain of polyethylene terephthalate molecules, and loads silver ions with high antibacterial performance onto the polyester molecular chain through ionic bonds, achieving an atomic-level highly uniform dispersion of silver ions in the polyester matrix. Thus, the antibacterial efficiency of silver ions is significantly improved, endowing its fiber products with excellent antibacterial properties.

[0050] Among them, the dispersion mode of silver ions in the polyester matrix is atomic-level uniform dispersion.

[0051] Among them, in the in-situ polymerized silver antibacterial black polyester, the primary particle size of carbon black is 16nm - 28nm, and the mass percentage content of carbon black added is 0.5% - 3.0%.

[0052] Among them, the fiber products spun from the in-situ polymerized black polyester have antibacterial properties.

[0053] Among them, for the filaments with a specification of 75D / 36F spun from the in-situ polymerized silver antibacterial black polyester, the antibacterial rate against Staphylococcus aureus is greater than 99% after being washed 50 times, the antibacterial rate against Escherichia coli is greater than 99%, and the antibacterial rate against Candida albicans is not less than 80%.

[0054] Preparation method of in-situ polymerized silver antibacterial black polyester

[0055] See Appendix Figure 1 and Appendix Figure 2 , the preparation method of the in-situ polymerized silver antibacterial black polyester provided by the present invention includes the following steps:

[0056] Step S1: Prepare dimethyl isophthalate-5-silver sulfonate;

[0057] Step S2: Dissolve silver dimethyl isophthalate-5-sulfonate in ethylene glycol. Through transesterification reaction, an ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate is obtained. In the ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate, the mass percentage content of silver diethylene glycol isophthalate-5-sulfonate is 1% - 10%.

[0058] Step S3: Prepare a first slurry with terephthalic acid and ethylene glycol. In this case, the molar ratio of ethylene glycol to terephthalic acid is 1.05 - 2.0.

[0059] Step S4: The first slurry undergoes an esterification reaction to obtain a polyester oligomer.

[0060] Step S5: Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. In the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5% - 15%; the addition amount of carbon black is 0.5% - 3.0% of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time.

[0061] Step S6: The black polyester oligomer and the ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate undergo in-situ pre-polymerization reaction, in-situ final polymerization reaction, filtration, cooling and solidification, and pelletizing to obtain in-situ polymerization silver antibacterial black polyester chips. The addition amount of silver diethylene glycol isophthalate-5-sulfonate is 80 ppm - 800 ppm of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time.

[0062] The in-situ polymerization silver antibacterial black polyester prepared by the preparation method provided by the present invention is to use silver diethylene glycol isophthalate 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 atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing its fiber products with excellent antibacterial properties.

[0063] Among them, the preparation of silver dimethyl isophthalate-5-sulfonate specifically includes the following steps:

[0064] Add an alkaline silver salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid. Through acid-base neutralization reaction, recrystallization, filtration, and drying, silver dimethyl 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 42.2% - 50.3% of the mass of dimethyl isophthalate-5-sulfonic acid; in the aqueous solution of dimethyl isophthalate-5-sulfonic acid, the mass percentage content of dimethyl isophthalate-5-sulfonic acid is 10% - 30%; the temperature of the acid-base neutralization reaction is 50°C - 90°C.

[0065] Among them, the temperature of the transesterification reaction is 160°C - 190°C.

[0066] Among them, in the step of obtaining the polyester oligomer through the esterification reaction of the first slurry, the esterification reaction temperature is 250°C - 270°C; the esterification reaction pressure is 100 kPa - 210 kPa, and the esterification rate of the polyester oligomer is 90% - 97%.

[0067] Among them, in the step of carrying out the in-situ pre-polymerization reaction on the black polyester oligomer and the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate, the in-situ pre-polymerization reaction temperature is 270°C - 290°C; the in-situ pre-polymerization reaction pressure is 2 kPa - 4 kPa; the intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester prepolymer prepared by the in-situ pre-polymerization reaction is 0.15 dL / g - 0.30 dL / g.

[0068] Among them, in the step of carrying out the in-situ final polymerization reaction on the in-situ polymerized silver antibacterial black polyester prepolymer, the in-situ final polymerization reaction temperature is 275°C - 290°C; the in-situ final polymerization reaction pressure is 100 Pa - 300 Pa; the intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester melt prepared by the in-situ final polymerization reaction is 0.58 dL / g - 0.72 dL / g.

