In-situ polymerization black antibacterial polyester and preparation method thereof
By using isophthalic acid of silver sulfonate ion groups as comonomer in polyester fibers, the silver ions are loaded onto the polyester molecular chain, solving the problem of low load efficiency of silver ion in in-situ polymerized black fibers, achieving efficient antibacterial performance and meeting the market's demand for antibacterial fibers.
Patent Information
- Application Number
- CN202311811286.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-26
- Publication Date
- 2025-06-27
AI Technical Summary
The prior art is difficult to effectively load silver ions in in-situ polymerization black fibers, resulting in insufficient antibacterial performance and unable to meet the market's rapid growth demand for antibacterial fibers.
By bonding isophthalic acid containing silver sulfonate ion groups as comonomer to the backbone of the polyethylene terephthalate molecular, the silver ions are loaded onto the polyester molecular chain by ionic bonds, the atomic-level highly uniform dispersion of the silver ions is achieved.
It greatly improves the antibacterial efficiency of silver ions and imparts excellent antibacterial properties to in-situ polymerized black polyester fibers, especially with high-efficiency antibacterial effects on Staphylococcus aureus, E. coli and Candida albicans.
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Figure CN120209278A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer material synthesis, and particularly relates to an in-situ polymerization black antibacterial polyester and a preparation method thereof. Background Art
[0002] Processing the solution-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 solution-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 solution-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 an in-situ polymerization black antibacterial polyester fiber can further expand the application fields of solution-dyed fibers. Summary of the Invention
[0003] In view of this, the present invention provides an in-situ polymerization black antibacterial polyester and a preparation method thereof, which can realize the loading of silver ions with high antibacterial performance, thereby endowing the fiber products spun from the in-situ polymerization black polyester with excellent antibacterial performance, and thus being more suitable for practical use.
[0004] In order to achieve the above first object, the technical solution of the in-situ polymerization black antibacterial polyester provided by the present invention is as follows:
[0005] The in-situ polymerization black antibacterial polyester provided by the present invention bonds isophthalic acid containing a sulfonic acid silver ion group as a comonomer to the main chain of the polyethylene terephthalate molecule, and loads silver ions onto the polyester molecular chain through ionic bonds.
[0006] The in-situ polymerization black antibacterial polyester provided by the present invention can also be further realized by the following technical measures.
[0007] Preferably, in the in-situ polymerization black antibacterial polyester, the primary particle size of carbon black is 16 nm - 28 nm.
[0008] Preferably, the fiber products spun from the in-situ polymerization black antibacterial polyester have antibacterial properties.
[0009] Preferably, for the filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, and the antibacterial rate against Candida albicans is not less than 81% after being washed 50 times.
[0010] In order to achieve the above second object, the technical solution of the preparation method of the in-situ polymerization black antibacterial polyester provided by the present invention is as follows:
[0011] The preparation method of the in-situ polymerization black antibacterial polyester provided by the present invention comprises the following steps:
[0012] Prepare silver 5-sulfoisophthalate;
[0013] The silver 5-sulfoisophthalate, terephthalic acid, and ethylene glycol are configured into a first slurry. Among them, the addition amount of the silver 5-sulfoisophthalate is 65 ppm - 650 ppm of the real-time output quality of the in-situ polymerization black antibacterial polyester. The molar ratio of ethylene glycol to the sum of terephthalic acid and silver 5-sulfoisophthalate is 1.05 - 2.0, and the addition amount of ethylene glycol is 33.3% - 64.3% of the real-time output quality of the in-situ polymerization black antibacterial polyester;
[0014] The first slurry undergoes an esterification reaction to obtain a silver-containing polyester oligomer;
[0015] The silver-containing polyester oligomer is mixed with a carbon black ethylene glycol slurry to obtain a black antibacterial polyester oligomer. Among them, the addition amount of carbon black mixed in the form of the carbon black ethylene glycol slurry is 0.5% - 3.0% of the real-time output quality of the in-situ polymerization black antibacterial polyester, and the mass percentage content of carbon black in the carbon black ethylene glycol slurry is 5% - 15%;
[0016] The black antibacterial polyester oligomer successively undergoes in-situ prepolymerization, in-situ final polymerization, filtration, cooling and solidification, and pelletizing to obtain the in-situ polymerization black antibacterial polyester chips.
