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

Abstract

The invention provides in-situ polymerization copper antibacterial black polyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. In the in-situ polymerization copper antibacterial black polyester, diethylene glycol isophthalate containing a sulfonate copper ion group is used as a comonomer to be bonded to a polyethylene glycol terephthalate molecular main chain, and blue copper ions with efficient antibacterial performance are loaded to a polyester molecular chain through ionic bonds; the carbon black pigment is uniformly dispersed in the in-situ polymerized copper antibacterial black polyester matrix, and blue copper ions loaded on a polyester molecular chain play a color complementing role on the in-situ polymerized black polyester. Through the preparation method of the in-situ polymerized copper antibacterial black polyester, the in-situ polymerized copper antibacterial black polyester can be prepared. The preparation method of the in-situ polymerization copper antibacterial black polyester can endow a fiber product spun by the in-situ polymerization black polyester with excellent blue phase and excellent antibacterial and antifungal properties.

Description

Technical Field

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

[0002] The processing of dope-dyed fibers into textiles can eliminate the dyeing process and has a prominent effect of reducing emissions and carbon. It is estimated that, compared with traditional post-spinning dyed polyester fibers, each ton of dope-dyed polyester fibers processed into textiles can reduce wastewater emissions by 32t and CO2 emissions by 1.2t. Benefiting from industrial upgrading and the drive of energy conservation and emission reduction policies, the output of dope-dyed fibers has increased rapidly in recent years and has become the main variety of differential polyester fibers. Among them, black fibers account for more than 80%. However, the in-situ polymerization black polyester fibers prepared by the existing technology have a hue biased towards brown and a dull color. Summary of the Invention

[0003] In view of this, the present invention provides an in-situ polymerization copper antibacterial black polyester and a preparation method thereof. The preparation method can endow the fiber products spun from the in-situ polymerization black polyester with excellent blue phase and excellent antibacterial and antifungal properties, thus being more suitable for practical use.

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

[0005] The present invention provides an in-situ polymerization copper antibacterial black polyester. In the in-situ polymerization copper antibacterial black polyester, diethylene glycol isophthalate containing a copper sulfonate ion group is bonded to the main chain of a polyethylene terephthalate molecule as a comonomer, and blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds. Carbon black pigments are uniformly dispersed in the matrix of the in-situ polymerization copper antibacterial black polyester, and the blue copper ions loaded onto the polyester molecular chain play a color compensation role for the in-situ polymerization black polyester.

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

[0007] Preferably, the primary particle size of the carbon black is 16nm - 28nm.

[0008] Preferably, the b value of the filament with a specification of 75D / 36F spun from the in-situ polymerization copper antibacterial black polyester is not higher than -0.65.

[0009] Preferably, after being washed 50 times, the in-situ polymerization copper antibacterial black polyester has a bacteriostatic rate against Staphylococcus aureus greater than 99%, a bacteriostatic rate against Escherichia coli greater than 99%, a bacteriostatic rate against Klebsiella pneumoniae greater than 99%, a bacteriostatic rate against Candida albicans greater than 99%, and a bacteriostatic rate against Trichophyton rubrum not less than 82%.

[0010] To achieve the above second object, the technical solution of the preparation method of in-situ polymerization copper antibacterial black polyester provided by the present invention is as follows:

[0011] The preparation method of in-situ polymerization copper antibacterial black polyester provided by the present invention includes the following steps:

[0012] Prepare copper dimethyl isophthalate-5-sulfonate;

[0013] Dissolve the copper dimethyl isophthalate-5-sulfonate in ethylene glycol, and through transesterification reaction, obtain an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate. Among them, in the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate, the mass percentage content of copper diethylene glycol isophthalate-5-sulfonate is 10%-30%;

[0014] Prepare a first slurry from terephthalic acid and ethylene glycol, where the molar ratio of glycol to acid between the terephthalic acid and ethylene glycol is 1.05-2.0;

[0015] Carry out an esterification reaction on the first slurry to obtain a polyester oligomer;

[0016] Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. Among them, the addition amount of the carbon black is 0.5%-3.0% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time, and in the ethylene glycol slurry of the carbon black, the mass percentage content of the carbon black is 5%-15%;

[0017] The black polyester oligomer and the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate are successively subjected to in-situ pre-polymerization, in-situ final polymerization, cooling, solidification, and pelletizing to obtain in-situ polymerization copper antibacterial black polyester chips. Among them, the addition amount of the copper diethylene glycol isophthalate-5-sulfonate is 0.6%-1.8% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time.

[0018] The preparation method of in-situ polymerization copper antibacterial black polyester provided by the present invention can also be further realized by adopting the following technical measures.