[0069] Example 1

[0070] (1) Silver oxide is added to an aqueous solution with a mass percentage of 20% of dimethyl 5-sulfoisophthalate. After carrying out an acid-base neutralization reaction at 80°C, recrystallization, filtration, and drying are carried out to obtain silver 5-sulfoisophthalate dimethyl ester, wherein the addition amount of silver oxide is 42.2% of the weight of dimethyl 5-sulfoisophthalate.

[0071] (2) The silver 5-sulfoisophthalate dimethyl ester prepared in step (1) is dissolved in ethylene glycol, and through a transesterification reaction, an ethylene glycol solution of silver 5-sulfoisophthalate diglycolate is prepared. Among them, the transesterification reaction temperature is 180°C, and the mass percentage of silver 5-sulfoisophthalate diglycolate in the prepared ethylene glycol solution of silver 5-sulfoisophthalate diglycolate is 1%.

[0072] (3) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, wherein the molar ratio of alcohol to acid in the slurry is 1.15;

[0073] (4) The slurry configured in step (3) is continuously transported into an esterification system for an esterification reaction to obtain a polyester oligomer; among them, the esterification rate of the polyester oligomer is 92%, the reaction temperature of the esterification reaction kettle is 260°C, and the reaction pressure is 170 kPa.

[0074] (5) Continuously convey the polyester oligomer prepared in step (4) into the in-situ polymerization polyester oligomer preparation kettle, mix it evenly with the ethylene glycol slurry in which carbon black is injected online, and obtain a black polyester oligomer; the carbon black addition amount is 1% of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time, the primary particle size of the carbon black is 20 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 10%.

[0075] (6) Continuously convey the black polyester oligomer prepared in step (5) in the oligomer pipeline, mix it evenly with the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate prepared in step (2) injected online, and then continuously convey it to the pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerization silver antibacterial black polyester prepolymer; the addition amount of silver 5-sulfoisophthalate diglycolate is 80 ppm of the mass of the in-situ polymerization silver antibacterial black 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 in-situ polymerization silver antibacterial black polyester prepolymer is 0.25 dL / g

[0076] (7) Continuously convey the in-situ polymerization silver antibacterial black polyester prepolymer prepared in step (6) to the final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerization silver antibacterial black polyester melt; the final polycondensation reaction temperature is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the prepared in-situ polymerization silver antibacterial black polyester melt is 0.67 dL / g

[0077] (8) Filter the in-situ polymerization silver antibacterial black polyester melt prepared in step (7), then cool, solidify and pelletize it to obtain in-situ polymerization silver antibacterial black polyester chips.

[0078] Example 2

[0079] (1) Add silver sulfide to an aqueous solution with a mass percentage of dimethyl 5-sulfoisophthalate of 10%, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain silver 5-sulfoisophthalate dimethyl ester, wherein the addition amount of silver sulfide is 45.2% of the weight of dimethyl 5-sulfoisophthalate

[0080] (2) Dissolve the silver 5-sulfoisophthalate dimethyl ester prepared in step (1) in ethylene glycol, and prepare an ethylene glycol solution of silver 5-sulfoisophthalate diglycolate through a transesterification reaction, wherein the transesterification reaction temperature is 180 °C, and the mass percentage of silver 5-sulfoisophthalate diglycolate in the prepared ethylene glycol solution of silver 5-sulfoisophthalate diglycolate is 1%.

[0081] (3) Prepare a slurry by mixing 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;

[0082] (4) Continuously convey the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer; wherein the esterification rate of the polyester oligomer is 92%, the reaction temperature of the esterification reaction kettle is 260 °C, and the reaction pressure is 170 kPa.

[0083] (5) Continuously convey the polyester oligomer prepared in step (4) into a reactor for in-situ polymerization of polyester oligomers, and mix it evenly with an ethylene glycol slurry in which carbon black is injected online to obtain a black polyester oligomer; the carbon black addition amount is 1.5% of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time, the primary particle size of the carbon black is 21 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 10%.

