In-situ polymerization blue-phase black antibacterial polyester and preparation method thereof

Abstract

The invention discloses in-situ polymerization blue-phase black antibacterial polyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. Copper ions contained in the polyester are dispersed in the in-situ polymerization blue-phase black antibacterial polyester, so that the in-situ polymerization blue-phase black antibacterial polyester has antibacterial performance on bacteria and fungi. The method comprises the following steps: adding alkaline copper salt into an m-phthalic acid-5-sulfonic acid aqueous solution to obtain a neutralization reaction product; and crystallizing, filtering and drying to obtain the 5-sulfoisophthalic acid copper salt. Mixing with ethylene glycol and terephthalic acid to obtain mixed slurry; carrying out esterification reaction to obtain a copper-containing polyester oligomer; continuously conveying into an in-situ polymerization polyester oligomer preparation kettle, and uniformly mixing with ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer; and carrying out in-situ prepolymerization, in-situ final polymerization, filtering, cooling, curing and pelletizing molding to obtain the in-situ polymerization blue-phase black antibacterial polyester chip. The blue phase antibacterial agent can endow a spun fiber product with blue phase and antibacterial performance.

Description

Technical Field

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

[0002] The processing of solution-dyed fibers into textiles can eliminate the dyeing process, with outstanding carbon emission reduction and carbon sequestration effects; it is estimated that, compared with traditional post-spinning dyed polyester fibers, for each ton of solution-dyed polyester fibers processed into textiles, 32 tons of wastewater and 1.2 tons of carbon dioxide can be reduced. 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 black fibers account for more than 80%. Summary of the Invention

[0003] In view of this, the present invention provides an in-situ polymerization blue-phase black antibacterial polyester and a preparation method thereof. The in-situ polymerization blue-phase black antibacterial polyester prepared by applying this method contains copper ions dispersed in the in-situ polymerization blue-phase black antibacterial polyester, realizing the loading of blue copper ions with high antibacterial performance, thereby endowing the fiber products spun from the in-situ polymerization black polyester with excellent blue phase and antibacterial and antifungal properties, 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 blue-phase black antibacterial polyester provided by the present invention is as follows:

[0005] The copper ions contained in the in-situ polymerization blue-phase black antibacterial polyester provided by the present invention are dispersed in the in-situ polymerization blue-phase black antibacterial polyester. Among them, isophthalic acid containing a copper sulfonate ion group is used as a comonomer and bonded to the main chain of the polyethylene terephthalate molecule, and blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, so that the in-situ polymerization blue-phase black antibacterial polyester has antibacterial properties against bacteria and fungi.

[0006] The in-situ polymerization blue-phase black antibacterial polyester provided by the present invention can also be further realized by adopting the following technical measures.

[0007] Preferably, the b value of the yellowness-blue index of the filament with a specification of 75D / 36F spun from the in-situ polymerization blue-phase black antibacterial polyester is not higher than -0.6. After the in-situ polymerization blue-phase black antibacterial polyester is washed 50 times, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, the antibacterial rate against Klebsiella pneumoniae is greater than 99%, the antibacterial rate against Candida albicans is greater than 99%, and the antibacterial rate against Trichophyton rubrum is not less than 80%.

[0008] Preferably, in the in-situ polymerized blue-phase black antibacterial polyester, the primary particle size of the carbon black is 16 nm - 28 nm, and the addition amount of the carbon black is 0.5% - 3.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester.

[0009] To achieve the above second object, the technical solution of the preparation method of the in-situ polymerized blue-phase black antibacterial polyester provided by the present invention is as follows:

[0010] The preparation method of the in-situ polymerized blue-phase black antibacterial polyester provided by the present invention includes the following steps:

[0011] Add an alkaline copper salt to an aqueous solution of isophthalic acid-5-sulfonic acid for a neutralization reaction to obtain a neutralization reaction product. Among them, in the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of the isophthalic acid-5-sulfonic acid solute is 10% - 30%, and the addition amount of the alkaline copper salt is 19.8% - 52.4% of the mass of the isophthalic acid-5-sulfonic acid solute;

