Antibacterial polyester fiber and its synthesis process

Abstract

The present application relates to the technical field of polyester fibers, and discloses an antibacterial polyester fiber and a synthesis process thereof. A novel p-vinylbenzenesulfonate betaine base antibacterial finishing agent containing double carboxyl groups and double quaternary ammonium salt groups is synthesized, and polyester fibers are subjected to ultraviolet light grafting under the action of a photoinitiator such as benzophenone, so that rich double quaternary ammonium salt functional groups and double carboxyl groups are grafted on the surface of the polyester fibers. The grafted double quaternary ammonium salt functional groups have stronger antibacterial performance, improve the sterilization and long-acting antibacterial performance of the polyester fibers, and quaternary ammonium salt and carboxyl groups serve as strong hydrophilic functional groups, improve the hydrophilicity of the surface of the polyester fibers, are conducive to enhancing the antistatic property and dye dyeability of the polyester fibers, and expand the application range of the polyester fibers in the aspects of antibacterial fibers, garment fabrics, medical textile products and the like.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber technology, specifically to an antibacterial polyester fiber and its synthesis process. Background Technology

[0002] Polyester fiber has advantages such as high strength and good elasticity, and can be made into fabrics and textiles. In the fields of clothing, apparel, and pharmaceutical textiles, the antibacterial and hydrophilic properties of polyester fiber are conducive to expanding the development and application of polyester fiber. For example, the literature "Research on the Finishing of Polyester Fabrics with Quaternary Ammonium Salt Antibacterial Agent" synthesized a new type of quaternary ammonium salt antibacterial agent DEMHMA. Using azobisisobutyronitrile as an initiator, antibacterial polyester fabrics were prepared by pad-baking finishing method, which have excellent antibacterial properties, thus expanding the development and application of polyester fiber fabrics in medical and health textiles.

[0003] The lack of hydrophilic polar groups in the molecular chain of polyester fiber results in poor hygroscopicity, hydrophilicity, and dyeing properties, limiting the application range of polyester fiber. The literature "Performance Study of Acrylic Acid Grafting on Polyester Surface" reports the use of low-temperature plasma treatment on the surface of polyester fabric, followed by grafting reaction with acrylic acid, which improves the hydrophilicity, moisture regain, and dyeability of polyester fabric. This invention uses a novel betaine-based antibacterial finishing agent to graft and modify polyester fiber, obtaining polyester fiber with excellent antibacterial and hydrophilic properties, which has better applications in the fields of clothing, medical and health textiles. Summary of the Invention

[0004] (a) Technical problems to be solved This invention provides an antibacterial polyester fiber and its synthesis process, which solves the problems of poor antibacterial properties and poor hydrophilicity of polyester fiber.

[0005] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: a synthesis process for antibacterial polyester fiber, comprising polyester fiber, antibacterial finishing agent, and photoinitiator, characterized in that: the synthesis process is as follows: dissolving p-vinylbenzenesulfonate betaine-based antibacterial finishing agent and photoinitiator in a reaction solvent, then adding polyester fiber and impregnating it, grafting reaction under ultraviolet light for 1-3 h, and washing the fiber fabric sequentially with ethanol and distilled water to obtain antibacterial polyester fiber.

[0006] Preferably, the photoinitiator includes benzophenone, dimethyl benzoate, and 2,4,6-trimethylbenzoyldiphenyloxyphosphine.

[0007] Preferably, the mass fraction of the 4-vinylbenzenesulfonate betaine antibacterial finishing agent in the reaction solution is 5-12%.

[0008] Preferably, the mass fraction of the photoinitiator in the controlled reaction solution is 3-7%.

[0009] Preferably, the reaction solvent includes acetone, ethanol, and tetrahydrofuran.

[0010] Preferably, the synthesis process of the 4-vinylbenzenesulfonate betaine base antibacterial finishing agent is as follows: (1) Add 1,3-dichloropropanol and p-vinylbenzenesulfonyl chloride to the solvent under ice bath, then add triethylamine dropwise, stir the reaction at 10-30 °C for 6-12 h, concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5-20 as the eluent to obtain p-vinylbenzenesulfonate dipropyl chloride.

[0011] (2) Add dipropyl chloride of p-vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, add aqueous solution of dimethylamine and potassium iodide catalyst, reflux at 70-100 °C for 6-18 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5-10 as eluent to obtain dipropyl tertiary amine of p-vinylbenzenesulfonate.

