Copper ion antibacterial copolyester and preparation method thereof

Abstract

The invention provides copper ion antibacterial copolyester and a preparation method thereof, and belongs to the technical field of high polymer material synthesis. In the copper ion antibacterial copolyester, isophthalic acid containing a sulfonate copper ion group is used as a comonomer to be bonded to a polyethylene glycol terephthalate molecular main chain, and copper ions with efficient antibacterial performance are loaded to a polyester molecular chain through ionic bonds. The preparation method comprises the following steps: preparing isophthalic acid-5-copper sulfonate; the preparation method comprises the following steps: preparing isophthalic acid-5-copper sulfonate, terephthalic acid and ethylene glycol into slurry; carrying out esterification reaction on the slurry to obtain a copper-containing polyester oligomer; the copper-containing polyester oligomer is sequentially subjected to pre-polycondensation, final polycondensation, filtration, cooling solidification and grain-sized dicing molding, and the copper ion antibacterial copolyester chip is obtained. The method can realize atomic-scale dispersion of copper ions, and endows polyester products with excellent antibacterial and antifungal properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly to a copper ion antibacterial copolyester and a preparation method thereof. Background Art

[0002] Polyester has good fiber-forming properties, mechanical properties, wear resistance, creep resistance, low water absorption, electrical insulation and other properties, and is widely used in fibers, packaging bottles, films, engineering plastics, etc. It is the second largest class of synthetic polymers after polyolefins. With the improvement of people's living standards and the enhancement of people's awareness of health and environment, the market demand for antibacterial polyester fibers, films and plastic products has increased rapidly. In the prior art, the antibacterial efficiency of polyester decreases significantly, and the fiber-forming and film-drawing processing properties of polyester deteriorate greatly. Summary of the Invention

[0003] In view of this, the present invention provides a copper ion antibacterial copolyester and a preparation method thereof, which can achieve atomic-level dispersion of copper ions, endow polyester products with excellent antibacterial and antifungal properties, and thus are more suitable for practical use.

[0004] In order to achieve the first above-mentioned object, the technical solution of the copper ion antibacterial copolyester provided by the present invention is as follows:

[0005] The present invention provides a copper ion antibacterial copolyester, in which isophthalic acid containing a copper sulfonate ion group is used as a comonomer and bonded to the main chain of polyethylene terephthalate molecules, and copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds.

[0006] The copper ion antibacterial copolyester provided by the present invention can also be further realized by the following technical measures.

[0007] Preferably, the copper ion antibacterial copolyester has antibacterial and antifungal properties.

[0008] Preferably, the copper ion antibacterial copolyester spun into filaments with a specification of 75D / 36F has a bacteriostatic rate of more than 99% against Staphylococcus aureus, a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of not less than 92% against Trichophyton rubrum after being washed 50 times.

[0009] In order to achieve the second above-mentioned object, the technical solution of the preparation method of the copper ion antibacterial copolyester provided by the present invention is as follows:

[0010] The preparation method of the copper ion antibacterial copolyester provided by the present invention can also be further realized by the following technical measures.

[0011] The preparation method of the copper ion antibacterial copolyester provided by the present invention includes the following steps:

[0012] Copper isophthalate-5-sulfonate was prepared;

[0013] The copper isophthalate-5-sulfonate, terephthalic acid, and ethylene glycol were formulated into a slurry. Among them, the addition amount of the copper isophthalate-5-sulfonate was 0.7%-2.0% of the real-time output quality of the copper ion antibacterial copolyester, and the molar ratio of ethylene glycol to terephthalic acid and copper isophthalate-5-sulfonate was 1.05-2.0. The addition amount of ethylene glycol was 33.7%-64.2% of the real-time output quality of the copper ion antibacterial copolyester;

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

[0015] The copper-containing polyester oligomer was successively subjected to pre-polycondensation, final polycondensation, filtration, cooling and solidification, and pelletizing to obtain copper ion antibacterial copolyester chips.