[0084] (6) Continuously convey the black polyester oligomer prepared in step (5) in an oligomer pipeline, mix it evenly with an ethylene glycol solution of silver 5-sulfoisophthalate diglycolate prepared in step (2) injected online, and then continuously convey it to a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization silver antibacterial black polyester prepolymer; wherein the addition amount of silver 5-sulfoisophthalate diglycolate is 160 ppm of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time, the pre-polycondensation reaction temperature is 280 °C, the reaction pressure is 2.0 kPa, and the intrinsic viscosity of the prepared in-situ polymerization silver antibacterial black polyester prepolymer is 0.28 dL / g.

[0085] (7) Continuously convey the in-situ polymerization silver antibacterial black polyester prepolymer prepared in step (6) to a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization silver antibacterial black polyester melt; wherein the final polycondensation reaction temperature is 285 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared in-situ polymerization silver antibacterial black polyester melt is 0.69 dL / g.

[0086] (8) Filter the in-situ polymerization silver antibacterial black polyester melt prepared in step (7), then cool, solidify, pelletize and form it to obtain in-situ polymerization silver antibacterial black polyester chips.

[0087] Example 3

[0088] (1) Add silver oxide to an aqueous solution with a mass percentage of dimethyl 5-sulfoisophthalate of 20%, carry out an acid-base neutralization reaction at 80 °C, and then perform recrystallization, filtration and drying to obtain silver 5-sulfoisophthalate dimethyl ester, wherein the addition amount of basic silver sulfate is 42.2% of the weight of dimethyl 5-sulfoisophthalate.

[0089] (2) Dissolve the silver 5-sulfoisophthalate dimethyl ester prepared in step (1) in ethylene glycol, and obtain an ethylene glycol solution of silver 5-sulfoisophthalate diethylene glycol ester through a transesterification reaction. The transesterification reaction temperature is 180 °C, and the mass percentage of silver 5-sulfoisophthalate diethylene glycol ester in the obtained ethylene glycol solution of silver 5-sulfoisophthalate diethylene glycol ester is 5%.

[0090] (3) Prepare a slurry from terephthalic acid and ethylene glycol according to a certain molar ratio, where the molar ratio of glycol to acid in the slurry is 1.05;

[0091] (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 reactors connected in series. The reaction temperature of the first esterification reactor is 265 °C and the reaction pressure is 170 kPa, and the reaction temperature of the second esterification reactor is 270 °C and the reaction pressure is 100 kPa.

[0092] (5) Continuously convey the polyester oligomer prepared in step (4) into a reactor for in-situ polymerization of polyester oligomers, and mix it evenly with an ethylene glycol slurry with carbon black injected online to obtain a black polyester oligomer; the carbon black addition amount is 2% of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time. The primary particle size of the carbon black is 20 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 10%.

[0093] (6) Mix the black polyester oligomer prepared in step (5) evenly with the ethylene glycol solution of silver 5-sulfoisophthalate diethylene glycol ester prepared in step (2) injected online in the oligomer pipeline, and then continuously convey it to a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerized silver antibacterial black polyester prepolymer; the addition amount of silver 5-sulfoisophthalate diethylene glycol ester is 400 ppm of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time. The pre-polycondensation reaction temperature is 275 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the obtained in-situ polymerized silver antibacterial black polyester prepolymer is 0.22 dL / g

[0094] (7) Continuously convey the in-situ polymerized silver antibacterial black polyester prepolymer prepared in step (6) to a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerized silver antibacterial black polyester melt; the final polycondensation reaction temperature is 280 °C and the reaction pressure is 250 Pa. The intrinsic viscosity of the obtained in-situ polymerized silver antibacterial black polyester melt is 0.65 dL / g.

[0095] (8) Filter the in-situ polymerized silver antibacterial black polyester melt prepared in step (7), and then cool, solidify, pelletize and form it to obtain in-situ polymerized silver antibacterial black polyester chips.

[0096] Example 4

[0097] (1) Silver oxide is added to an aqueous solution with a mass percentage of 30% of dimethyl isophthalate-5-sulfonic acid. After an acid-base neutralization reaction at 90 °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.

[0098] (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 transesterification reaction temperature is 190 °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 10%.

[0099] (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.

[0100] (4) The slurry configured in step (3) is continuously fed into an esterification system for an esterification reaction to obtain a polyester oligomer. The esterification rate of the polyester oligomer is 92%, and the reaction temperature of the esterification reaction kettle is 260 °C and the reaction pressure is 170 kPa.