[0019] Preferably, the preparation of copper dimethyl isophthalate-5-sulfonate specifically is:

[0020] Add an alkaline copper salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid. After acid-base neutralization reaction, recrystallization, filtration, and drying, copper dimethyl isophthalate-5-sulfonate is obtained. Among them,

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

[0022] The addition amount of the basic copper salt in the dimethyl isophthalate-5-sulfonic acid aqueous solution is 17.8%-47.1% of the mass of the dimethyl isophthalate-5-sulfonic acid solute;

[0023] The reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

[0024] Preferably, the basic copper salt is selected from at least one of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0025] Preferably, in the step of dissolving copper dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate through a transesterification reaction, the temperature of the transesterification reaction is 160°C-190°C.

[0026] Preferably, in the step of subjecting the slurry to an esterification reaction to obtain a polyester oligomer, the reaction temperature of the esterification reaction is 250°C-270°C, the reaction pressure of the esterification reaction is 100 kPa-210 kPa, and the esterification rate of the polyester oligomer is 90%-97%.

[0027] Preferably, the step of mixing the polyester oligomer with the ethylene glycol slurry of carbon black to obtain a black polyester oligomer is specifically as follows:

[0028] The polyester oligomer is continuously conveyed into the in-situ polymerization polyester oligomer preparation kettle and mixed evenly with the ethylene glycol slurry of carbon black injected online to obtain the black polyester oligomer.

[0029] Preferably, the in-situ prepolymerization reaction of the black polyester oligomer and the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate is specifically as follows:

[0030] After the black polyester oligomer is mixed evenly with the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate injected online in the oligomer pipeline, it is continuously conveyed to the prepolymerization system for in-situ prepolymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer, wherein

[0031] The reaction temperature of the in-situ prepolymerization reaction is 270°C-290°C;

[0032] The reaction pressure of the in-situ prepolymerization reaction is 2 kPa-4 kPa;

[0033] The intrinsic viscosity of the in-situ polymerization copper antibacterial black polyester prepolymer is 0.15 dL / g-0.30 dL / g.

[0034] Preferably, the in-situ final polymerization reaction of the in-situ polymerization copper antibacterial black polyester prepolymer is specifically as follows:

[0035] The in-situ polymerization copper antibacterial black polyester prepolymer is continuously conveyed to a final polymerization system for in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt, wherein,

[0036] The reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C;

[0037] The reaction pressure of the in-situ final polymerization reaction is 100 Pa - 400 Pa;

[0038] The intrinsic viscosity of the in-situ polymerization copper antibacterial black polyester melt is 0.55 dL / g - 0.72 dL / g.

[0039] Preferably, in the step of mixing the polyester oligomer with the ethylene glycol slurry of carbon black to obtain a black polyester oligomer, the ethylene glycol slurry of carbon black is mixed with the polyester oligomer in an on-line injection manner.

[0040] The preparation method of the in-situ polymerization copper antibacterial black polyester provided by the present invention is to use diethylene glycol isophthalate containing a sulfonic acid copper ion group as a comonomer to be bonded to the main chain of a polyethylene terephthalate molecule, and load blue copper ions with high antibacterial performance 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 in the in-situ polymerization copper antibacterial black polyester product; then, carbon black pigment is uniformly dispersed in the polyester matrix through in-situ polymerization, and the blue copper ions loaded on the polyester molecular chain can play a complementary color role for the in-situ polymerization black polyester, thereby endowing the fiber products spun from the in-situ polymerization copper antibacterial black polyester with an excellent blue phase. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] 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:

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

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

[0044] In view of this, the present invention provides an in-situ polymerization copper antibacterial black polyester and a preparation method thereof, which can endow the fiber products spun from the in-situ polymerization black polyester with excellent blue phase and antibacterial and antifungal properties, thus being more suitable for practical use.

[0045] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following combines the drawings and preferred embodiments to detail the specific implementation manners, structures, features and effects of an in-situ polymerization copper antibacterial black polyester and a preparation method thereof proposed according to the present invention. In the following description, different "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. In addition, the specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0046] The term "and / or" in this article is merely a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B is specifically understood as: it can include both A and B at the same time, A can exist alone, or B can exist alone, and any of the above three situations can be satisfied.

[0047] In-situ polymerized copper antibacterial black polyester

[0048] The present invention provides an in-situ polymerization copper antibacterial black polyester. In the in-situ polymerization copper antibacterial black polyester, diethylene glycol isophthalate containing copper sulfonate ion groups is bonded to the main chain of polyethylene terephthalate molecules as a comonomer, and blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds. Carbon black pigments are uniformly dispersed in the in-situ polymerization copper antibacterial black polyester matrix, and the blue copper ions loaded on the polyester molecular chain play a color compensation role for the in-situ polymerization black polyester.

[0049] Among them, the primary particle size of the carbon black is 16nm - 28nm.

[0050] Among them, the b value of the filament with a specification of 75D / 36F spun from the in-situ polymerization copper antibacterial black polyester is not higher than -0.65.

[0051] Among them, after being washed 50 times, the antibacterial rate of the in-situ polymerization copper antibacterial black polyester 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 82%.