[0016] Preferably, the preparation of copper isophthalate-5-sulfonate specifically includes the following steps:

[0017] An alkaline copper salt was added to an aqueous solution of isophthalic acid-5-sulfonic acid. The alkaline copper salt and the isophthalic acid-5-sulfonic acid were successively subjected to an acid-base neutralization reaction, recrystallization, filtration, and drying to obtain copper isophthalate-5-sulfonate. Among them,

[0018] In the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of isophthalic acid-5-sulfonic acid was 10%-30%;

[0019] The addition amount of the alkaline copper salt was 19.8%-52.4% of the mass of the isophthalic acid-5-sulfonic acid;

[0020] The reaction temperature of the acid-base neutralization reaction was 50°C-90°C.

[0021] Preferably, the alkaline copper salt was selected from one or a mixture of several of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0022] Preferably, the slurry was subjected to an esterification reaction to obtain a copper-containing polyester oligomer, which specifically included the following steps:

[0023] The slurry was continuously transported into an esterification system and subjected to an esterification reaction to obtain a copper-containing polyester oligomer.

[0024] Preferably, in the step of continuously transporting the slurry into an esterification system and subjecting it to an esterification reaction to obtain a copper-containing polyester oligomer, the esterification reaction temperature was 250°C-270°C, the esterification reaction pressure was 100 kPa-210 kPa, and the esterification rate of the copper-containing polyester oligomer was 90%-97%.

[0025] Preferably, the prepolycondensation of the copper-containing polyester oligomer specifically includes the following steps:

[0026] Continuously convey the copper-containing polyester oligomer to a prepolycondensation system for prepolycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer. Among them, the prepolycondensation reaction temperature is 270°C - 290°C, the prepolycondensation reaction pressure is 2 kPa - 4 kPa, and the intrinsic viscosity of the copper ion antibacterial copolyester prepolymer is 0.15 dL / g - 0.30 dL / g.

[0027] Preferably, the final polycondensation of the copper ion antibacterial copolyester prepolymer specifically includes the following steps:

[0028] Continuously convey the copper ion antibacterial copolyester prepolymer to a final polycondensation system for final polycondensation reaction to obtain a copper ion antibacterial copolyester melt. Among them, the final polycondensation reaction temperature is 275°C - 290°C, the final polycondensation reaction pressure is 100 Pa - 400 Pa, and the intrinsic viscosity of the copper ion antibacterial copolyester melt is 0.55 dL / g - 0.75 dL / g.

[0029] The copper ion antibacterial copolyester prepared by the preparation method of the copper ion antibacterial copolyester provided by the present invention bonds isophthalic acid containing a copper sulfonate ion group as a comonomer to the main chain of the polyethylene terephthalate molecule, and loads 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 copper ion antibacterial efficiency, and endowing the polyester product with excellent antibacterial and antifungal properties. Description of the Drawings

[0030] By reading the detailed description of the preferred embodiments below, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present invention. Moreover, throughout the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0031] Attached Figure 1 is a process flow chart of the preparation method of the copper ion antibacterial copolyester provided by the embodiment of the present invention;

[0032] Attached Figure 2 is a schematic diagram of the change relationship of substances during the preparation process of the copper ion antibacterial copolyester provided by the embodiment of the present invention. Detailed Embodiments

[0033] In view of this, the present invention provides a copper ion antibacterial copolyester and a preparation method thereof, which can improve the copper ion antibacterial efficiency and endow the polyester product with excellent antibacterial and antifungal properties, thereby being more suitable for practical use.

[0034] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, the following, in conjunction with the accompanying drawings and preferred embodiments, details a copper ion antibacterial copolyester and its preparation method according to the present invention, including its specific implementation manner, structure, characteristics, and effects. 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 article, the term "and / or" merely describes the associated relationship of associated objects, indicating that three relationships can exist. For example, A and / or B is specifically understood as: it can include both A and B simultaneously, A can exist alone, or B can exist alone, and it can possess any one of the above three situations.

[0036] Copper ion antibacterial copolyester

[0037] The present invention provides a copper ion antibacterial copolyester, in which isophthalic acid containing a copper sulfonate ion group is used as a comonomer and bonded to the main chain of a polyethylene terephthalate molecule, and copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds.