[0017] The preparation method of the in-situ polymerization black antibacterial polyester provided by the present invention can also be further realized by adopting the following technical measures.
[0018] Preferably, the preparation of silver 5-sulfoisophthalate specifically comprises the following steps:
[0019] Add an alkaline silver salt to an aqueous solution of 5-sulfoisophthalic acid. After an acid-base neutralization reaction, recrystallize, filter, and dry to obtain silver 5-sulfoisophthalate. Among them,
[0020] The alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate;
[0021] The addition amount of the alkaline silver salt is 47.1% - 56.0% of the mass of 5-sulfoisophthalic acid;
[0022] In the aqueous solution of 5-sulfoisophthalic acid, the mass percentage content of 5-sulfoisophthalic acid is 10% - 30%;
[0023] The reaction temperature of the acid-base neutralization reaction is 50°C - 90°C.
[0024] Preferably, in the step of obtaining the silver-containing polyester oligomer by subjecting the first slurry to an esterification reaction,
[0025] the first slurry is continuously fed into an esterification reaction system for esterification reaction;
[0026] the esterification reaction temperature is 250°C - 270°C;
[0027] the esterification reaction pressure is 100 kPa - 210 kPa;
[0028] the esterification rate of the silver-containing polyester oligomer is 90% - 97%.
[0030] Preferably, in the step of mixing the silver-containing polyester oligomer and the ethylene glycol slurry of carbon black to obtain a black antibacterial polyester oligomer, the ethylene glycol slurry of carbon black is mixed with the silver-containing polyester oligomer in an on-line injection manner.
[0031] Preferably, in the step of subjecting the black antibacterial polyester oligomer to in-situ prepolymerization,
[0032] the in-situ prepolymerization reaction temperature is 270°C - 290°C;
[0033] the in-situ prepolymerization reaction pressure is 2 kPa - 4 kPa;
[0034] the intrinsic viscosity of the in-situ polymerized black antibacterial polyester prepolymer prepared by the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g.
[0035] Preferably, in the step of subjecting the in-situ polymerized black antibacterial polyester prepolymer to in-situ final polymerization,
[0036] the in-situ final polymerization reaction temperature is 275°C - 290°C;
[0037] the in-situ final polymerization reaction pressure is 100 Pa - 300 Pa;
[0038] the intrinsic viscosity of the in-situ polymerized black antibacterial polyester melt prepared by the in-situ final polymerization reaction is 0.58 dL / g - 0.72 dL / g.
[0039] The in-situ polymerized black antibacterial polyester prepared by the method for preparing in-situ polymerized black antibacterial polyester provided by the present invention has isophthalic acid containing a sulfonic acid silver ion group as a comonomer bonded to the main chain of the polyethylene terephthalate molecule, and silver ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions, and thus endowing the in-situ polymerized black polyester fiber product with excellent antibacterial performance. 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 for the preparation method of in-situ polymerization black antibacterial polyester provided by an embodiment of the present invention;
[0042] FIG Figure 2 is a schematic diagram of the material change relationship involved in the preparation method of in-situ polymerization black antibacterial polyester provided by an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0043] In view of this, the present invention provides an in-situ polymerization black antibacterial polyester and a preparation method thereof, which can achieve the loading of silver ions with high antibacterial performance, thereby endowing the fiber products spun from the in-situ polymerization black polyester with excellent antibacterial performance, and 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 predetermined invention purpose, the following combines the drawings and preferred embodiments to detail the specific embodiments, structures, features and effects of an in-situ polymerization black antibacterial 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.