[0052] Preparation method of in-situ polymerized copper antibacterial black polyester

[0053] The preparation method of the in-situ polymerization copper antibacterial black polyester provided by the present invention includes the following steps:

[0054] Step S1: Prepare copper dimethyl isophthalate-5-sulfonate;

[0055] Step S2: Dissolve copper dimethyl isophthalate-5-sulfonate in ethylene glycol, and through transesterification reaction, obtain an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate. Among them, in the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate, the mass percentage content of copper diethylene glycol isophthalate-5-sulfonate is 10%-30%;

[0056] Step S3: Prepare a first slurry with terephthalic acid and ethylene glycol. Among them, the molar ratio of glycol to acid between terephthalic acid and ethylene glycol is 1.05-2.0;

[0057] Step S4: Carry out an esterification reaction on the first slurry to obtain a polyester oligomer;

[0058] Step S5: Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. Among them, the addition amount of carbon black is 0.5%-3.0% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time, and in the ethylene glycol slurry of carbon black, the mass percentage content of carbon black is 5%-15%;

[0059] Step S6: The black polyester oligomer and the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate are successively subjected to in-situ prepolymerization, final polymerization, cooling, solidification, and pelletizing to obtain in-situ polymerization copper antibacterial black polyester chips. Among them, the addition amount of copper diethylene glycol isophthalate-5-sulfonate is 0.6%-1.8% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time.

[0060] Among them, the specific preparation of copper dimethyl isophthalate-5-sulfonate is as follows:

[0061] Add an alkaline copper salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid. After an acid-base neutralization reaction, recrystallization, filtration, and drying, copper dimethyl isophthalate-5-sulfonate is obtained. Among them,

[0062] In the aqueous solution of dimethyl isophthalate-5-sulfonic acid, the mass percentage content of dimethyl isophthalate-5-sulfonic acid is 10%-30%;

[0063] The addition amount of the alkaline copper salt in the aqueous solution of dimethyl isophthalate-5-sulfonic acid is 17.8%-47.1% of the mass of the dimethyl isophthalate-5-sulfonic acid solute;

[0064] The reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

[0065] Among them, the alkaline copper salt is selected from at least one of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0066] Among them, in the step of dissolving copper dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate through transesterification reaction, the temperature of the transesterification reaction is 160°C - 190°C.

[0067] Among them, in the step of subjecting the slurry to an esterification reaction to obtain a polyester oligomer, the reaction temperature of the esterification reaction is 250°C - 270°C, the reaction pressure of the esterification reaction is 100 kPa - 210 kPa, and the esterification rate of the polyester oligomer is 90% - 97%.

[0068] Among them, the step of mixing the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer is specifically as follows.

[0069] The polyester oligomer is continuously conveyed into the in-situ polymerization polyester oligomer preparation kettle and mixed evenly with the ethylene glycol slurry of carbon black injected online to obtain a black polyester oligomer.

[0070] Among them, the in-situ pre-polymerization reaction of the black polyester oligomer and the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate is specifically as follows.

[0071] After the black polyester oligomer is mixed evenly with the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate injected online in the oligomer pipeline, it is continuously conveyed to the pre-polymerization system for in-situ pre-polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer. Among them,

[0072] The reaction temperature of the in-situ pre-polymerization reaction is 270°C - 290°C;

[0073] The reaction pressure of the in-situ pre-polymerization reaction is 2 kPa - 4 kPa;

[0074] The intrinsic viscosity of the in-situ polymerization copper antibacterial black polyester prepolymer is 0.15 dL / g - 0.30 dL / g.

[0075] Among them, the in-situ final polymerization reaction of the in-situ polymerization copper antibacterial black polyester prepolymer is specifically as follows.

[0076] The in-situ polymerization copper antibacterial black polyester prepolymer is continuously conveyed to the final polymerization system for in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt. Among them,

[0077] The reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C;

[0078] The reaction pressure of the in-situ final polymerization reaction is 100 Pa - 400 Pa;

[0079] The intrinsic viscosity of the in-situ polymerization copper antibacterial black polyester melt is 0.55 dL / g - 0.72 dL / g.

[0080] In the step of mixing a polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer, the ethylene glycol slurry of carbon black is mixed with the polyester oligomer in an on-line injection manner.

[0081] Example 1

[0082] (1) Cupric sulfate basic is added to an aqueous solution with a mass percentage content of dimethyl isophthalate-5-sulfonic acid of 20%. After an acid-base neutralization reaction at 80 °C, recrystallization, filtration, and drying are carried out to obtain copper dimethyl isophthalate-5-sulfonate, wherein the addition amount of cupric sulfate basic is 47.1% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0083] (2) The copper dimethyl isophthalate-5-sulfonate prepared in step (1) is dissolved in ethylene glycol, and an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate is prepared through a transesterification reaction. The transesterification reaction temperature is 180 °C, and the mass percentage content of copper diethylene glycol isophthalate-5-sulfonate in the prepared ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate is 15%.

[0084] (3) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, wherein the molar ratio of alcohol to acid in the slurry is 1.15.