[0038] The copper ion antibacterial copolyester 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 a polyethylene terephthalate molecule. 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 and endowing the polyester products with excellent antibacterial and antifungal properties.

[0039] Among them, the copper ion antibacterial copolyester has antibacterial and antifungal properties.

[0040] Among them, for the filaments spun from the copper ion antibacterial copolyester with a specification of 75D / 36F, after being washed 50 times, the antibacterial rate against Staphylococcus aureus is greater than 99%, the antibacterial rate against Escherichia coli is greater than 99%, and the antibacterial rate against Trichophyton rubrum is not less than 92%.

[0041] Preparation method of copper ion antibacterial copolyester

[0042] The preparation method of the copper ion antibacterial copolyester provided by the present invention includes the following steps:

[0043] Step S1: Prepare copper isophthalate-5-sulfonate;

[0044] Step S2: Prepare a slurry from isophthalic acid-5-sulfonic acid copper, terephthalic acid, and ethylene glycol. Among them, the addition amount of isophthalic acid-5-sulfonic acid copper is 0.7%-2.0% of the real-time output quality of the copper ion antibacterial copolyester, the molar ratio of glycol to terephthalic acid and isophthalic acid-5-sulfonic acid copper is 1.05-2.0, and the addition amount of ethylene glycol is 33.7%-64.2% of the real-time output quality of the copper ion antibacterial copolyester;

[0045] Step S3: Subject the slurry to an esterification reaction to obtain a copper-containing polyester oligomer;

[0046] Step S4: The copper-containing polyester oligomer is successively subjected to pre-polycondensation, final polycondensation, filtration, cooling and solidification, and pelletizing to obtain copper ion antibacterial copolyester chips.

[0047] The copper ion antibacterial copolyester prepared by the preparation method of the copper ion antibacterial copolyester provided by the present invention bonds isophthalic acid containing a sulfonic acid copper ion group as a comonomer to the main chain of the polyethylene terephthalate molecule, and loads 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, and thus endowing the polyester products with excellent antibacterial and antifungal properties.

[0048] Among them, the preparation of isophthalic acid-5-sulfonic acid copper specifically includes the following steps:

[0049] Add an alkaline copper salt to an aqueous solution of isophthalic acid-5-sulfonic acid. The alkaline copper salt and isophthalic acid-5-sulfonic acid successively undergo an acid-base neutralization reaction, recrystallization, filtration, and drying to obtain isophthalic acid-5-sulfonic acid copper. Among them, in the aqueous solution of isophthalic acid-5-sulfonic acid, the mass percentage content of isophthalic acid-5-sulfonic acid is 10%-30%; the addition amount of the alkaline copper salt is 19.8%-52.4% of the mass of isophthalic acid-5-sulfonic acid; the reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

[0050] Among them, the alkaline copper salt is selected from one or a mixture of several of copper hydroxide, basic copper carbonate, and basic copper sulfate.

[0051] Among them, the slurry undergoes an esterification reaction to obtain a copper-containing polyester oligomer, which specifically includes the following steps:

[0052] Continuously convey the slurry into an esterification system, and through an esterification reaction, obtain a copper-containing polyester oligomer.

[0053] Among them, in the step of continuously transporting the slurry into the esterification system and obtaining the copper-containing polyester oligomer through the esterification reaction, the esterification reaction temperature is 250°C - 270°C, the esterification reaction pressure is 100 kPa - 210 kPa, and the esterification rate of the copper-containing polyester oligomer is 90% - 97%.

[0054] Among them, the pre-polycondensation of the copper-containing polyester oligomer specifically includes the following steps:

[0055] Continuously transport the copper-containing polyester oligomer into the pre-polycondensation system for pre-polycondensation reaction to obtain the copper ion antibacterial copolyester prepolymer. Among them, the pre-polycondensation reaction temperature is 270°C - 290°C, the pre-polycondensation reaction pressure is 2 kPa - 4 kPa, and the intrinsic viscosity of the copper ion antibacterial copolyester prepolymer is 0.15 dL / g - 0.30 dL / g.