[0045] The term "and / or" in this article is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B is specifically understood as: A and B can be included simultaneously, A can exist alone, or B can exist alone, and any of the above three situations can be satisfied.
[0046] In-situ polymerization black antibacterial polyester
[0047] The in-situ polymerization black antibacterial polyester provided by the present invention uses isophthalic acid containing a sulfonic acid silver ion group as a comonomer and bonds it to the main chain of the polyethylene terephthalate molecule, and loads silver ions onto the polyester molecular chain through ionic bonds.
[0048] The in-situ polymerization black antibacterial polyester prepared by the preparation method provided by the present invention is obtained by bonding isophthalic acid containing sulfonic acid silver ion groups 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 atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions and endowing the in-situ polymerization black polyester fiber product with excellent antibacterial performance.
[0049] Among them, in the in-situ polymerization black antibacterial polyester, the primary particle size of carbon black is 16nm - 28nm.
[0050] Among them, the fiber product spun from the in-situ polymerization black antibacterial polyester has antibacterial properties.
[0051] Among them, for the filament with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, and the antibacterial rate against Candida albicans is not less than 81% after being washed 50 times.
[0052] Preparation method of in-situ polymerization black antibacterial polyester
[0053] See Appendix Figure 1 and Appendix Figure 2 The preparation method of the in-situ polymerization black antibacterial polyester provided by the present invention includes the following steps:
[0054] Step S1: Prepare silver 5-sulfoisophthalate;
[0055] Step S2: Configure silver 5-sulfoisophthalate, terephthalic acid, and ethylene glycol into a first slurry. Among them, the addition amount of silver 5-sulfoisophthalate is 65ppm - 650ppm of the real-time output quality of the in-situ polymerization black antibacterial polyester, the molar ratio of ethylene glycol to terephthalic acid and silver 5-sulfoisophthalate is 1.05 - 2.0, and the addition amount of ethylene glycol is 33.3% - 64.3% of the real-time output quality of the in-situ polymerization black antibacterial polyester;
[0056] Step S3: Subject the first slurry to an esterification reaction to obtain a silver-containing polyester oligomer;
[0057] Step S4: Mix the silver-containing polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black antibacterial polyester oligomer. Among them, the addition amount of carbon black mixed in the form of an ethylene glycol slurry of carbon black is 0.5% - 3.0% of the real-time output quality of the in-situ polymerization black antibacterial polyester, and the mass percentage of carbon black in the ethylene glycol slurry of carbon black is 5% - 15%;
[0058] Step S5: The black antibacterial polyester oligomer is successively subjected to in-situ prepolymerization, in-situ final polymerization, filtration, cooling and solidification, and pelletizing to obtain in-situ polymerized black antibacterial polyester chips.
[0059] The in-situ polymerized black antibacterial polyester prepared by the preparation method of in-situ polymerized black antibacterial polyester provided by the present invention is obtained by bonding isophthalic acid containing sulfonic acid silver ion groups 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 atomic-level highly uniform dispersion of silver ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of silver ions, and endowing the in-situ polymerized black polyester fiber product with excellent antibacterial performance.
[0060] Among them, the preparation of silver 5-sulfoisophthalate specifically includes the following steps:
[0061] An alkaline silver salt is added to an aqueous solution of 5-sulfoisophthalic acid, and after an acid-base neutralization reaction, recrystallization, filtration, and drying are carried out to obtain silver 5-sulfoisophthalate, 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 47.1%-56.0% of the mass of 5-sulfoisophthalic acid; in the aqueous solution of 5-sulfoisophthalic acid, the mass percentage content of 5-sulfoisophthalic acid is 10%-30%; the reaction temperature of the acid-base neutralization reaction is 50°C-90°C.
[0062] Among them, in the step of obtaining a silver-containing polyester oligomer by subjecting the first slurry to an esterification reaction, the first slurry is continuously fed into an esterification reaction system for esterification reaction; the esterification reaction temperature is 250°C-270°C; the esterification reaction pressure is 100 kPa-210 kPa, and the esterification rate of the silver-containing polyester oligomer is 90%-97%.