[0101] (5) The polyester oligomer prepared in step (4) is continuously fed into an in-situ polymerization polyester oligomer preparation kettle and mixed evenly with an ethylene glycol slurry in which carbon black is injected online to obtain a black polyester oligomer. The addition amount of carbon black is 3% of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time. The primary particle size of carbon black is 28 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 15%.

[0102] (6) The black polyester oligomer prepared in step (5) is mixed evenly with the ethylene glycol solution of silver diethylene glycol isophthalate-5-sulfonate prepared in step (2) injected online in the oligomer pipeline and then continuously fed into a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization silver antibacterial black polyester prepolymer. The addition amount of silver diethylene glycol isophthalate-5-sulfonate is 800 ppm of the mass of the in-situ polymerization silver antibacterial black polyester produced in real time. The pre-polycondensation reaction temperature is 270 °C and the reaction pressure is 4 kPa. The intrinsic viscosity of the prepared in-situ polymerization silver antibacterial black polyester prepolymer is 0.15 dL / g.

[0103] (7) Continuously convey the in-situ polymerized silver antibacterial black polyester prepolymer prepared in step (6) to the final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized silver antibacterial black polyester melt; wherein the final polycondensation reaction temperature is 275 °C, the reaction pressure is 300 Pa, and the intrinsic viscosity of the prepared in-situ polymerized silver antibacterial black polyester melt is 0.58 dL / g.

[0104] (8) Filter, cool, solidify and pelletize the in-situ polymerized silver antibacterial black polyester melt prepared in step (7) to obtain in-situ polymerized silver antibacterial black polyester chips.

[0105] Example 5

[0106] (1) Add silver carbonate to an aqueous solution with a mass percentage of 10% of dimethyl isophthalate-5-sulfonic acid, carry out an acid-base neutralization reaction at 50 °C, and then perform recrystallization, filtration and drying to obtain dimethyl isophthalate-5-sulfonic acid silver, wherein the addition amount of silver carbonate is 50.3% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0107] (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, wherein the ester exchange reaction temperature is 160 °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%.

[0108] (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 2.0.

[0109] (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 90%, the reaction temperature of the esterification reaction kettle is 250 °C, and the reaction pressure is 210 kPa.

[0110] (5) Continuously convey the polyester oligomer prepared in step (4) into a preparation kettle for in-situ polymerized polyester oligomers, and mix it evenly with an ethylene glycol slurry with carbon black injected online to obtain a black polyester oligomer; the addition amount of carbon black is 0.5% of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time, the primary particle size of carbon black is 16 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 5%.

[0111] (6) The black polyester oligomer prepared in step (5) is mixed evenly with the ethylene glycol solution of silver 5-sulfoisophthalate diglycolate prepared in step (2) by online injection in the oligomer pipeline and then continuously conveyed to the prepolycondensation system for in-situ prepolymerization reaction to obtain an in-situ polymerized silver antibacterial black polyester prepolymer; the addition amount of silver 5-sulfoisophthalate diglycolate is 240 ppm of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time. The prepolycondensation reaction temperature is 290 °C and the reaction pressure is 2.0 kPa. The intrinsic viscosity of the prepared in-situ polymerized silver antibacterial black polyester prepolymer is 0.30 dL / g.

[0112] (7) The in-situ polymerized silver antibacterial black polyester prepolymer prepared in step (6) is continuously conveyed to the final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized silver antibacterial black polyester melt; the final polycondensation reaction temperature is 290 °C and the reaction pressure is 100 Pa. The intrinsic viscosity of the prepared in-situ polymerized silver antibacterial black polyester melt is 0.72 dL / g.

[0113] (8) The in-situ polymerized silver antibacterial black polyester melt prepared in step (7) is filtered, cooled, solidified, pelletized and formed to obtain in-situ polymerized silver antibacterial black polyester chips.

[0114] Comparative Example 1

[0115] (1) 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 1.15.

[0116] (2) The slurry configured in step (1) is continuously conveyed into an esterification reaction kettle for esterification reaction to obtain a silver-containing polyester oligomer; the esterification rate of the polyester oligomer is 92%. The reaction temperature of the esterification reaction kettle is 260 °C and the reaction pressure is 170 kPa.