[0012] (3) Add dipropyl tertiary amine p-vinylbenzenesulfonate and bromoacetic acid in a molar ratio of 1:2.5-4 to ethanol, reflux at 70-90 °C for 6-18 h, concentrate under reduced pressure after reaction, wash the product with diethyl ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent. Preferably, the solvent in (1) includes tetrahydrofuran, toluene, xylene, dichloromethane, 1,2-dichloroethane, and trichloromethane.

[0013] Preferably, the molar ratio of 1,3-dichloropropanol, vinylbenzenesulfonyl chloride and triethylamine in (1) is 1:1-1.5:0.8-1.5.

[0014] Preferably, the molar ratio of dipropyl chloride of vinylbenzenesulfonate, dimethylamine and potassium iodide in (2) is 1:3-5:0.01-0.02.

[0015] (iii) Beneficial technical effects A novel antibacterial finishing agent containing dicarboxyl and quaternary ammonium salt groups was synthesized by sulfonation reaction of 1,3-dichloropropanol and p-vinylbenzenesulfonyl chloride, followed by reaction with dimethylamine and bromoacetic acid. This agent was then grafted onto polyester fibers using ultraviolet light under the action of photoinitiators such as benzophenone, resulting in abundant quaternary ammonium salt functional groups and dicarboxyl groups grafted onto the polyester fiber surface.

[0016] The quaternary ammonium salt functional groups grafted onto polyester fibers exhibit stronger antibacterial properties, demonstrating a strong ability to inhibit and kill bacteria such as Escherichia coli. This significantly improves the bactericidal and long-lasting antibacterial properties of polyester fibers. Furthermore, the quaternary ammonium salt and carboxyl groups, as strongly hydrophilic functional groups, enhance the hydrophilicity of the polyester fiber surface, which is beneficial for improving the antistatic properties and dyeability of polyester fibers. This expands the application range of polyester fibers in antibacterial fibers, clothing fabrics, medical textiles, and other fields. Detailed Implementation

[0017] Example 1 (1) 10 mmol of 1,3-dichloropropanol and 12 mmol of p-vinylbenzenesulfonyl chloride were added to toluene under ice bath conditions, followed by the addition of 14 mmol of triethylamine. The mixture was stirred at 20 °C for 8 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography with a volume ratio of ethyl acetate:petroleum ether = 1:10 as the eluent. The dipropyl chloride of p-vinylbenzenesulfonate was obtained.

[0018] (2) Add 5 mmol of dipropyl chloride of vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution containing 15 mmol of dimethylamine and 0.07 mol of potassium iodide catalyst, reflux at 80 °C for 12 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5 as the eluent to obtain dipropyl tertiary amine of vinylbenzenesulfonate.

[0019] (3) Add 4 mmol of dipropylamine p-vinylbenzenesulfonate and 12 mmol of bromoacetic acid to ethanol, reflux at 90 °C for 12 h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

[0020] (4) Polyester fibers were added to a tetrahydrofuran solution containing 5% 4-vinylbenzenesulfonate betaine antibacterial finishing agent and 3% photoinitiator benzophenone and impregnated. The grafting reaction was carried out under ultraviolet light for 3 h. After the reaction, the fiber fabric was washed with ethanol and distilled water in sequence to obtain antibacterial polyester fibers.

[0021] Example 2 (1) 10 mmol of 1,3-dichloropropanol and 10 mmol of p-vinylbenzenesulfonyl chloride were added to tetrahydrofuran under ice bath conditions, followed by the addition of 15 mmol of triethylamine. The mixture was stirred at 10 °C for 12 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography with a volume ratio of ethyl acetate:petroleum ether = 1:10 as the eluent. The dipropyl chloride of p-vinylbenzenesulfonate was obtained.

[0022] (2) Add 5 mmol of dipropyl chloride of vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution containing 20 mmol of dimethylamine and 0.05 mol of potassium iodide catalyst, reflux at 100 °C for 6 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5 as the eluent to obtain dipropyl tertiary amine of vinylbenzenesulfonate.

[0023] (3) Add 4 mmol of dipropylamine p-vinylbenzenesulfonate and 12 mmol of bromoacetic acid to ethanol, reflux at 80 °C for 12 h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

[0024] (4) Polyester fibers were added to a tetrahydrofuran solution containing 7% 4-vinylbenzenesulfonate betaine antibacterial finishing agent and 4% photoinitiator 2,4,6-trimethylbenzoyl diphenyloxyphosphine and impregnated. The grafting reaction was carried out under ultraviolet light for 2 h. After the reaction, the fiber fabric was washed with ethanol and distilled water in sequence to obtain antibacterial polyester fibers.