[0056] Among them, the final polycondensation of the copper ion antibacterial copolyester prepolymer specifically includes the following steps:

[0057] Continuously transport the copper ion antibacterial copolyester prepolymer into the final polycondensation system for final polycondensation reaction to obtain the copper ion antibacterial copolyester melt. Among them, the final polycondensation reaction temperature is 275°C - 290°C, the final polycondensation reaction pressure is 100 Pa - 400 Pa, and the intrinsic viscosity of the copper ion antibacterial copolyester melt is 0.55 dL / g - 0.75 dL / g.

[0058] Example 1

[0059] (1) Add basic copper sulfate to an aqueous solution with a mass percentage of 20% of isophthalic acid-5-sulfonic acid, carry out an acid-base neutralization reaction at 80°C, and then perform recrystallization, filtration, and drying to obtain copper isophthalate-5-sulfonate. The addition amount of basic copper sulfate is 52.4% of the weight of isophthalic acid-5-sulfonic acid.

[0060] (2) Configure the copper isophthalate-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol into a slurry 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 isophthalate-5-sulfonate is 0.9% of the mass of the copper ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 36.8% of the mass of the copper ion antibacterial copolyester produced in real time.

[0061] (3) Continuously transport the slurry prepared in step (2) into the esterification reactor for esterification reaction to obtain the copper-containing polyester oligomer; among them, the esterification rate of the copper-containing polyester oligomer is 96%. The esterification reaction system consists of two esterification reactors connected in series. Among them, the reaction temperature of the first esterification reactor is 255°C and the reaction pressure is 170 kPa, and the reaction temperature of the second esterification reactor is 260°C and the reaction pressure is 120 kPa.

[0062] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) to a prepolycondensation system for prepolycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer; wherein the prepolycondensation reaction temperature is 275 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester prepolymer is 0.20 dL / g

[0063] (5) Continuously convey the copper ion antibacterial copolyester prepolymer prepared in step (4) to a final polycondensation system for final polycondensation reaction to obtain a copper ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 280 °C, the reaction pressure is 300 Pa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester melt is 0.65 dL / g

[0064] (6) Filter the copper ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain copper ion antibacterial copolyester chips.

[0065] Example 2

[0066] (1) Add copper hydroxide to an aqueous solution with a mass percentage of 10% of isophthalic acid-5-sulfonic acid, carry out an acid-base neutralization reaction at 50 °C, then recrystallize, filter and dry to obtain copper isophthalic acid-5-sulfonate, wherein the addition amount of copper hydroxide is 19.8% of the weight of isophthalic acid-5-sulfonic acid.

[0067] (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 2.0% of the mass of the copper ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 63.4% of the mass of the copper ion antibacterial copolyester produced in real time.

[0068] (3) Continuously convey the slurry prepared in step (2) to an esterification reaction kettle for esterification reaction to obtain a copper-containing polyester oligomer; wherein the esterification rate of the copper-containing polyester oligomer is 90%, and the reaction temperature of the esterification reaction kettle is 250 °C, and the reaction pressure is 210 kPa.

[0069] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) to a prepolycondensation system for prepolycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer; wherein the prepolycondensation reaction temperature is 280 °C, the reaction pressure is 4 kPa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester prepolymer is 0.18 dL / g

[0070] (5) Continuously convey the copper ion antibacterial copolyester prepolymer prepared in step (4) to the final polycondensation system for final polycondensation reaction to obtain a copper ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 280 °C, the reaction pressure is 400 Pa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester melt is 0.55 dL / g

[0071] (6) Filter the copper ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain copper ion antibacterial copolyester chips.

[0072] Example 3

[0073] (1) Add basic copper sulfate to an aqueous solution with a mass percentage of isophthalic acid-5-sulfonic acid of 20%. After carrying out an acid-base neutralization reaction at 90 °C, recrystallize, filter and dry to obtain copper isophthalate-5-sulfonate, wherein the addition amount of basic copper sulfate is 52.4% of the weight of isophthalic acid-5-sulfonic acid

[0074] (2) Prepare a slurry by mixing the copper isophthalate-5-sulfonate prepared in step (1) 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 1.05, the addition amount of copper isophthalate-5-sulfonate is 0.8% of the real-time output mass of the copper ion antibacterial copolyester, and the addition amount of ethylene glycol is 33.7% of the real-time output mass of the copper ion antibacterial copolyester.