[0012] The neutralization reaction product is successively subjected to crystallization, filtration, and drying to obtain copper isophthalate-5-sulfonate;

[0013] Mix the copper isophthalate-5-sulfonate with ethylene glycol and terephthalic acid to obtain a mixed slurry. Among them, the molar ratio of ethylene glycol to terephthalic acid and copper isophthalate-5-sulfonate is 1.05 - 2.0, the addition amount of the copper isophthalate-5-sulfonate is 0.4% - 1.3% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of the ethylene glycol is 33.0% - 64.1% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time;

[0014] The mixed slurry undergoes an esterification reaction to obtain a copper-containing polyester oligomer;

[0015] The copper-containing polyester oligomer is continuously transported into an in-situ polymerization polyester oligomer preparation kettle and mixed evenly with an ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer. Among them, the addition amount of the carbon black is 0.5% - 3.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time; in the ethylene glycol slurry of carbon black, the mass percentage content of the carbon black is 5% - 15%;

[0016] The blue-phase black antibacterial polyester oligomer is successively subjected to in-situ pre-polymerization, in-situ final polymerization, filtration, cooling, curing, and pelletizing to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0017] The preparation method of the in-situ polymerized blue-phase black antibacterial polyester provided by the present invention can also be further realized by the following technical measures.

[0018] Preferably, the in-situ prepolymerization step of the blue-phase black antibacterial polyester oligomer is specifically to continuously convey the blue-phase black antibacterial polyester oligomer to a prepolycondensation system for in-situ prepolymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester prepolymer.

[0019] Preferably, the in-situ final polymerization step of the in-situ polymerized blue-phase black antibacterial polyester prepolymer is specifically to continuously convey the in-situ polymerized blue-phase black antibacterial polyester prepolymer to a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester melt.

[0020] Preferably, the basic copper salt is selected from one or a mixture of several of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0021] Preferably, during the step of obtaining a copper-containing polyester oligomer by subjecting the mixed slurry to an esterification reaction, the esterification rate of the copper-containing polyester oligomer is 90%-97%.

[0022] Preferably, during the step of continuously conveying the copper-containing polyester oligomer into a reactor for preparing an in-situ polymerized polyester oligomer and mixing it evenly with an ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer, the addition method of the ethylene glycol slurry of carbon black in the reactor for preparing the in-situ polymerized polyester oligomer is online injection.

[0023] Preferably,

[0024] the temperature of the neutralization reaction is 50°C - 90°C;

[0025] the temperature of the esterification reaction is 250°C - 270°C, and the reaction pressure is 100 kPa - 210 kPa;

[0026] the reaction temperature of the in-situ prepolymerization reaction is 270°C - 290°C, and the reaction pressure is 2 kPa - 4 kPa. The intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester prepolymer obtained through the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g;

[0027] the reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C, and the reaction pressure is 100 Pa - 400 Pa. The intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester melt obtained through the final polycondensation reaction is 0.55 dL / g - 0.72 dL / g.

[0028] The in-situ polymerization blue-phase black antibacterial polyester provided by the present invention uses isophthalic acid containing sulfonic acid copper ion groups as a comonomer to be bonded to the main chain of polyethylene terephthalate molecules, and highly efficient antibacterial blue copper ions are loaded onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of copper ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of copper ions; then, carbon black pigments are uniformly dispersed in the polyester matrix through in-situ polymerization, and the blue copper ions loaded on the polyester molecular chain can play a color compensation role for the in-situ polymerization black polyester, thereby endowing its fiber products with excellent blue phases. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] 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:

[0030] Attached Figure 1 It is a flowchart of the changes of various substances in the preparation method of the in-situ polymerization blue-phase black antibacterial polyester provided by the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] In view of this, the present invention provides an in-situ polymerization blue-phase black antibacterial polyester and a preparation method thereof. The in-situ polymerization blue-phase black antibacterial polyester prepared by applying this method has copper ions dispersed therein, realizing the loading of highly efficient antibacterial blue copper ions, thereby endowing the fiber products spun from the in-situ polymerization black polyester with excellent blue phases and excellent antibacterial and antifungal properties, and thus being more suitable for practical use.