[0085] (4) The slurry configured in step (3) is continuously fed into an esterification system for an esterification reaction to obtain a polyester oligomer. The esterification rate of the polyester oligomer is 92%, the reaction temperature of the esterification reaction kettle is 260 °C, and the reaction pressure is 170 kPa.

[0086] (5) The polyester oligomer prepared in step (4) is continuously fed into an in-situ polymerization polyester oligomer preparation kettle and mixed evenly with an ethylene glycol slurry of on-line injected carbon black to obtain a black polyester oligomer. The carbon black addition amount is 1% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The primary particle size of the carbon black is 20 nm, and the mass percentage content of carbon black in the ethylene glycol slurry of carbon black is 10%.

[0087] (6) The black polyester oligomer prepared in step (5) is mixed evenly with the ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate prepared in step (2) by on-line injection in the oligomer pipeline and then continuously fed into a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer. The addition amount of copper diethylene glycol isophthalate-5-sulfonate is 0.8% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. 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 polymerization copper antibacterial black polyester prepolymer is 0.25 dL / g.

[0088] (7) Continuously convey the in-situ polymerization copper antibacterial black polyester prepolymer prepared in step (6) to the final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt; wherein the temperature of the in-situ final polymerization reaction is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the prepared in-situ polymerization copper antibacterial black polyester melt is 0.67 dL / g

[0089] (8) Filter, cool, solidify and pelletize the in-situ polymerization copper antibacterial black polyester melt prepared in step (7) to obtain in-situ polymerization copper antibacterial black polyester chips.

[0090] Example 2

[0091] (1) Add basic copper carbonate to an aqueous solution with a mass percentage of dimethyl isophthalate-5-sulfonic acid of 10%, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration and drying to obtain copper dimethyl isophthalate-5-sulfonate, wherein the addition amount of basic copper carbonate is 20.2% of the weight of dimethyl isophthalate-5-sulfonic acid

[0092] (2) Dissolve the copper dimethyl isophthalate-5-sulfonate prepared in step (1) in ethylene glycol, and prepare an ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate through a transesterification reaction, wherein the temperature of the transesterification reaction is 180 °C, and the mass percentage of copper diethylene glycol isophthalate-5-sulfonate in the prepared ethylene glycol solution of copper diethylene glycol isophthalate-5-sulfonate is 15%.

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

[0094] (4) Continuously convey the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer; wherein the esterification rate of the polyester oligomer is 92%, and the reaction temperature of the esterification reaction kettle is 260 °C and the reaction pressure is 170 kPa.

[0095] (5) Continuously convey the polyester oligomer prepared in step (4) into an in-situ polymerization polyester oligomer preparation kettle, and mix it evenly with an ethylene glycol slurry into which carbon black is injected online to obtain a black polyester oligomer; the addition amount of carbon black is 1.5% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time, the primary particle size of the carbon black is 21 nm, and the mass percentage of carbon black in the ethylene glycol slurry of carbon black is 10%.

[0096] (6) The black polyester oligomer prepared in step (5) is mixed evenly with the ethylene glycol solution of copper 5-sulfoisophthalate diglycolate prepared in step (2) by on-line injection in the oligomer pipeline and then continuously conveyed to the prepolymerization system for in-situ prepolymerization reaction to obtain an in-situ polymerized copper antibacterial black polyester prepolymer; the addition amount of copper 5-sulfoisophthalate diglycolate is 1.0% of the mass of the in-situ polymerized copper antibacterial black polyester produced in real time, the temperature of the in-situ prepolymerization reaction is 280 °C, the reaction pressure is 2.0 kPa, and the intrinsic viscosity of the prepared in-situ polymerized copper antibacterial black polyester prepolymer is 0.28 dL / g.

[0097] (7) The in-situ polymerized copper antibacterial black polyester prepolymer prepared in step (6) is continuously conveyed to the final polymerization system for in-situ final polymerization reaction to obtain an in-situ polymerized copper antibacterial black polyester melt; the temperature of the in-situ final polymerization reaction is 285 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared in-situ polymerized copper antibacterial black polyester melt is 0.69 dL / g.

[0098] (8) The in-situ polymerized copper antibacterial black polyester melt prepared in step (7) is filtered, cooled, solidified and pelletized to obtain in-situ polymerized copper antibacterial black polyester chips.

[0099] Example 3

[0100] (1) Basic copper sulfate is added to an aqueous solution with a mass percentage of dimethyl 5-sulfoisophthalate of 20%, and after an acid-base neutralization reaction at 80 °C, recrystallization, filtration and drying are carried out to obtain copper 5-sulfoisophthalate dimethyl ester, and the addition amount of basic copper sulfate is 47.1% of the weight of dimethyl 5-sulfoisophthalate.