[0025] Example 3 (1) 10 mmol of 1,3-dichloropropanol and 10 mmol of p-vinylbenzenesulfonyl chloride were added to dichloromethane under ice bath conditions, followed by the addition of 8 mmol of triethylamine. The mixture was stirred at 20 °C for 6 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography with a volume ratio of ethyl acetate:petroleum ether = 1:20 as the eluent. The dipropyl chloride of p-vinylbenzenesulfonate was obtained.

[0026] (2) Add 5 mmol of dipropyl chloride of vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution containing 25 mmol of dimethylamine and 0.1 mol of potassium iodide catalyst, reflux at 100 °C for 12 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5 as the eluent to obtain dipropyl tertiary amine of vinylbenzenesulfonate.

[0027] (3) Add 4 mmol of dipropylamine p-vinylbenzenesulfonate and 16 mmol of bromoacetic acid to ethanol, reflux at 90 °C for 6 h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

[0028] (4) Polyester fibers were added to an acetone solution containing 8% 4-vinylbenzenesulfonate betaine antibacterial finishing agent and 6% photoinitiator benzophenone and impregnated. The grafting reaction was carried out under ultraviolet light for 2 h. After the reaction, the fiber fabric was washed with ethanol and distilled water in sequence to obtain antibacterial polyester fibers.

[0029] Example 4 (1) 10 mmol of 1,3-dichloropropanol and 15 mmol of p-vinylbenzenesulfonyl chloride were added to 1,2-dichloroethane in an ice bath, followed by the addition of 15 mmol of triethylamine. The mixture was stirred at 20 °C for 12 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography with a volume ratio of ethyl acetate:petroleum ether = 1:20 as the eluent. The dipropyl chloride of p-vinylbenzenesulfonate was obtained.

[0030] (2) Add 5 mmol of dipropyl chloride of vinylbenzene sulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution containing 18 mmol of dimethylamine and 0.08 mol of potassium iodide catalyst, reflux at 100 °C for 12 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:10 as the eluent to obtain dipropyl tertiary amine of vinylbenzene sulfonate.

[0031] (3) Add 4 mmol of dipropylamine p-vinylbenzenesulfonate and 15 mmol of bromoacetic acid to ethanol, reflux at 70 °C for 12 h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

[0032] (4) Polyester fibers were added to an ethanol solution containing 10% 4-vinylbenzenesulfonate betaine antibacterial finishing agent and 7% photoinitiator benzophenone and impregnated. The grafting reaction was carried out under ultraviolet light for 2 h. After the reaction, the fiber fabric was washed with ethanol and distilled water in sequence to obtain antibacterial polyester fibers.

[0033] Example 5 (1) 10 mmol of 1,3-dichloropropanol and 12 mmol of p-vinylbenzenesulfonyl chloride were added to dichloromethane under ice bath conditions, followed by the addition of 10 mmol of triethylamine. The mixture was stirred at 20 °C for 12 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography with a volume ratio of ethyl acetate:petroleum ether = 1:5 as the eluent. The dipropyl chloride of p-vinylbenzenesulfonate was obtained.

[0034] (2) Add 5 mmol of dipropyl chloride of vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution containing 25 mmol of dimethylamine and 0.05 mol of potassium iodide catalyst, reflux at 100 °C for 12 h, cool and concentrate under reduced pressure after reaction, and perform column chromatography separation with ethyl acetate: petroleum ether = 1:5 as the eluent to obtain dipropyl tertiary amine of vinylbenzenesulfonate.

[0035] (3) Add 4 mmol of dipropylamine p-vinylbenzenesulfonate and 12 mmol of bromoacetic acid to ethanol, reflux at 80 °C for 12 h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

[0036] (4) Polyester fibers were added to an acetone solution containing 12% 4-vinylbenzenesulfonate betaine antibacterial finishing agent and 7% photoinitiator benzoin dimethyl ether and impregnated. The grafting reaction was carried out under ultraviolet light for 1 h. After the reaction, the fiber fabric was washed with ethanol and distilled water in sequence to obtain antibacterial polyester fibers.