[0032] After arduous efforts, the inventors found that

[0033] The main methods for preparing the dope-dyed black polyester fiber are mainly the masterbatch method and the in-situ polymerization method. Compared with the masterbatch method, the in-situ polymerization method for preparing the dope-dyed black polyester fiber has smaller carbon black dispersion particle sizes and better mechanical properties. However, the smaller the carbon black dispersion particle size, the stronger its scattering ability for blue light, resulting in the hue of the in-situ polymerization black polyester fiber tending to be a brown phase and the color being dull.

[0034] 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 blue-phase 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.

[0035] 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 at the same time, A can exist alone, or B can exist alone, and it can have any of the above three situations.

[0036] In-situ Polymerized Blue Phase Black Antibacterial Polyester

[0037] The copper ions contained in the in-situ polymerized blue-phase black antibacterial polyester provided by the present invention are dispersed in the in-situ polymerized blue-phase black antibacterial polyester. Among them, isophthalic acid containing a copper sulfonate ion group is used as a comonomer and bonded to the main chain of the polyethylene terephthalate molecule. The blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, so that the in-situ polymerized blue-phase black antibacterial polyester has antibacterial properties against bacteria and fungi.

[0038] The in-situ polymerized blue-phase black antibacterial polyester provided by the present invention uses isophthalic acid containing a copper sulfonate ion group as a comonomer and bonds it to the main chain of the polyethylene terephthalate molecule. The blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of copper ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of copper ions; then, carbon black pigments are uniformly dispersed in the polyester matrix through in-situ polymerization. The blue copper ions loaded on the polyester molecular chain can play a color compensation role for the in-situ polymerized black polyester, thereby endowing its fiber products with an excellent blue phase.

[0039] Among them, the b value of the filament with a specification of 75D / 36F spun from the in-situ polymerized blue-phase black antibacterial polyester is not higher than -0.6. After the in-situ polymerized blue-phase black antibacterial polyester is washed 50 times, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, the antibacterial rate against Klebsiella pneumoniae is greater than 99%, the antibacterial rate against Candida albicans is greater than 99%, and the antibacterial rate against Trichophyton rubrum is not less than 80%.

[0040] Among them, in the in-situ polymerized blue-phase black antibacterial polyester, the primary particle size of carbon black is 16nm - 28nm, and the addition amount of carbon black is 0.5% - 3.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester.

[0041] Preparation Method of In-situ Polymerized Blue Phase Black Antibacterial Polyester

[0042] See the appendix Figure 1 , the preparation method of the in-situ polymerized blue-phase black antibacterial polyester provided by the present invention includes the following steps:

[0043] Step S1: Add an alkaline copper salt to an aqueous solution of isophthalic acid-5-sulfonic acid to carry out a neutralization reaction to obtain a neutralization reaction product. Among them, in the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of the isophthalic acid-5-sulfonic acid solute is 10%-30%, and the addition amount of the alkaline copper salt is 19.8%-52.4% of the mass of the isophthalic acid-5-sulfonic acid solute;

[0044] Step S2: The neutralization reaction product is successively subjected to crystallization, filtration, and drying to obtain copper isophthalate-5-sulfonate;

[0045] Step S3: Mix copper isophthalate-5-sulfonate with ethylene glycol and terephthalic acid to obtain a mixed slurry. Among them, the molar ratio of ethylene glycol to terephthalic acid and copper isophthalate-5-sulfonate is 1.05-2.0, the addition amount of copper isophthalate-5-sulfonate is 0.4%-1.3% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 33.0%-64.1% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time;

[0046] Step S4: The mixed slurry undergoes an esterification reaction to obtain a copper-containing polyester oligomer;

[0047] Step S5: Continuously convey the copper-containing polyester oligomer into an in-situ polymerization polyester oligomer preparation kettle, and mix it evenly with the ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer. Among them, the addition amount of carbon black is 0.5%-3.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time; in the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5%-15%;