[0075] (3) Continuously convey the slurry prepared in step (2) into an esterification reactor for esterification reaction to obtain a copper-containing polyester oligomer; wherein 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.

[0076] (4) Continuously convey the copper-containing polyester oligomer prepared in step (3) to the pre-polycondensation system for pre-polycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer; wherein the pre-polycondensation reaction temperature is 280 °C, the reaction pressure is 3 kPa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester prepolymer is 0.23 dL / g

[0077] (5) Continuously convey the copper ion antibacterial copolyester prepolymer prepared in step (4) to the final polycondensation system for final polycondensation reaction to obtain a copper ion antibacterial copolyester melt; wherein the final polycondensation reaction temperature is 285 °C, the reaction pressure is 200 Pa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester melt is 0.68 dL / g

[0078] (6) Filter the copper ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain copper ion antibacterial copolyester chips.

[0079] Example 4

[0080] (1) Cupric carbonate hydroxide is added to an aqueous solution with a mass percentage of 30% of isophthalic acid-5-sulfonic acid. After an acid-base neutralization reaction at 90 °C, recrystallization, filtration, and drying are carried out to obtain copper isophthalate-5-sulfonate, where the addition amount of cupric carbonate hydroxide is 22.5% of the weight of isophthalic acid-5-sulfonic acid.

[0081] (2) The copper isophthalate-5-sulfonate prepared in step (1), terephthalic acid, and ethylene glycol are configured into a slurry according to a certain molar ratio. The molar ratio of alcohol to acid in the slurry is 1.15. The addition amount of copper isophthalate-5-sulfonate is 1.3% of the mass of the copper ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 36.7% of the mass of the copper ion antibacterial copolyester produced in real time.

[0082] (3) The slurry configured in step (2) is continuously fed into an esterification reactor for an 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 connected in series. The reaction temperature of the first esterification reactor is 260 °C and the reaction pressure is 170 kPa. The reaction temperature of the second esterification reactor is 265 °C and the reaction pressure is 120 kPa.

[0083] (4) The copper-containing polyester oligomer prepared in step (3) is continuously fed into a pre-polycondensation system for a pre-polycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer. The pre-polycondensation reaction temperature is 270 °C and the reaction pressure is 4 kPa. The intrinsic viscosity of the prepared copper ion antibacterial copolyester prepolymer is 0.15 dL / g.

[0084] (5) The copper ion antibacterial copolyester prepolymer prepared in step (4) is continuously fed into a final polycondensation system for a final polycondensation reaction to obtain a copper ion antibacterial copolyester melt. The final polycondensation reaction temperature is 275 °C and the reaction pressure is 100 Pa. The intrinsic viscosity of the prepared copper ion antibacterial copolyester melt is 0.62 dL / g.

[0085] (6) The copper ion antibacterial copolyester melt prepared in step (5) is filtered, cooled, solidified, and pelletized to obtain copper ion antibacterial copolyester chips.

[0086] Example 5

[0087] (1) Cupric carbonate hydroxide is added to an aqueous solution with a mass percentage of 30% of isophthalic acid-5-sulfonic acid. After an acid-base neutralization reaction at 90 °C, recrystallization, filtration, and drying are carried out to obtain copper isophthalate-5-sulfonate, where the addition amount of cupric carbonate hydroxide is 22.5% of the weight of isophthalic acid-5-sulfonic acid.

[0088] (2) Prepare a slurry by mixing isophthalic acid-5-sulfonic acid copper prepared in step (1) with terephthalic acid and ethylene glycol in a certain molar ratio. The molar ratio of glycol to acid in the slurry is 2.0, the addition amount of isophthalic acid-5-sulfonic acid copper is 0.7% of the mass of the copper ion antibacterial copolyester produced in real time, and the addition amount of ethylene glycol is 64.2% of the mass of the copper ion antibacterial copolyester produced in real time.

[0089] (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.