[0037] Antibacterial performance test: The antibacterial polyester fibers from Examples 1-5 were respectively made into membrane samples with a diameter of 2 cm. Then, the membrane samples were added to a solution containing phosphate buffer and 10 7 The CFU / mL Escherichia coli suspension was placed in a flask and shaken at 37 °C for 1 h. Then, 2 mL of the sample solution was weighed as the shaken suspension and grafted onto the surface of a culture dish containing agar medium using the agar pouring method, which served as the experimental group.

[0038] Ordinary polyester fibers were used to prepare a membrane sample with a diameter of 2 cm. The membrane sample was then added to a solution containing phosphate buffer and 10... 8 The CFU / mL Escherichia coli suspension was placed in a flask and shaken at 37 °C for 1 h. Then, 2 mL of the sample solution was weighed as the shaken suspension and grafted onto the surface of a culture dish containing agar medium using the agar pouring method as a blank control.

[0039] The experimental group and the blank group were incubated at 37 ℃ for 24 h and viable bacteria were counted. The inhibition rate was determined by the formula: inhibition rate = (number of colonies in blank group - number of colonies in experimental group) ÷ number of colonies in blank group × 100%. sample Total bacterial count Antibacterial rate Example 1 9 93.3 Example 2 5 96.3 Example 3 3 97.8 Example 4 0 100% Example 5 2 98.5 Blank group 135 -

[0040] The water contact angle of the antibacterial polyester fiber sample was tested using a JC2000 contact angle measuring instrument. sample Water contact angle Example 1 82.3° Example 2 73.0° Example 3 70.2° Example 4 52.7° Example 5 58.2°

[0041] The water contact angle is used to characterize the hydrophilicity of fibers. The smaller the water contact angle, the better the hydrophilicity. The smallest water contact angle of the antibacterial polyester fiber sample is 52.7°.

Claims

1. A process for synthesizing antibacterial polyester fiber, comprising polyester fiber, an antibacterial finishing agent, and a photoinitiator, characterized in that: The synthesis process is as follows: dissolve the antibacterial finishing agent of polyvinylbenzene sulfonate betaine base and the photoinitiator in the reaction solvent, then add polyester fiber and impregnate it, and perform the grafting reaction under ultraviolet light for 1-3 hours. After the reaction, wash the fiber fabric with ethanol and distilled water in sequence to obtain antibacterial polyester fiber. The synthesis process of the p-vinylbenzenesulfonate betaine base antibacterial finishing agent is as follows: (1) Add 1,3-dichloropropanol and p-vinylbenzenesulfonyl chloride to the solvent under ice bath, then add triethylamine dropwise, stir the reaction at 10-30℃ for 6-12h, and then perform column chromatography to separate p-vinylbenzenesulfonate dipropyl chloride. (2) Add dipropyl chloride of p-vinylbenzenesulfonate to tetrahydrofuran, stir to dissolve, then add an aqueous solution of dimethylamine and potassium iodide catalyst, reflux at 70-100℃ for 6-18h, and then perform column chromatography to separate the dipropyl tertiary amine of p-vinylbenzenesulfonate. (3) Add dipropylamine p-vinylbenzenesulfonate and bromoacetic acid in a molar ratio of 1:2.5-4 to ethanol, reflux at 70-90℃ for 6-18h, concentrate under reduced pressure after reaction, wash the product with ether, add ethanol, and then recrystallize to obtain p-vinylbenzenesulfonate betaine base antibacterial finishing agent.

2. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The photoinitiator includes benzophenone, dimethyl benzoate, and 2,4,6-trimethylbenzoyldiphenyloxyphosphine.

3. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The mass fraction of the antibacterial finishing agent, p-vinylbenzenesulfonate betaine base, in the reaction solvent is 5-12%.

4. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The mass fraction of photoinitiator in the reaction solvent is 3-7%.

5. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The reaction solvents include acetone, ethanol, and tetrahydrofuran.

6. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The solvent in (1) includes tetrahydrofuran, toluene, xylene, dichloromethane, 1,2-dichloroethane, and trichloromethane.

7. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The molar ratio of 1,3-dichloropropanol, p-vinylbenzenesulfonyl chloride, and triethylamine in (1) is 1:1-1.5:0.8-1.

5.

8. The synthesis process of antibacterial polyester fiber according to claim 1, characterized in that: The molar ratio of dipropyl chloride of vinylbenzenesulfonate, dimethylamine, and potassium iodide in (2) is 1:3-5:0.01-0.02.

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