[0048] Step S6: The blue-phase black antibacterial polyester oligomer is successively subjected to in-situ prepolymerization, in-situ final polymerization, filtration, cooling, curing, and pelletizing to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0049] The in-situ polymerized blue-phase black antibacterial polyester provided by the present invention uses isophthalic acid containing a sulfonic acid copper ion group as a comonomer and bonds it to the main chain of the polyethylene terephthalate molecule. The highly efficient antibacterial blue copper ions are loaded onto the polyester molecular chain through ionic bonds, realizing the atomic-level highly uniform dispersion of copper ions in the polyester matrix, thereby greatly improving the antibacterial efficiency of copper ions; then, carbon black pigment is uniformly dispersed in the polyester matrix through in-situ polymerization. The blue copper ions loaded on the polyester molecular chain can play a color compensation role for the in-situ polymerized black polyester, thereby endowing its fiber products with an excellent blue phase.

[0050] Among them, the in-situ prepolymerization step of the blue-phase black antibacterial polyester oligomer is specifically to continuously convey the blue-phase black antibacterial polyester oligomer to a pre-polycondensation system for in-situ prepolymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester prepolymer.

[0051] Among them, the in-situ final polymerization step of the in-situ polymerization blue-phase black antibacterial polyester prepolymer specifically is to continuously convey the in-situ polymerization blue-phase black antibacterial polyester prepolymer to the final condensation polymerization system for in-situ final polymerization reaction to obtain an in-situ polymerization blue-phase black antibacterial polyester melt.

[0052] Among them, the basic copper salt is selected from one or a mixture of several of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0053] Among them, during the step of obtaining the copper-containing polyester oligomer by subjecting the mixed slurry to an esterification reaction, the esterification rate of the copper-containing polyester oligomer is 90%-97%.

[0054] Among them, during the step of continuously conveying the copper-containing polyester oligomer into the in-situ polymerization polyester oligomer preparation kettle and mixing it evenly with the ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer, the addition method of the ethylene glycol slurry of carbon black in the in-situ polymerization polyester oligomer preparation kettle is on-line injection. In this case, the continuous preparation of the in-situ polymerization blue-phase black antibacterial polyester provided in the embodiment of the present invention can be realized.

[0055] Among them, the temperature of the neutralization reaction is 50°C - 90°C; the temperature of the esterification reaction is 250°C - 270°C, and the reaction pressure is 100 kPa - 210 kPa; the reaction temperature of the in-situ prepolymerization reaction is 270°C - 290°C, and the reaction pressure is 2 kPa - 4 kPa. The intrinsic viscosity of the in-situ polymerization blue-phase black antibacterial polyester prepolymer obtained through the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g; the reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C, and the reaction pressure is 100 Pa - 400 Pa. The intrinsic viscosity of the in-situ polymerization blue-phase black antibacterial polyester melt obtained through the in-situ final polymerization reaction is 0.55 dL / g - 0.72 dL / g.

[0056] Example 1

[0057] (1) Copper basic sulfate 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 copper isophthalic acid-5-sulfonate, where the addition amount of copper basic sulfate is 52.4% of the weight of isophthalic acid-5-sulfonic acid.

[0058] (2) The copper isophthalic acid-5-sulfonate prepared in step (1) is configured into a slurry with terephthalic acid and ethylene glycol according to a certain molar ratio. Among them, the molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of copper isophthalic acid-5-sulfonate is 0.7% of the real-time output quality of the in-situ polymerization blue-phase black antibacterial polyester, and the addition amount of ethylene glycol is 36.5% of the real-time output quality of the in-situ polymerization blue-phase black antibacterial polyester.

[0059] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; the esterification rate of the copper-containing polyester oligomer is 92%, the reaction temperature of the esterification reactor is 260 °C, and the reaction pressure is 170 kPa.

[0060] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) 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 blue-phase black antibacterial polyester oligomer; the carbon black addition amount is 1% of the mass of the in-situ polymerized blue-phase 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%.