[0101] (2) The copper 5-sulfoisophthalate dimethyl ester prepared in step (1) is dissolved in ethylene glycol, and through a transesterification reaction, an ethylene glycol solution of copper 5-sulfoisophthalate diglycolate is prepared. The temperature of the transesterification reaction is 180 °C, and the mass percentage of copper 5-sulfoisophthalate diglycolate in the prepared ethylene glycol solution of copper 5-sulfoisophthalate diglycolate is 20%.

[0102] (3) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, and the molar ratio of alcohol to acid in the slurry is 1.05.

[0103] (4) Continuously convey the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer; the esterification rate of the polyester oligomer is 97%. The esterification reaction system consists of two esterification kettles connected in series. The reaction temperature of the first esterification kettle is 265 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification kettle is 270 °C and the reaction pressure is 100 kPa.

[0104] (5) Continuously convey the polyester oligomer prepared in step (4) into a preparation kettle 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 2% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The primary particle size of the carbon black is 20 nm, and the mass percentage of carbon black in the ethylene glycol slurry of carbon black is 10%.

[0105] (6) Continuously convey the black polyester oligomer prepared in step (5) in an oligomer pipeline, mix it evenly with an ethylene glycol solution of copper 5-sulfoisophthalate diglycolate prepared in step (2) injected online, and then continuously convey it to a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer; the addition amount of copper 5-sulfoisophthalate diglycolate is 1.2% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The in-situ pre-polymerization reaction temperature is 275 °C and the reaction pressure is 3 kPa. The intrinsic viscosity of the prepared in-situ polymerization copper antibacterial black polyester prepolymer is 0.22 dL / g.

[0106] (7) Continuously convey the in-situ polymerization copper antibacterial black polyester prepolymer prepared in step (6) to a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt; the in-situ final polymerization reaction temperature is 280 °C and the reaction pressure is 250 Pa. The intrinsic viscosity of the prepared in-situ polymerization copper antibacterial black polyester melt is 0.65 dL / g.

[0107] (8) Filter, cool, solidify, and pelletize the in-situ polymerization copper antibacterial black polyester melt prepared in step (7) to obtain in-situ polymerization copper antibacterial black polyester chips.

[0108] Example 4

[0109] (1) Add basic copper carbonate to an aqueous solution with a mass percentage of dimethyl 5-sulfoisophthalate of 30%, carry out an acid-base neutralization reaction at 90 °C, and then perform recrystallization, filtration, and drying to obtain copper 5-sulfoisophthalate dimethyl ester. The addition amount of basic copper carbonate is 22.5% of the weight of dimethyl 5-sulfoisophthalate.

[0110] (2) Dissolve the copper 5-sulfoisophthalate dimethyl ester prepared in step (1) in ethylene glycol, and obtain an ethylene glycol solution of copper 5-sulfoisophthalate bis(2-hydroxyethyl) ester through a transesterification reaction. The transesterification reaction temperature is 190 °C, and the mass percentage of copper 5-sulfoisophthalate bis(2-hydroxyethyl) ester in the obtained ethylene glycol solution of copper 5-sulfoisophthalate bis(2-hydroxyethyl) ester is 30%.

[0111] (3) Prepare a slurry from terephthalic acid and ethylene glycol according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry is 1.15;

[0112] (4) Continuously convey the slurry prepared in step (3) into an esterification system for an esterification reaction to obtain a polyester oligomer; the esterification rate of the oligomer is 92%, and the reaction temperature in the esterification reaction kettle is 260 °C and the reaction pressure is 170 kPa.

[0113] (5) Continuously convey the polyester oligomer prepared in step (4) into a reactor for in-situ polymerization of polyester oligomers, and mix it evenly with an ethylene glycol slurry in which carbon black is injected online to obtain a black polyester oligomer; the carbon black addition amount is 3% of the mass of the in-situ polymerization copper antibacterial black 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 slurry of carbon black is 15%.

[0114] (6) Mix the black polyester oligomer prepared in step (5) evenly with the ethylene glycol solution of copper 5-sulfoisophthalate bis(2-hydroxyethyl) ester prepared in step (2) injected online in the oligomer pipeline, and then continuously convey it to a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer; the addition amount of copper 5-sulfoisophthalate bis(2-hydroxyethyl) ester is 1.8% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The in-situ pre-polymerization reaction temperature is 270 °C and the reaction pressure is 4 kPa. The intrinsic viscosity of the obtained in-situ polymerization copper antibacterial black polyester prepolymer is 0.15 dL / g.

[0115] (7) Continuously convey the in-situ polymerization copper antibacterial black polyester prepolymer prepared in step (6) to a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt; the in-situ final polymerization reaction temperature is 275 °C and the reaction pressure is 400 Pa. The intrinsic viscosity of the obtained in-situ polymerization copper antibacterial black polyester melt is 0.55 dL / g.

[0116] (8) Filter the in-situ polymerization copper antibacterial black polyester melt prepared in step (7), then cool, solidify and pelletize it to obtain in-situ polymerization copper antibacterial black polyester chips.