[0063] Among them, in the step of mixing the ethylene glycol slurry of the silver-containing polyester oligomer and carbon black to obtain a black antibacterial polyester oligomer, the ethylene glycol slurry of carbon black is mixed with the silver-containing polyester oligomer in an on-line injection manner.
[0064] Among them, in the step of subjecting the black antibacterial polyester oligomer to in-situ prepolymerization, the in-situ prepolymerization reaction temperature is 270°C-290°C; the in-situ prepolymerization reaction pressure is 2 kPa-4 kPa; the intrinsic viscosity of the in-situ polymerized black antibacterial polyester prepolymer prepared by the in-situ prepolymerization reaction is 0.15 dL / g-0.30 dL / g.
[0065] During the step of in-situ final polymerization of the in-situ polymerized black antibacterial 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 black antibacterial polyester melt prepared by the in-situ final polymerization reaction is 0.58 dL / g - 0.72 dL / g.
[0066] Example 1
[0067] (1) Silver oxide is added to an aqueous solution with a mass percentage of 20% of isophthalic acid-5-sulfonic acid. After an acid-base neutralization reaction at 80°C, recrystallization, filtration, and drying are carried out to obtain silver isophthalate-5-sulfonate, where the addition amount of silver oxide is 47.1% of the weight of isophthalic acid-5-sulfonic acid.
[0068] (2) The silver isophthalate-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of silver isophthalate-5-sulfonate is 65 ppm of the mass of the in-situ polymerized black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 36.8% of the mass of the in-situ polymerized black antibacterial polyester produced in real time.
[0069] (3) The slurry configured in step (2) is continuously transported into an esterification reaction kettle for an esterification reaction to obtain a silver-containing polyester oligomer; the esterification rate of the silver-containing polyester oligomer is 92%, the reaction temperature of the esterification reaction kettle is 260°C, and the reaction pressure is 170 kPa.
[0070] (4) The silver-containing polyester oligomer prepared in step (3) is continuously transported into a kettle for preparing in-situ polymerized polyester oligomers and mixed evenly with an ethylene glycol slurry in which carbon black is injected online to obtain a black antibacterial polyester oligomer; the addition amount of carbon black is 1% of the mass of the in-situ polymerized black antibacterial 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%.
[0071] (5) The black antibacterial polyester oligomer prepared in step (4) is continuously transported to a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerized black antibacterial polyester prepolymer; the pre-polycondensation reaction temperature is 280°C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the in-situ polymerized black antibacterial polyester prepolymer prepared is 0.25 dL / g.
[0072] (6) The in-situ polymerized black antibacterial polyester prepolymer prepared in step (5) is continuously transported to a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerized black antibacterial polyester melt; the final polycondensation reaction temperature is 285°C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the in-situ polymerized black antibacterial polyester melt prepared is 0.67 dL / g.
[0073] (7) Filter the in-situ polymerization black antibacterial polyester melt prepared in step (6), then cool, solidify and pelletize it to obtain in-situ polymerization black antibacterial polyester chips.
[0074] Example 2
[0075] (1) Add silver oxide to an aqueous solution with a mass percentage of 30% of isophthalic acid-5-sulfonic acid. After carrying out an acid-base neutralization reaction at 90 °C, recrystallize, filter and dry to obtain silver isophthalate-5-sulfonate, where the addition amount of silver oxide is 47.1% of the weight of isophthalic acid-5-sulfonic acid.
[0076] (2) Prepare a slurry by mixing the silver isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of silver isophthalate-5-sulfonate is 160 ppm of the mass of the in-situ polymerization black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 36.6% of the mass of the in-situ polymerization black antibacterial polyester produced in real time.
[0077] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer. The esterification rate of the silver-containing polyester oligomer is 92%. The reaction temperature of the esterification reactor is 260 °C and the reaction pressure is 170 kPa.