[0061] (5) Continuously convey the blue-phase 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 blue-phase black antibacterial polyester prepolymer; the in-situ pre-polymerization reaction temperature is 280 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester prepolymer is 0.25 dL / g

[0062] (6) Continuously convey the in-situ polymerized blue-phase 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 blue-phase black antibacterial polyester melt; the in-situ final polymerization reaction temperature is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester melt is 0.67 dL / g

[0063] (7) Filter, cool, solidify and pelletize the in-situ polymerized blue-phase black antibacterial polyester melt prepared in step (6) to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0064] Example 2

[0065] (1) Add basic copper sulfate to an aqueous solution with a mass percentage of isophthalic acid-5-sulfonic acid of 20%, carry out an acid-base neutralization reaction at 90 °C, and then carry out recrystallization, filtration and drying to obtain copper isophthalate-5-sulfonate, where the addition amount of basic copper sulfate is 52.4% of the weight of isophthalic acid-5-sulfonic acid

[0066] (2) Prepare a slurry by mixing the copper isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.05. The addition amount of copper isophthalate-5-sulfonate is 0.9% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 33.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time.

[0067] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; the esterification rate of the copper-containing polyester oligomer is 97%. The esterification reaction system consists of two esterification reactors in series. The reaction temperature of the first esterification reactor is 265 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification reactor is 270 °C and the reaction pressure is 100 kPa.

[0068] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) 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 blue-phase black antibacterial polyester oligomer; the carbon black addition amount is 2% of the mass of the in-situ polymerized blue-phase 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%.

[0069] (5) Continuously convey the blue-phase 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 blue-phase black antibacterial polyester prepolymer; the in-situ pre-polymerization reaction temperature is 275 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the obtained in-situ polymerized blue-phase black antibacterial polyester prepolymer is 0.22 dL / g.

[0070] (6) Continuously convey the in-situ polymerized blue-phase 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 blue-phase black antibacterial polyester melt; the in-situ final polymerization reaction temperature is 280 °C and the reaction pressure is 250 Pa. The intrinsic viscosity of the obtained in-situ polymerized blue-phase black antibacterial polyester melt is 0.65 dL / g.

[0071] (7) Filter the in-situ polymerized blue-phase black antibacterial polyester melt prepared in step (6), then cool, solidify and pelletize it to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0072] Example 3

[0073] (1) Add copper hydroxide to an aqueous solution with a mass percentage of isophthalic acid-5-sulfonic acid of 10%. After carrying out an acid-base neutralization reaction at 50 °C, recrystallize, filter and dry to obtain copper isophthalic acid-5-sulfonate. The addition amount of copper hydroxide is 19.8% of the weight of isophthalic acid-5-sulfonic acid.

[0074] (2) Prepare a slurry by mixing the copper isophthalic acid-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 2.0. The addition amount of copper isophthalic acid-5-sulfonate is 0.4% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 64.1% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time.

[0075] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; the esterification rate of the copper-containing polyester oligomer is 90%, the reaction temperature of the esterification reactor is 250 °C, and the reaction pressure is 210 kPa.

[0076] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) 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 blue-phase black antibacterial polyester oligomer; the carbon black addition amount is 0.5% of the mass of the in-situ polymerized blue-phase 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%.

[0077] (5) Continuously convey the blue-phase 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 blue-phase black antibacterial polyester prepolymer; the in-situ pre-polymerization reaction temperature is 290 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester prepolymer is 0.30 dL / g

[0078] (6) Continuously convey the in-situ polymerized blue-phase 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 blue-phase black antibacterial polyester melt; the in-situ final polymerization reaction temperature is 290 °C, the reaction pressure is 100 Pa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester melt is 0.72 dL / g

[0079] (7) Filter the in-situ polymerized blue-phase black antibacterial polyester melt prepared in step (6), then cool, solidify and pelletize it to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0080] Example 4

[0081] (1) Add basic copper carbonate to an aqueous solution with a mass percentage of isophthalic acid-5-sulfonic acid of 30%, carry out an acid-base neutralization reaction at 90 °C, and then carry out recrystallization, filtration and drying to obtain copper isophthalate-5-sulfonate, where the addition amount of basic copper carbonate is 22.5% of the weight of isophthalic acid-5-sulfonic acid

[0082] (2) Prepare a slurry by mixing the copper isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of copper isophthalate-5-sulfonate is 1.3% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 35.6% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time.