[0117] Example 5

[0118] (1) Cupric hydroxide was added to an aqueous solution with a mass percentage of 10% of dimethyl isophthalate-5-sulfonic acid. After an acid-base neutralization reaction at 50 °C, recrystallization, filtration, and drying were carried out to obtain cupric dimethyl isophthalate-5-sulfonate, where the addition amount of cupric hydroxide was 17.8% of the weight of dimethyl isophthalate-5-sulfonic acid.

[0119] (2) The cupric dimethyl isophthalate-5-sulfonate prepared in step (1) was dissolved in ethylene glycol, and an ethylene glycol solution of cupric diethylene glycol isophthalate-5-sulfonate was prepared through a transesterification reaction. The transesterification reaction temperature was 160 °C, and the mass percentage of cupric diethylene glycol isophthalate-5-sulfonate in the prepared ethylene glycol solution of cupric diethylene glycol isophthalate-5-sulfonate was 10%.

[0120] (3) Terephthalic acid and ethylene glycol were configured into a slurry according to a certain molar ratio, where the molar ratio of alcohol to acid in the slurry was 2.0.

[0121] (4) The slurry configured in step (3) was continuously fed into an esterification system for an esterification reaction to obtain a polyester oligomer. The esterification rate of the oligomer was 90%, the reaction temperature of the esterification reaction kettle was 250 °C, and the reaction pressure was 210 kPa.

[0122] (5) The polyester oligomer prepared in step (4) was continuously fed into an in-situ polymerization polyester oligomer preparation kettle and mixed evenly with an ethylene glycol slurry in which carbon black was injected online to obtain a black polyester oligomer. The addition amount of carbon black was 0.5% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The primary particle size of the carbon black was 16 nm, and the mass percentage of carbon black in the ethylene glycol slurry of carbon black was 5%.

[0123] (6) The black polyester oligomer prepared in step (5) was mixed evenly with the ethylene glycol solution of cupric diethylene glycol isophthalate-5-sulfonate prepared in step (2) injected online in the oligomer pipeline and then continuously fed into a pre-polycondensation system for an in-situ pre-polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester prepolymer. The addition amount of cupric diethylene glycol isophthalate-5-sulfonate was 0.6% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time. The in-situ pre-polymerization reaction temperature was 290 °C, the reaction pressure was 2.0 kPa, and the intrinsic viscosity of the prepared in-situ polymerization copper antibacterial black polyester prepolymer was 0.30 dL / g.

[0124] (7) The in-situ polymerization copper antibacterial black polyester prepolymer prepared in step (6) was continuously fed into a final polycondensation system for an in-situ final polymerization reaction to obtain an in-situ polymerization copper antibacterial black polyester melt. The in-situ final polymerization reaction temperature was 290 °C, the reaction pressure was 100 Pa, and the intrinsic viscosity of the prepared in-situ polymerization copper antibacterial black polyester melt was 0.72 dL / g.

[0125] (8) The in-situ polymerization copper antibacterial black polyester melt prepared in step (7) is filtered, cooled, solidified and pelletized to obtain in-situ polymerization copper antibacterial black polyester chips.

[0126] Comparative Example 1

[0127] (1) Terephthalic acid and ethylene glycol are configured into a slurry according to a certain molar ratio, and the molar ratio of alcohol to acid in the slurry is 1.15.

[0128] (2) The slurry configured in step (1) is continuously fed 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.

[0129] (3) The polyester oligomer prepared in step (2) is continuously fed into a reactor for preparing in-situ polymerization polyester oligomers and mixed 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 polymerization 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 slurry of carbon black is 10%.

[0130] (4) The black polyester oligomer prepared in step (3) is continuously fed into a pre-polycondensation system for in-situ pre-polymerization reaction to obtain an in-situ polymerization black polyester prepolymer; the in-situ pre-polymerization reaction temperature is 280 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the in-situ polymerization black polyester prepolymer prepared is 0.25 dL / g.

[0131] (5) The in-situ polymerization black polyester prepolymer prepared in step (4) is continuously fed into a final polycondensation system for in-situ final polymerization reaction to obtain an in-situ polymerization black polyester melt; the in-situ final polymerization reaction temperature is 285 °C, the reaction pressure is 250 Pa, and the intrinsic viscosity of the in-situ polymerization black polyester melt prepared is 0.67 dL / g.

[0132] (6) The in-situ polymerization black polyester melt prepared in step (5) is filtered, cooled, solidified and pelletized to obtain in-situ polymerization black polyester chips.

[0133] Experimental Example 1

[0134] (1) The in-situ polymerization copper antibacterial black polyester chips prepared in Examples 1-5 and the in-situ polymerization black polyester chips prepared in Comparative Example 1 are dried in a rotary drum with a vacuum degree less than 100 Pa and a drying temperature of 150 °C until the water content is less than 30 ppm.

[0135] (2) The dried slices prepared in step (1) are melt-spun 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.