[0078] (4) Continuously convey the silver-containing polyester oligomer prepared in step (3) into a reactor for preparing in-situ polymerization polyester oligomers, and mix it evenly with an ethylene glycol slurry with carbon black injected online to obtain a black antibacterial polyester oligomer. The addition amount of carbon black is 1.5% of the mass of the in-situ polymerization black antibacterial 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%.
[0079] (5) Continuously convey the black antibacterial polyester oligomer prepared in step (4) to a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerization black antibacterial polyester prepolymer. The pre-polycondensation reaction temperature is 280 °C and the reaction pressure is 2 kPa. The intrinsic viscosity of the obtained in-situ polymerization black antibacterial polyester prepolymer is 0.28 dL / g.
[0080] (6) Continuously convey the in-situ polymerization black antibacterial polyester prepolymer prepared in step (5) to a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerization black antibacterial polyester melt. The final polycondensation reaction temperature is 285 °C and the reaction pressure is 200 Pa. The intrinsic viscosity of the obtained in-situ polymerization black antibacterial polyester melt is 0.69 dL / g.
[0081] (7) Filter the in-situ polymerized black antibacterial polyester melt obtained in step (6), then cool, solidify and pelletize it to obtain in-situ polymerized black antibacterial polyester chips.
[0082] Example 3
[0083] (1) Add silver sulfide to an aqueous solution with a mass percentage of 10% of isophthalic acid-5-sulfonic acid. After carrying out an acid-base neutralization reaction at 90 °C, recrystallize, filter and dry to obtain silver isophthalate-5-sulfonate, where the addition amount of silver sulfide is 50.3% of the weight of isophthalic acid-5-sulfonic acid.
[0084] (2) Prepare a slurry by mixing the silver isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.05. The addition amount of silver isophthalate-5-sulfonate is 325 ppm of the mass of the in-situ polymerized black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 33.3% of the mass of the in-situ polymerized black antibacterial polyester produced in real time.
[0085] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a silver-containing polyester oligomer. The esterification rate of the silver-containing polyester oligomer is 97%. The esterification reaction system consists of two esterification reactors connected in series. The reaction temperature of the first esterification reactor is 265 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification reactor is 270 °C and the reaction pressure is 100 kPa.
[0086] (4) Continuously convey the silver-containing polyester oligomer prepared in step (3) into a reactor for preparing in-situ polymerized polyester oligomers, and mix it evenly with an ethylene glycol slurry with carbon black injected online to obtain a black antibacterial polyester oligomer. The addition amount of carbon black is 2% of the mass of the in-situ polymerized black antibacterial 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%.
[0087] (5) Continuously convey the black antibacterial polyester oligomer prepared in step (4) to a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerized black antibacterial polyester prepolymer. The pre-polycondensation reaction temperature is 275 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the obtained in-situ polymerized black antibacterial polyester prepolymer is 0.22 dL / g.
[0088] (6) Continuously convey the in-situ polymerized black antibacterial polyester prepolymer prepared in step (5) to a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized black antibacterial 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 black antibacterial polyester melt is 0.65 dL / g.
[0089] (7) The in-situ polymerization black antibacterial polyester melt prepared in step (6) is filtered, cooled, solidified, and pelletized to obtain in-situ polymerization black antibacterial polyester chips.
[0090] Example 4
[0091] (1) Silver oxide is added to an aqueous solution with a mass percentage of 30% of isophthalic acid-5-sulfonic acid. After an acid-base neutralization reaction at 90 °C, recrystallization, filtration, and drying are carried out to obtain silver isophthalate-5-sulfonate, where the addition amount of silver oxide is 47.1% of the weight of isophthalic acid-5-sulfonic acid.
[0092] (2) The silver isophthalate-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of silver isophthalate-5-sulfonate is 650 ppm of the mass of the in-situ polymerization black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 36.1% of the mass of the in-situ polymerization black antibacterial polyester produced in real time.