[0090] (4) Continuously convey the blue-phase black antibacterial polyester oligomer prepared in step (3) to a prepolycondensation system for prepolycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer. The prepolycondensation reaction temperature is 290 °C, the reaction pressure is 2 kPa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester prepolymer is 0.30 dL / g.

[0091] (5) Continuously convey the copper ion antibacterial copolyester prepolymer prepared in step (4) to a final polycondensation system for final polycondensation reaction to obtain a copper ion antibacterial copolyester melt. The final polycondensation reaction temperature is 290 °C, the reaction pressure is 100 Pa, and the intrinsic viscosity of the prepared copper ion antibacterial copolyester melt is 0.75 dL / g.

[0092] (6) Filter the copper ion antibacterial copolyester melt prepared in step (5), then cool, solidify and pelletize it to obtain copper ion antibacterial copolyester chips.

[0093] Experimental example 1

[0094] (1) Dry the copper ion antibacterial copolyester chips prepared in Examples 1-5 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.

[0095] (2) Carry out melt spinning on the dried chips prepared in step 1 on a melt spinning machine to obtain a pre-oriented yarn with a specification of 120 D / 36 F. The melt spinning temperature is 290 °C and the spinning speed is 3000 m / min.

[0096] (3) Carry out stretching and processing on the pre-oriented yarn prepared in step (2) on a flat drawing machine to obtain a drawn yarn with a specification of 75 D / 36 F. The drawing ratio is 1.6 times, the drawing temperature is 80 °C, and the setting temperature is 130 °C.

[0097] (4) Weave the filaments with a specification of 75D / 36F prepared in step (3) into a garter, then wash it 50 times under test condition A1M in GB / T 12490-1990 of the national standard, and then test the antibacterial rates of the garter against Staphylococcus aureus and Escherichia coli after washing 50 times according to GB / T 20944.3-2007 of the national standard, and test the antibacterial rate of the garter against Trichophyton rubrum after washing 50 times according to GB / T20944.2-2007 of the national standard. The test results are shown in Table 1.

[0098] Table 1 Test results of antibacterial properties of filaments with a specification of 75D / 36F spun from the copper ion antibacterial copolyester chips prepared in Examples 1-5

[0099]

[0100] As can be seen from Table 1, the antibacterial rates of the filaments with a specification of 75D / 36F spun from the copper ion antibacterial copolyester chips prepared in Examples 1-5 against Trichophyton rubrum are not less than 92% after 50 times of water washing, and the antibacterial rates against Staphylococcus aureus and Escherichia coli are both greater than 99%. According to the regulations of the national standards "GB / T20944.2-2007 Evaluation of antibacterial properties of textiles - Part 2: Absorption method" and "GB / T 20944.3-2007 Evaluation of antibacterial properties of textiles - Part 3: Oscillation method": when the antibacterial rate of Staphylococcus aureus and Escherichia coli ≥ 70% and the antibacterial rate of Trichophyton rubrum ≥ 90%, the textiles have antibacterial effects. This shows that the copper ion antibacterial copolyesters prepared in Examples 1-5 all have good antibacterial effects. The antibacterial rate of the filaments with a specification of 75D / 36F spun from the copper ion antibacterial copolyester chips prepared in Example 5 against Trichophyton rubrum is 92% after 50 times of water washing, and the antibacterial rates against Staphylococcus aureus and Escherichia coli are both greater than 99%. This further shows that the copolymer addition of copper isophthalate-5-sulfonate relative to 0.7% of the weight of the copper ion antibacterial copolyester can endow the polyester products with excellent antibacterial properties, especially the antibacterial properties against bacteria.

[0101] 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 know the basic creative concepts. Therefore, the appended claims are intended to be construed to include the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0102] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. A copper ion antibacterial copolyester, characterized in that, Isophthalic acid containing a copper ion sulfonate group is copolymerized into the main chain of polyethylene terephthalate molecules, and copper ions with high antibacterial performance are loaded onto the polyester molecular chain through ionic bonds.

2. The copper ion antibacterial copolyester according to claim 1, wherein The copper ion antibacterial copolyester has antibacterial and antifungal properties.