[0083] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; the esterification rate of the copper-containing polyester oligomer is 92%, the reaction temperature of the esterification reactor is 260 °C, and the reaction pressure is 170 kPa.

[0084] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) 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 blue-phase black antibacterial polyester oligomer; the carbon black addition amount is 3% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, the primary particle size of the carbon black is 28 nm, and the mass percentage of carbon black in the ethylene glycol-based slurry of carbon black is 15%.

[0085] (5) Continuously convey the blue-phase black antibacterial polyester oligomer prepared in step (4) into a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester prepolymer; the in-situ pre-polymerization reaction temperature is 270 °C, the reaction pressure is 4 kPa, and the intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester prepolymer prepared is 0.15 dL / g.

[0086] (6) Continuously convey the in-situ polymerized blue-phase black antibacterial polyester prepolymer prepared in step (5) into a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester melt; the in-situ final polymerization reaction temperature is 275 °C, the reaction pressure is 400 Pa, and the intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester melt prepared is 0.55 dL / g.

[0087] (7) Filter the in-situ polymerized blue-phase black antibacterial polyester melt prepared in step (6), then cool, solidify and pelletize it to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0088] Example 5

[0089] (1) Add basic copper carbonate to an aqueous solution with a mass percentage of isophthalic acid-5-sulfonic acid of 30%, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain copper isophthalate-5-sulfonate, where the addition amount of basic copper carbonate is 22.5% of the weight of isophthalic acid-5-sulfonic acid.

[0090] (2) Prepare a slurry by mixing copper isophthalate-5-sulfonate prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of copper isophthalate-5-sulfonate is 1.1% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 36.2% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time.

[0091] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; the esterification rate of the copper-containing polyester oligomer is 92%, the reaction temperature of the esterification reactor is 260 °C, and the reaction pressure is 170 kPa.

[0092] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) 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 blue-phase black antibacterial polyester oligomer; the carbon black addition amount is 1.5% of the mass of the in-situ polymerized blue-phase 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%.

[0093] (5) Continuously convey the blue-phase 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 blue-phase black antibacterial polyester prepolymer; the in-situ pre-polymerization reaction temperature is 280 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester prepolymer is 0.28 dL / g

[0094] (6) Continuously convey the in-situ polymerized blue-phase 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 blue-phase black antibacterial polyester melt; the in-situ final polymerization reaction temperature is 285 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared in-situ polymerized blue-phase black antibacterial polyester melt is 0.69 dL / g

[0095] (7) Filter the in-situ polymerized blue-phase black antibacterial polyester melt prepared in step (6), then cool, solidify and pelletize it to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

[0096] Comparative Example 1

[0097] (1) Prepare a slurry from terephthalic acid and ethylene glycol according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry is 1.15.

[0098] (2) Continuously convey the slurry prepared in step (1) into an esterification reactor for esterification reaction to obtain a copper-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.

[0099] (3) Continuously convey 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 with carbon black 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%.

[0100] (4) Continuously convey the black polyester oligomer prepared in step (3) to a prepolycondensation system for in-situ prepolymerization reaction to obtain an in-situ polymerized black polyester prepolymer; wherein the in-situ prepolymerization 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.

[0101] (5) Continuously convey 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; wherein the in-situ final polymerization 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.

[0102] (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.

[0103] Experimental Example 1

[0104] (1) Dry the in-situ polymerized blue-phase black antibacterial 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.

[0105] (2) Perform melt spinning on 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.

[0106] (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.

[0107] (4) Use the YG108A multi-station yarn color card machine of Changzhou No. 1 Textile Equipment Co., Ltd. to make a color card from the filaments with a specification of 75 D / 36 F obtained in step (3). The width of the color card is 35 mm, the winding speed is 450 r / min, the winding width is 40 mm, the winding density is 0.12 mm / r, and the number of winding layers is 4 layers. Then use the Data Color 400 desktop color difference meter of Datacolor Company of the United States to test the color of the color card to obtain the b value of the yellow-blue index of the filaments with a specification of 75 D / 36 F.