[0093] (3) The slurry configured in step (2) is continuously transported into an esterification reaction kettle for an esterification reaction to obtain a silver-containing polyester oligomer. The esterification rate of the silver-containing polyester oligomer is 92%. The reaction temperature of the esterification reaction kettle is 260 °C, and the reaction pressure is 170 kPa.
[0094] (4) The silver-containing polyester oligomer prepared in step (3) is continuously transported into a kettle for preparing in-situ polymerization polyester oligomers and mixed evenly with an ethylene glycol slurry with carbon black injected online to obtain a black antibacterial polyester oligomer. The addition amount of carbon black is 3% of the mass of the in-situ polymerization black antibacterial 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%.
[0095] (5) The black antibacterial polyester oligomer prepared in step (4) is continuously transported into a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization black antibacterial polyester prepolymer. The pre-polycondensation reaction temperature is 270 °C, the reaction pressure is 4 kPa, and the intrinsic viscosity of the prepared in-situ polymerization black antibacterial polyester prepolymer is 0.15 dL / g.
[0096] (6) The in-situ polymerization black antibacterial polyester prepolymer prepared in step (5) is continuously transported into a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization black antibacterial polyester melt. The final polycondensation reaction temperature is 275 °C, the reaction pressure is 300 Pa, and the intrinsic viscosity of the prepared in-situ polymerization black antibacterial polyester melt is 0.58 dL / g.
[0097] (7) The in-situ polymerization black antibacterial polyester melt prepared in step (6) is filtered, cooled, solidified, and pelletized to obtain in-situ polymerization black antibacterial polyester chips.
[0098] Example 5
[0099] (1) Silver carbonate is added to an aqueous solution with a mass percentage of 10% of isophthalic acid-5-sulfonic acid. After an acid-base neutralization reaction at 50 °C, recrystallization, filtration, and drying are carried out to obtain silver isophthalic acid-5-sulfonate, where the addition amount of silver carbonate is 56.0% of the weight of isophthalic acid-5-sulfonic acid.
[0100] (2) The silver isophthalic acid-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 2.0. The addition amount of silver isophthalic acid-5-sulfonate is 245 ppm of the mass of the in-situ polymerization black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 64.3% of the mass of the in-situ polymerization black antibacterial polyester produced in real time.
[0101] (3) The slurry configured in step (2) is continuously fed into an esterification reaction kettle for an esterification reaction to obtain a silver-containing polyester oligomer. The esterification rate of the silver-containing polyester oligomer is 90%. The reaction temperature of the esterification reaction kettle is 250 °C, and the reaction pressure is 210 kPa.
[0102] (4) The silver-containing polyester oligomer prepared in step (3) is continuously fed into a preparation kettle for in-situ polymerization polyester oligomers and mixed evenly with an ethylene glycol slurry with carbon black injected online to obtain a black antibacterial polyester oligomer. The addition amount of carbon black is 0.5% of the mass of the in-situ polymerization black antibacterial polyester produced in real time. The primary particle size of the carbon black is 16 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 5%.
[0103] (5) The black antibacterial polyester oligomer prepared in step (4) is continuously fed into a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization black antibacterial polyester prepolymer. The pre-polycondensation reaction temperature is 290 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared in-situ polymerization black antibacterial polyester prepolymer is 0.30 dL / g.
[0104] (6) The in-situ polymerization black antibacterial polyester prepolymer prepared in step (5) is continuously fed into a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization black antibacterial polyester melt. The final polycondensation reaction temperature is 290 °C, the reaction pressure is 100 Pa, and the intrinsic viscosity of the prepared in-situ polymerization black antibacterial polyester melt is 0.72 dL / g.
[0105] (7) The in-situ polymerization black antibacterial polyester melt prepared in step (6) is filtered, cooled, solidified, and pelletized to obtain in-situ polymerization black antibacterial polyester chips.
[0106] Comparative Example 1
[0107] (1) Prepare a slurry by mixing terephthalic acid and ethylene glycol in a certain molar ratio, where the molar ratio of glycol to acid in the slurry is 1.15.