[0136] (3) The pre-oriented yarn prepared in step (2) is drawn and processed on a flat drawing machine to prepare a drawn yarn with a specification of 75 D / 36 F, where the draw ratio is 1.6 times, the drawing temperature is 80 °C, and the setting temperature is 130 °C.

[0137] (4) The filaments with a specification of 75 D / 36 F prepared in step (3) are made into a color card by using the YG108A multi-station yarn color card machine of Changzhou No. 1 Textile Equipment Co., Ltd. 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, the color of the color card is tested by using the Data Color 400 desktop color difference meter of Datacolor Company of the United States to obtain the b value of the yellow-blue index of the filaments with a specification of 75 D / 36 F.

[0138] (5) The filaments with a specification of 75 D / 36 F prepared in step (3) are woven into a garter, and then washed 50 times under the test condition A1M in GB / T 12490-1990. Then, the antibacterial rates of the garter against Staphylococcus aureus, Escherichia coli, and Candida albicans after washing 50 times are tested according to GB / T 20944.3-2007, and the antibacterial rates of the garter against Klebsiella pneumoniae and Trichophyton rubrum after washing 50 times are tested according to GB / T 20944.2-2007. The test results are shown in Table 1.

[0139] Table 1 Test results of the b value of the yellow-blue index and antibacterial properties of the filaments with a specification of 75 D / 36 F spun from the in-situ polymerization copper antibacterial black polyester slices prepared in Examples 1 to 5 and the in-situ polymerization black polyester slices prepared in Comparative Example 1

[0140]

[0141] As can be seen from Table 1, through the synergistic effect of component control and process parameter control, in-situ polymerization copper antibacterial black polyester chips were prepared in Examples 1 to 5. The b value of the yellowness-blue index of the filaments with a specification of 75D / 36F spun was not higher than -0.65; after 50 washes, the antibacterial rates against the fungus Trichophyton rubrum were not less than 82%, the antibacterial rate against Candida albicans was greater than 99%, and the antibacterial rates against the bacteria Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae were all greater than 99%; this indicates that the filaments with a specification of 75D / 36F spun from the in-situ polymerization copper antibacterial black polyester chips prepared in Examples 1 to 5 all have excellent blue phases and excellent antifungal and antibacterial properties. The b value of the yellowness-blue index of the filaments with a specification of 75D / 36F spun from the in-situ polymerization black polyester chips prepared in Comparative Example 1 was -0.34. After 50 washes, the antibacterial rate against the fungus Trichophyton rubrum was 19%, the antibacterial rate against Candida albicans was 72%, the antibacterial rate against the bacteria Staphylococcus aureus was 96%, the antibacterial rate against Escherichia coli was 91%, and the antibacterial rate against Klebsiella pneumoniae was 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 copper antibacterial black polyester prepared in Example 1 with the same carbon black content, the b value of the yellowness-blue index increased by 0.35, and the antibacterial rates against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Candida albicans, and Trichophyton rubrum after 50 washes decreased, among which the antibacterial rates against fungi such as Candida albicans and Trichophyton rubrum decreased more significantly; this indicates that the copolymer addition of copper 5-sulfoisophthalate diglycolate equivalent to 0.8% of the weight of the in-situ polymerization copper antibacterial black polyester can significantly improve the blue phase and antibacterial properties of the in-situ polymerization black polyester, especially the antibacterial properties against fungi.

[0142] 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 concepts. 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.

[0143] 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 changes and modifications.

Claims

1. An in-situ polymerized copper antibacterial black polyester, characterized in that, In the in-situ polymerization copper antibacterial black polyester, diethylene glycol isophthalate containing copper sulfonate ion groups is bonded to the main chain of polyethylene terephthalate molecules as a comonomer, and blue copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds. Carbon black pigments are uniformly dispersed in the matrix of the in-situ polymerization copper antibacterial black polyester, and the blue copper ions loaded on the polyester molecular chain play a color compensation role for the in-situ polymerization black polyester.

2. The in-situ polymerization copper antibacterial black polyester according to claim 1, wherein The primary particle size of the carbon black is 16nm - 28nm.

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

65.

4. The in-situ polymerization copper antibacterial black polyester according to claim 1, wherein, After being washed 50 times, the in-situ polymerization copper antibacterial black polyester has a bacteriostatic rate against Staphylococcus aureus greater than 99%, a bacteriostatic rate against Escherichia coli greater than 99%, a bacteriostatic rate against Klebsiella pneumoniae greater than 99%, a bacteriostatic rate against Candida albicans greater than 99%, and a bacteriostatic rate against Trichophyton rubrum not less than 82%.

5. The preparation method of the in-situ polymerized copper antibacterial black polyester according to any one of claims 1-4, characterized in that, It includes the following steps: Prepare dimethyl isophthalate-5-sulfonate copper. Dissolve the dimethyl isophthalate-5-sulfonate copper in ethylene glycol, and through transesterification reaction, obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate copper. Among them, in the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate copper, the mass percentage content of diethylene glycol isophthalate-5-sulfonate copper is 10% - 30%. Prepare a first slurry with terephthalic acid and ethylene glycol. Among them, the molar ratio of glycol to acid between the terephthalic acid and ethylene glycol is 1.05 - 2.