3. The copper ion antibacterial copolyester according to claim 1, characterized in that, The filaments of the copper ion antibacterial copolyester with a specification of 75D / 36F after being washed 50 times have a bacteriostatic rate of more than 99% against Staphylococcus aureus, a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of not less than 92% against Trichophyton rubrum.

4. The preparation method of the copper ion antibacterial copolyester according to any one of claims 1-3, characterized in that, It includes the following steps: Prepare copper 5-sulfoisophthalate. Form a slurry with the copper 5-sulfoisophthalate, terephthalic acid, and ethylene glycol. Among them, the addition amount of the copper 5-sulfoisophthalate is 0.7%-2.0% of the real-time output quality of the copper ion antibacterial copolyester, the molar ratio of ethylene glycol to terephthalic acid and copper 5-sulfoisophthalate is 1.05-2.0, and the addition amount of ethylene glycol is 33.7%-64.2% of the real-time output quality of the copper ion antibacterial copolyester. Carry out an esterification reaction on the slurry to obtain a copper-containing polyester oligomer. The copper-containing polyester oligomer is successively subjected to pre-polycondensation, final polycondensation, filtration, cooling and solidification, and pelletizing to obtain copper ion antibacterial copolyester chips.

5. The preparation method of the copper ion antibacterial copolyester according to claim 4, characterized in that, The preparation of copper 5-sulfoisophthalate specifically includes the following steps: Add an alkaline copper salt to an aqueous solution of 5-sulfoisophthalic acid. The alkaline copper salt and the 5-sulfoisophthalic acid are successively subjected to an acid-base neutralization reaction, recrystallization, filtration, and drying to obtain copper 5-sulfoisophthalate. Among them, In the aqueous solution of 5-sulfoisophthalic acid, the mass percentage content of 5-sulfoisophthalic acid is 10%-30%. The addition amount of the alkaline copper salt is 19.8%-52.4% of the mass of 5-sulfoisophthalic acid. The reaction temperature of the acid-base neutralization reaction is 50°C-90°C.

6. The preparation method of the copper ion antibacterial copolyester according to claim 5, wherein, The alkaline copper salt is selected from one or a mixture of copper hydroxide, basic copper carbonate, and basic copper sulfate.

7. The preparation method of the copper ion antibacterial copolyester according to claim 4, characterized in that, The esterification reaction of the slurry to obtain a copper-containing polyester oligomer specifically includes the following steps: Continuously convey the slurry into an esterification system, and through an esterification reaction, obtain a copper-containing polyester oligomer.

8. The preparation method of the copper ion antibacterial copolyester according to claim 7, characterized in that, In the process of continuously conveying the slurry into an esterification system and obtaining a copper-containing polyester oligomer through an esterification reaction, the esterification reaction temperature is 250°C-270°C, the esterification reaction pressure is 100 kPa-210 kPa, and the esterification rate of the copper-containing polyester oligomer is 90%-97%.

9. The preparation method of the copper ion antibacterial copolyester according to claim 4, characterized in that, The pre-polycondensation of the copper-containing polyester oligomer specifically includes the following steps: Continuously convey the copper-containing polyester oligomer into a pre-polycondensation system for a pre-polycondensation reaction to obtain a copper ion antibacterial copolyester prepolymer. Among them, the pre-polycondensation reaction temperature is 270°C-290°C, the pre-polycondensation reaction pressure is 2 kPa-4 kPa, and the intrinsic viscosity of the copper ion antibacterial copolyester prepolymer is 0.15 dL / g-0.30 dL / g.

10. The preparation method of the copper ion antibacterial copolyester according to claim 9, characterized in that, The final polycondensation of the copper ion antibacterial copolyester prepolymer specifically includes the following steps: Continuously convey the copper ion antibacterial copolyester prepolymer to a final polycondensation system for a final polycondensation reaction to obtain a copper ion antibacterial copolyester melt, wherein the temperature of the final polycondensation reaction is 275°C - 290°C, the pressure of the final polycondensation reaction is 100 Pa - 400 Pa, and the intrinsic viscosity of the copper ion antibacterial copolyester melt is 0.55 dL / g - 0.75 dL / g.

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