[0108] (2) Continuously transport the slurry prepared in step (1) into an esterification reactor 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 reactor is 260 °C, and the reaction pressure is 170 kPa.
[0109] (3) Continuously transport the polyester oligomer prepared in step (2) 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% 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%.
[0110] (4) Continuously transport the black polyester oligomer prepared in step (3) to a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerized black polyester prepolymer; the pre-polycondensation reaction temperature is 280 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared in-situ polymerized black polyester prepolymer is 0.25 dL / g.
[0111] (5) Continuously transport the in-situ polymerized black polyester prepolymer prepared in step (4) to a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized 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 polymerized black polyester melt is 0.67 dL / g.
[0112] (6) Filter the in-situ polymerized black polyester melt prepared in step (5), then cool, solidify, and pelletize it to obtain in-situ polymerized black polyester chips.
[0113] Experimental Example 1
[0114] (1) Dry the in-situ polymerized black antibacterial polyester chips prepared in Examples 1 to 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.
[0115] (2) Melt-spin the dried chips obtained in step 1 on a melt spinning machine to prepare a pre-oriented yarn with a specification of 120 D / 36 F, where the melt spinning temperature is 290 °C and the spinning speed is 3000 m / min.
[0116] (3) The pre-oriented yarn prepared in step (2) is drawn and processed on a flat drawing machine to prepare drawn yarn with a specification of 75D / 36F, where the draw ratio is 1.6 times, the draw temperature is 80 °C, and the setting temperature is 130 °C.
[0117] (4) The filaments with a specification of 75D / 36F prepared in step (3) are woven into a garter belt, then washed 50 times under test condition A1M in GB / T 12490-1990, and then the antibacterial rates of the garter belt against Staphylococcus aureus, Escherichia coli, and Candida albicans after 50 washes are tested according to GB / T 20944.3-2007. The test results are shown in Table 1.
[0118] Table 1 Antibacterial performance test results of filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester chips prepared in Examples 1-5 and the in-situ polymerization black polyester chips prepared in Comparative Example 1
[0119]
[0120]
[0121] As can be seen from Table 1, the antibacterial rates of the filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester chips prepared in Examples 1-5 against Staphylococcus aureus and Escherichia coli are both greater than 99% after 50 washes with water, and the antibacterial rate against Candida albicans is not less than 81%; this indicates that the filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester chips prepared in Examples 1-5 all have excellent antibacterial performance. The antibacterial rate of the filaments with a specification of 75D / 36F spun from the in-situ polymerization black polyester chips prepared in Comparative Example 1 against Candida albicans is 72% after 50 washes with water, the antibacterial rate against Staphylococcus aureus is 96%, and the antibacterial rate against Escherichia coli is 91%, indicating that the presence of nano-carbon black can endow the in-situ polymerization black polyester fiber with antibacterial performance; however, compared with the filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester prepared in Example 1 with the same carbon black content, the antibacterial rates against Staphylococcus aureus, Escherichia coli, and Candida albicans are all reduced after 50 washes with water, and the reduction in the antibacterial rate against the fungus Candida albicans is more significant; this indicates that the copolymer addition of 65 ppm of silver isophthalate-5-sulfonate relative to the weight of the in-situ polymerization black antibacterial polyester can significantly improve the antibacterial performance of the in-situ polymerization black polyester, especially the antibacterial performance against the fungus Candida albicans.
[0122] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they learn 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.
[0123] 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 black antibacterial polyester, characterized in that, Take isophthalic acid containing a sulfonic acid silver ion group as a comonomer and bond it to the main chain of polyethylene terephthalate molecules, and load silver ions onto the polyester molecular chain through ionic bonds.
2. The in-situ polymerized black antibacterial polyester according to claim 1, characterized in that, In the in-situ polymerization black antibacterial polyester, the primary particle size of carbon black is 16 nm - 28 nm.