[0108] (5) Weave the filaments with a specification of 75D / 36F prepared in step (3) into a garter belt, then wash it 50 times under test condition A1M in GB / T 12490-1990 of the national standard. Then, test the antibacterial rates of the garter belt against Staphylococcus aureus, Escherichia coli, and Candida albicans after 50 washes according to GB / T 20944.3-2007 of the national standard, and test the antibacterial rates of the garter belt against Klebsiella pneumoniae and Trichophyton rubrum after 50 washes according to GB / T 20944.2-2007 of the national standard. The test results are shown in Table 1.

[0109] Table 1 Test results of the yellow-blue index b value and antibacterial properties of the filaments with a specification of 75D / 36F spun from the in-situ polymerization blue-phase black antibacterial polyester chips prepared in Examples 1-5 and the in-situ polymerization black polyester chips prepared in Comparative Example 1

[0110]

[0111] As can be seen from Table 1, the yellow-blue index b values of the filaments with a specification of 75D / 36F spun from the in-situ polymerization blue-phase black antibacterial polyester chips prepared in Examples 1-5 are all not higher than -0.6; after 50 washes with water, the antibacterial rate against the fungus Trichophyton rubrum is not less than 80%, the antibacterial rate against Candida albicans is greater than 99%, and the antibacterial rates against the bacteria Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae are all greater than 99%; this indicates that the filaments with a specification of 75D / 36F spun from the in-situ polymerization blue-phase black antibacterial polyester chips prepared in Examples 1-5 all have excellent blue phases and excellent antifungal and antibacterial properties. The yellow-blue index b value of the filaments with a specification of 75D / 36F spun from the in-situ polymerization black polyester chips prepared in Comparative Example 1 is -0.34. After 50 washes with water, the antibacterial rate against the fungus Trichophyton rubrum is 19%, the antibacterial rate against Candida albicans is 72%, the antibacterial rate against the bacteria Staphylococcus aureus is greater than 96%, the antibacterial rate against Escherichia coli is 91%, and the antibacterial rate against Klebsiella pneumoniae is 97%, indicating that the presence of nano-carbon black can endow the in-situ polymerization black polyester fiber with antibacterial properties; however, compared with the filaments with a specification of 75D / 36F spun from the in-situ polymerization blue-phase black antibacterial polyester prepared in Example 1 with the same carbon black content, the yellow-blue index b value has increased by 0.4, and the antibacterial rates against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Candida albicans, and Trichophyton rubrum after 50 washes with water have all decreased, and the antibacterial rates against fungi such as Candida albicans and Trichophyton rubrum have decreased more significantly; this indicates that the copolymer addition of 0.7% of copper m-phthalate-5-sulfonate relative to the weight of the in-situ polymerization blue-phase black antibacterial polyester can significantly improve the blue phase and antibacterial properties of the in-situ polymerization black polyester, especially the antibacterial properties against fungi.

[0112] Although the preferred embodiments of the present invention have been described, additional changes and modifications can be made by those skilled in the art once they learn 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.

[0113] 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 blue-phase black antibacterial polyester, characterized in that, The copper ions contained in the in-situ polymerized blue-phase black antibacterial polyester are dispersed in the in-situ polymerized blue-phase black antibacterial polyester. Among them, isophthalic acid containing copper sulfonate ion groups is bonded to the main chain of the polyethylene terephthalate molecule as a comonomer, and blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds, so that the in-situ polymerized blue-phase black antibacterial polyester has antibacterial properties against bacteria and fungi.

2. The in-situ polymerization blue phase black antibacterial polyester according to claim 1, wherein, The b value of the yellowness-blue index of the filament with a specification of 75D / 36F spun from the in-situ polymerized blue-phase black antibacterial polyester is not higher than -0.