[0117] (3) The polyester oligomer prepared in step (2) is continuously conveyed into an in-situ polymerized polyester oligomer preparation kettle and mixed evenly with the ethylene glycol slurry of online-injected carbon black to obtain a black polyester oligomer; the addition amount of carbon black is 1% of the mass of the in-situ polymerized black polyester produced in real time. The primary particle size of the carbon black is 20 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 10%.

[0118] (4) The black polyester oligomer prepared in step (3) is continuously conveyed to the prepolycondensation system for in-situ prepolymerization reaction to obtain an in-situ polymerized black polyester prepolymer; the prepolycondensation reaction temperature is 280 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the prepared in-situ polymerized black polyester prepolymer is 0.25 dL / g

[0119] (5) Continuously convey the in-situ polymerized black polyester prepolymer prepared in step (4) to the final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized black polyester melt; wherein the final polycondensation reaction temperature is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the prepared in-situ polymerized black polyester melt is 0.67 dL / g

[0120] (6) Filter, cool, solidify and pelletize the in-situ polymerized black polyester melt prepared in step (5) to obtain in-situ polymerized black polyester chips.

[0121] Experimental Example 1

[0122] (1) Dry the in-situ polymerized silver antibacterial black polyester chips prepared in Examples 1-5 and the in-situ polymerized black polyester chips prepared in Comparative Example 1 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.

[0123] (2) Melt-spin the dried chips obtained in step 1 on a melt spinning machine to prepare a partially oriented yarn with a specification of 120 D / 36 F, wherein the melt spinning temperature is 290 °C and the spinning speed is 3000 m / min.

[0124] (3) Draw and process the partially oriented yarn obtained in step (2) on a flat drawing machine to prepare a drawn yarn with a specification of 75 D / 36 F, wherein the draw ratio is 1.6 times, the drawing temperature is 80 °C, and the setting temperature is 130 °C

[0125] (4) Weave the filaments with a specification of 75 D / 36 F obtained in step (3) into a garter, then wash it 50 times according to test condition A1M in GB / T 12490-1990, and then test the antibacterial rates of the garter against Staphylococcus aureus, Escherichia coli, and Candida albicans after washing 50 times according to GB / T 20944.3-2007. The test results are shown in Table 1

[0126] Table 1 Test results of antibacterial properties of filaments with a specification of 75 D / 36 F spun from the in-situ polymerized silver antibacterial black polyester chips prepared in Examples 1-5 and the in-situ polymerized black polyester chips prepared in Comparative Example 1

[0127]

[0128] As can be seen from Table 1, the filament yarns with a specification of 75D / 36F spun from the in-situ polymerization silver antibacterial black polyester chips prepared in Examples 1 to 5 had a bacteriostatic rate of more than 99% against Staphylococcus aureus and Escherichia coli after 50 washes, and a bacteriostatic rate of not less than 80% against Candida albicans; this indicates that the filament yarns with a specification of 75D / 36F spun from the in-situ polymerization silver antibacterial black polyester chips prepared in Examples 1 to 5 all had excellent antibacterial properties. The filament yarns with a specification of 75D / 36F spun from the in-situ polymerization black polyester chips prepared in Comparative Example 1 had a bacteriostatic rate of 72% against Candida albicans, 96% against Staphylococcus aureus, and 91% against Escherichia coli after 50 washes, indicating that the presence of nano carbon black could endow the in-situ polymerization black polyester fiber with antibacterial properties; however, compared with the filament yarns with a specification of 75D / 36F spun from the in-situ polymerization silver antibacterial black polyester prepared in Example 1 with the same carbon black content, the bacteriostatic rates against Staphylococcus aureus, Escherichia coli, and Candida albicans decreased after 50 washes, and the decrease in the bacteriostatic rate against the fungus Candida albicans was more significant; this indicates that the copolymer addition of 80 ppm of silver isophthalate diglycolate-5-sulfonate relative to the weight of the in-situ polymerization silver antibacterial black polyester could significantly improve the antibacterial properties of the in-situ polymerization black polyester, especially the antibacterial properties against the fungus Candida albicans.

[0129] 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 to include the preferred embodiments as well as all changes and modifications falling within the scope of the present invention.