3. The in-situ polymerized black antibacterial polyester according to claim 1, wherein The fiber products spun from the in-situ polymerization black antibacterial polyester have antibacterial properties.
4. The in-situ polymerized black antibacterial polyester according to claim 1, characterized in that, After the filaments with a specification of 75D / 36F spun from the in-situ polymerization black antibacterial polyester are washed 50 times, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, and the antibacterial rate against Candida albicans is not less than 81%.
5. The preparation method of the in-situ polymerized black antibacterial polyester according to any one of claims 1-4, characterized in that, It includes the following steps: Prepare isophthalic acid-5-sulfonic acid silver; Configure the isophthalic acid-5-sulfonic acid silver, terephthalic acid, and ethylene glycol into a first slurry. Among them, the addition amount of the isophthalic acid-5-sulfonic acid silver is 65 ppm - 650 ppm of the mass of the in-situ polymerization black antibacterial polyester produced in real time, and the molar ratio of ethylene glycol to terephthalic acid and isophthalic acid-5-sulfonic acid silver is 1.05 - 2.
0. The addition amount of ethylene glycol is 33.3% - 64.3% of the mass of the in-situ polymerization black antibacterial polyester produced in real time; The first slurry undergoes an esterification reaction to obtain a silver-containing polyester oligomer; Mix the silver-containing polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black antibacterial polyester oligomer. Among them, the addition amount of carbon black mixed in the form of an ethylene glycol slurry of carbon black is 0.5% - 3.0% of the mass of the in-situ polymerization black antibacterial polyester produced in real time, and the mass percentage content of carbon black in the ethylene glycol slurry of carbon black is 5% - 15%; The black antibacterial polyester oligomer undergoes in-situ pre-polymerization, in-situ final polymerization, filtration, cooling and solidification, and pelletizing in sequence to obtain the in-situ polymerization black antibacterial polyester chips.
6. The preparation method of the in-situ polymerized black antibacterial polyester according to claim 5, characterized in that, The specific steps for preparing the isophthalic acid-5-sulfonic acid silver include the following: Add an alkaline silver salt to an aqueous solution of isophthalic acid-5-sulfonic acid, and after an acid-base neutralization reaction, perform recrystallization, filtration, and drying to obtain isophthalic acid-5-sulfonic acid silver. Among them, The alkaline silver salt is selected from one or a mixture of several of silver oxide, silver sulfide, and silver carbonate; The addition amount of the alkaline silver salt is 47.1% - 56.0% of the mass of the isophthalic acid-5-sulfonic acid; In the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of isophthalic acid-5-sulfonic acid is 10% - 30%; The reaction temperature of the acid-base neutralization reaction is 50°C - 90°C.
7. The preparation method of the in-situ polymerized black antibacterial polyester according to claim 5, characterized in that, During the step of obtaining a silver-containing polyester oligomer by subjecting the first slurry to an esterification reaction, The first slurry is continuously conveyed into an esterification reaction system for an esterification reaction; The esterification reaction temperature is 250°C - 270°C; The esterification reaction pressure is 100 kPa - 210 kPa; The esterification rate of the silver-containing polyester oligomer is 90% - 97%.
8. The preparation method of the in-situ polymerized black antibacterial polyester according to claim 5, characterized in that, During the step of mixing the silver-containing polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black antibacterial polyester oligomer, the ethylene glycol slurry of carbon black is mixed with the silver-containing polyester oligomer in an on-line injection manner.
9. The preparation method of the in-situ polymerized black antibacterial polyester according to claim 5, characterized in that, During the step of in-situ prepolymerization of the black antibacterial polyester oligomer, 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 black antibacterial polyester prepolymer prepared by the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g.
10. The preparation method of the in-situ polymerized black antibacterial polyester according to claim 9, characterized in that, During the step of in-situ final polymerization of the in-situ polymerized black antibacterial 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 black antibacterial polyester melt prepared by the in-situ final polymerization reaction is 0.58 dL / g - 0.72 dL / g.