6. After being washed 50 times, the in-situ polymerized blue-phase black antibacterial polyester has an antibacterial rate against Staphylococcus aureus greater than 99%, an antibacterial rate against Escherichia coli greater than 99%, an antibacterial rate against Klebsiella pneumoniae greater than 99%, an antibacterial rate against Candida albicans greater than 99%, and an antibacterial rate against Trichophyton rubrum not less than 80%.

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

4. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to any one of claims 1-3, characterized in that, It includes the following steps: Adding an alkaline copper salt to an aqueous solution of isophthalic acid-5-sulfonic acid to carry out a neutralization reaction to obtain a neutralization reaction product. Among them, in the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of the isophthalic acid-5-sulfonic acid solute is 10% - 30%, and the addition amount of the alkaline copper salt is 19.8% - 52.4% of the mass of the isophthalic acid-5-sulfonic acid solute; The neutralization reaction product is successively subjected to crystallization, filtration, and drying to obtain copper isophthalate-5-sulfonate; Mixing the copper isophthalate-5-sulfonate with ethylene glycol and terephthalic acid to obtain a mixed slurry. Among them, the molar ratio of ethylene glycol to terephthalic acid and copper isophthalate-5-sulfonate is 1.05 - 2.0, the addition amount of copper isophthalate-5-sulfonate is 0.4% - 1.3% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time, and the addition amount of ethylene glycol is 33.0% - 64.1% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time; The mixed slurry undergoes an esterification reaction to obtain a copper-containing polyester oligomer; The copper-containing polyester oligomer is continuously transported into an in-situ polymerization polyester oligomer preparation kettle and mixed evenly with an ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer. Among them, the addition amount of carbon black is 0.5% - 3.0% of the mass of the in-situ polymerized blue-phase black antibacterial polyester produced in real time; in the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5% - 15%; The blue-phase black antibacterial polyester oligomer is successively subjected to in-situ pre-polymerization, in-situ final polymerization, filtration, cooling, solidification, and pelletizing to obtain in-situ polymerized blue-phase black antibacterial polyester chips.

5. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to claim 4, characterized in that, The in-situ pre-polymerization step of the blue-phase black antibacterial polyester oligomer is specifically to continuously transport the blue-phase black antibacterial polyester oligomer to a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester prepolymer.

6. The preparation method of the in-situ polymerized blue phase black antibacterial polyester according to claim 5, characterized in that, The in-situ final polymerization step of the in-situ polymerized blue-phase black antibacterial polyester prepolymer is specifically as follows: continuously convey the in-situ polymerized blue-phase black antibacterial polyester prepolymer to a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerized blue-phase black antibacterial polyester melt.

7. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to claim 4, characterized in that, The basic copper salt is selected from one or a mixture of several of copper hydroxide, basic copper carbonate, and basic copper sulfate.

8. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to claim 4, characterized in that, During the step of obtaining the copper-containing polyester oligomer by subjecting the mixed slurry to an esterification reaction, the esterification rate of the copper-containing polyester oligomer is 90%-97%.

9. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to claim 4, characterized in that, During the step of continuously conveying the copper-containing polyester oligomer into a reactor for preparing in-situ polymerized polyester oligomer and mixing it evenly with an ethylene glycol slurry of carbon black to obtain a blue-phase black antibacterial polyester oligomer, the addition method of the ethylene glycol slurry of carbon black in the reactor for preparing in-situ polymerized polyester oligomer is online injection.

10. The preparation method of the in-situ polymerized blue-phase black antibacterial polyester according to claim 4, wherein the temperature of the neutralization reaction is 50°C - 90°C; the temperature of the esterification reaction is 250°C - 270°C, and the reaction pressure is 100 kPa - 210 kPa; the reaction temperature of the in-situ prepolymerization reaction is 270°C - 290°C, and the reaction pressure is 2 kPa - 4 kPa. The intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester prepolymer obtained through the in-situ prepolymerization reaction is 0.15 dL / g - 0.30 dL / g; the reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C, and the reaction pressure is 100 Pa - 400 Pa. The intrinsic viscosity of the in-situ polymerized blue-phase black antibacterial polyester melt obtained through the final polycondensation reaction is 0.55 dL / g - 0.72 dL / g.

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