[0130] 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. An in-situ polymerized silver antibacterial black polyester, characterized in that, Dimethyl isophthalate-5-sulfonate containing silver ion groups is copolymerized into 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 silver ions to be dispersed in the polyester matrix.

2. The in-situ polymerized silver antibacterial black polyester according to claim 1, characterized in that, The dispersion mode of the silver ions dispersed in the polyester matrix is atomic-level uniform dispersion.

3. The in-situ polymerized silver antibacterial black polyester according to claim 1, characterized in that, In the in-situ polymerized silver antibacterial black polyester, the primary particle size of the carbon black is 16 nm - 28 nm, and the mass percentage content of the added carbon black is 0.5% - 3.0%.

4. The in-situ polymerized silver antibacterial black polyester according to claim 1, wherein The fiber products spun from the in-situ polymerized black polyester have antibacterial properties.

5. The in-situ polymerized silver antibacterial black polyester according to claim 1, characterized in that, The filaments with a specification of 75D / 36F spun from the in-situ polymerized silver antibacterial black polyester have a bacteriostatic rate of more than 99% against Staphylococcus aureus, a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of not less than 80% against Candida albicans after being washed 50 times.

6. The preparation method of the in-situ polymerized silver antibacterial black polyester according to any one of claims 1-5, 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 through transesterification reaction, obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver. Among them, in the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver, the mass percentage content of diethylene glycol isophthalate-5-sulfonate silver is 1% - 10%. Prepare a first slurry with terephthalic acid and ethylene glycol, where the molar ratio of ethylene glycol to terephthalic acid is 1.05 - 2.

0. The first slurry undergoes an esterification reaction to obtain a polyester oligomer. Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. Among them, in the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5% - 15%; the addition amount of the carbon black is 0.5% - 3.0% of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time. The black polyester oligomer and the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate silver undergo in-situ pre-polymerization reaction, in-situ final polymerization reaction, filtration, cooling and solidification, and pelletizing to obtain the in-situ polymerized silver antibacterial black polyester chips. Among them, the addition amount of diethylene glycol isophthalate-5-sulfonate silver is 80 ppm - 800 ppm of the mass of the in-situ polymerized silver antibacterial black polyester produced in real time.

7. The preparation method of the in-situ polymerized silver antibacterial black polyester according to claim 6, characterized in that, The specific steps for preparing dimethyl isophthalate-5-sulfonate silver include the following: Add an alkaline silver salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid, and through an acid-base neutralization reaction, recrystallization, filtration, and drying, obtain dimethyl isophthalate-5-sulfonate silver. Among them, The alkaline silver salt is selected from one or a mixture 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 the dimethyl isophthalate-5-sulfonic acid; In the aqueous solution of dimethyl isophthalate-5-sulfonic acid, the mass percentage content of dimethyl isophthalate-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 in-situ polymerized silver antibacterial black polyester according to claim 6, characterized in that, The temperature of the transesterification reaction is 160°C - 190°C.

9. The preparation method of the in-situ polymerized silver antibacterial black polyester according to claim 6, characterized in that, In the step of obtaining a polyester oligomer by subjecting the first slurry to an esterification reaction, the temperature of the esterification reaction is 250°C - 270°C; the pressure of the esterification reaction is 100 kPa - 210 kPa; the esterification rate of the polyester oligomer is 90% - 97%.

10. The preparation method of the in-situ polymerized silver antibacterial black polyester according to claim 6, characterized in that, In the step of carrying out an in-situ prepolymerization reaction on the black polyester oligomer and an ethylene glycol solution of silver 5-sulfoisophthalate diglycolate, the temperature of the in-situ prepolymerization reaction is 270°C - 290°C; the pressure of the in-situ prepolymerization reaction is 2 kPa - 4 kPa; the intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester prepolymer prepared by the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g; Preferably, in the step of carrying out an in-situ final polymerization reaction on the in-situ polymerized silver antibacterial black polyester prepolymer, the temperature of the in-situ final polymerization reaction is 275°C - 290°C; the pressure of the in-situ final polymerization reaction is 100 Pa - 300 Pa; the intrinsic viscosity of the in-situ polymerized silver antibacterial black polyester melt prepared by the in-situ final polymerization reaction is 0.58 dL / g - 0.72 dL / g.

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