0. The first slurry undergoes an esterification reaction to obtain a polyester oligomer. Mix the polyester oligomer with an ethylene glycol slurry of carbon black to obtain a black polyester oligomer. Among them, the addition amount of the carbon black is 0.5% - 3.0% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time, and in the ethylene glycol slurry of the carbon black, the mass percentage content of the carbon black is 5% - 15%. The black polyester oligomer and the ethylene glycol solution of diethylene glycol isophthalate-5-sulfonate copper are successively subjected to in-situ pre-polymerization, in-situ final polymerization, cooling, curing, and pelletizing to obtain in-situ polymerization copper antibacterial black polyester chips. Among them, the addition amount of the diethylene glycol isophthalate-5-sulfonate copper is 0.6% - 1.8% of the mass of the in-situ polymerization copper antibacterial black polyester produced in real time.

6. The preparation method of the in-situ polymerized copper antibacterial black polyester according to claim 5, characterized in that, The specific preparation of the dimethyl isophthalate-5-sulfonate copper is as follows: Add an alkaline copper salt to an aqueous solution of dimethyl isophthalate-5-sulfonic acid. After an acid-base neutralization reaction, recrystallization, filtration, and drying, dimethyl isophthalate-5-sulfonate copper is obtained. Among them, In the aqueous solution of dimethyl isophthalate-5-sulfonic acid, the mass percentage content of dimethyl isophthalate-5-sulfonic acid is 10% - 30%. The addition amount of the alkaline copper salt in the aqueous solution of dimethyl isophthalate-5-sulfonic acid is 17.8% - 47.1% of the mass of the dimethyl isophthalate-5-sulfonic acid solute. The reaction temperature of the acid-base neutralization reaction is 50°C - 90°C.

7. The preparation method of the in-situ polymerized copper antibacterial black polyester according to claim 6, characterized in that, The basic copper salt is selected from at least one of copper hydroxide, basic copper carbonate, and basic copper sulfate.

8. The preparation method of the in-situ polymerized copper antibacterial black polyester according to claim 5, characterized in that, In the step of dissolving copper dimethyl isophthalate-5-sulfonate in ethylene glycol and obtaining a glycol solution of copper diethylene glycol isophthalate-5-sulfonate through a transesterification reaction, the temperature of the transesterification reaction is 160°C - 190°C.

9. The preparation method of the in-situ polymerized copper antibacterial black polyester according to claim 5, characterized in that, In the step of subjecting the slurry to an esterification reaction to obtain a polyester oligomer, the reaction temperature of the esterification reaction is 250°C - 270°C, the reaction pressure of the esterification reaction is 100 kPa - 210 kPa, and the esterification rate of the polyester oligomer is 90% - 97%.

10. The preparation method of the in-situ polymerized copper antibacterial black polyester according to claim 5, characterized in that, The step of mixing the polyester oligomer with a glycol slurry of carbon black to obtain a black polyester oligomer specifically is continuously conveying the polyester oligomer into a reactor for in-situ polymerization of polyester oligomers, and mixing it evenly with the glycol slurry of carbon black injected online to obtain the black polyester oligomer; Preferably, the in-situ pre-polymerization reaction of the black polyester oligomer and the glycol solution of copper diethylene glycol isophthalate-5-sulfonate specifically is after the black polyester oligomer is mixed evenly with the glycol solution of copper diethylene glycol isophthalate-5-sulfonate injected online in the oligomer pipeline, it is continuously conveyed to a pre-polymerization system for in-situ pre-polymerization reaction to obtain an in-situ polymerized copper antibacterial black polyester prepolymer, wherein the reaction temperature of the in-situ pre-polymerization reaction is 270°C - 290°C; the reaction pressure of the in-situ pre-polymerization reaction is 2 kPa - 4 kPa; the intrinsic viscosity of the in-situ polymerized copper antibacterial black polyester prepolymer is 0.15 dL / g - 0.30 dL / g; Preferably, the in-situ final polymerization reaction of the in-situ polymerized copper antibacterial black polyester prepolymer specifically is continuously conveying the in-situ polymerized copper antibacterial black polyester prepolymer to a final polymerization system for in-situ final polymerization reaction to obtain an in-situ polymerized copper antibacterial black polyester melt, wherein the reaction temperature of the in-situ final polymerization reaction is 275°C - 290°C; the reaction pressure of the in-situ final polymerization reaction is 100 Pa - 400 Pa; the intrinsic viscosity of the in-situ polymerized copper antibacterial black polyester melt is 0.55 dL / g - 0.72 dL / g; Preferably, in the step of mixing the polyester oligomer with a glycol slurry of carbon black to obtain a black polyester oligomer, the glycol slurry of carbon black is mixed with the polyester oligomer in an online injection manner.

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