Preparation method of bio-based nylon fiber modified by nitrogen-containing ionic liquid
By polymerizing the nitrogen-containing ionic liquid with the bio-based nylon salt and subjecting electron beam irradiation and melt spinning, a bio-based nylon fiber modified with the nitrogen-containing ionic liquid is obtained, which solves the problem of loss of antibacterial components in the prior art and achieves efficient antibacterial properties.
Patent Information
- Application Number
- CN202510103296.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-22
- Publication Date
- 2025-04-25
AI Technical Summary
In the prior art, polyamide composite materials prepared by ordinary physical blending methods are prone to precipitation during long-term use, resulting in the loss of antibacterial components and reducing the antibacterial properties of the material.
By polymerizing the nitrogen-containing ionic liquid with the bio-based nylon salt, an ionic liquid doped prepolymer is obtained, and electron beam irradiation and melt spinning is performed to obtain a bio-based nylon fiber modified with nitrogen-containing ionic liquid.
Connect ionic liquid and polymer molecules through chemical bonds, avoiding the loss of ionic liquid due to migration and other reasons during long-term use, significantly improving the antibacterial properties of the fiber, with a bacterial rate of up to 99.9%.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of bio-based nylon fiber modification, and in particular to a method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid. Background Art
[0002] The positive charge of the ionic liquid interacts with the negative charge on the bacterial surface through electrostatic attraction and aggregates on the bacterial wall, causing the bacteria to lyse and die. In addition, its long alkyl chain easily enters the hydrophobic area of the bacterial lipid membrane to kill the bacteria. However, the polyamide composite material made of ionic liquid by ordinary physical blending method is prone to precipitation and other phenomena in long-term use, resulting in the loss of antibacterial components and reducing the antibacterial performance of the material.
[0003] Therefore, it is of great significance to study a preparation method of bio-based nylon fiber modified by nitrogen-containing ionic liquid to improve the antibacterial properties of bio-based nylon fiber. Summary of the invention
[0004] The purpose of the present invention is to provide a method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid, so as to solve the problem that the antibacterial performance of polyamide composite materials prepared by ionic liquid through ordinary physical blending method in the prior art is reduced during long-term use.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a method for preparing a bio-based nylon fiber modified by a nitrogen-containing ionic liquid, comprising the following steps:
[0007] (1) polymerizing a nitrogen-containing ionic liquid and a bio-based nylon salt to obtain an ionic liquid-doped prepolymer;
[0008] (2) The ionic liquid-doped prepolymer is subjected to electron beam irradiation and melt spinning to produce bio-based nylon fibers modified with nitrogen-containing ionic liquid.
[0009] Preferably, in step (1), the cation of the nitrogen-containing ionic liquid comprises an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation, a quaternary phosphonium salt cation, a pyridine cation, a pyrrole cation or a piperidine cation, and the anion comprises a fluoride ion, a chloride ion, a bromide ion, a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a phosphate ion, a toluenesulfonate ion, a dihydrogen phosphate ion, a diethyl phosphate, a dihydrogen phosphate ion, a nitrate ion, a methylsulfate ion, a methylsulfate ion, a chloroaluminate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a trifluoromethylsulfonate ion, a thiocyanate ion, an acetate ion, a di(2,4,4 bis(trifluoromethyl)imide, bis(trifluoromethanesulfonyl)imide, bis(phthalato)borate, bromochlorate, decylbenzenesulfonate, dichlorocuprate, bis(pentafluoroethyl)phosphinate, bis(salicylate)borate, bis(trifluoromethanesulfonyl)methane, (dodecyl)benzenesulfonate, diethylphosphonate, ethyl sulfate, ethyl sulfonate, tetracyanoborate, tetrakis(hydrogensulfate)borate, tetrakis(methylsulfate)borate, tris(pentafluoroethyl)trifluorophosphate or trifluoroacetate.
[0010] Preferably, the mass ratio of the nitrogen-containing ionic liquid to the bio-based nylon salt is 0.0001-0.99:100.
[0011] Preferably, the bio-based nylon salt comprises nylon 56 salt, nylon 54 salt, nylon 510 salt, nylon 512 salt or nylon 513 salt.
[0012] Preferably, in step (1), the polymerization comprises prepolymerization and final polymerization.
[0013] Preferably, the temperature during the prepolymerization is 200-270° C., the rotation speed is 10-30 rpm, and the first mixing time is 5-15 min.
[0014] Preferably, the final polymerization temperature is 200-270° C., the rotation speed is 50-70 rpm, and the time is 15-25 min.
[0015] Preferably, in step (2), the electron beam irradiation dosage is 1 to 800 kGy and the time is 8 to 18 h.
[0016] Preferably, in step (2), melt spinning is carried out in a protective atmosphere, the melt spinning temperature is 250 to 290° C., and the pressure is 500 to 1200 kPa.
[0017] Beneficial effects of the present invention:
[0018] The present invention polymerizes nitrogen-containing ionic liquid and bio-based nylon salt and then irradiates with electron beams, so that small molecules of nitrogen-containing ionic liquid can fully contact with bio-based nylon salt, thereby being grafted onto polymer molecular chains, and connecting ionic liquid and polymer molecules through chemical bonds, thereby avoiding loss of ionic liquid due to migration and other reasons during long-term use.
[0019] The antibacterial rate of the bio-based nylon fiber modified by the nitrogen-containing ionic liquid of the present invention on Escherichia coli and Staphylococcus aureus is as high as 99.9%. DETAILED DESCRIPTION
[0020] The present invention provides a method for preparing a bio-based nylon fiber modified by a nitrogen-containing ionic liquid, comprising the following steps:
[0021] (1) polymerizing a nitrogen-containing ionic liquid and a bio-based nylon salt to obtain an ionic liquid-doped prepolymer;
[0022] (2) The ionic liquid-doped prepolymer is subjected to electron beam irradiation and melt spinning to produce bio-based nylon fibers modified with nitrogen-containing ionic liquid.
[0023] In the present invention, the nitrogen-containing ionic liquid and the bio-based nylon salt are preferably dried separately before polymerization, and the purpose of drying is to remove moisture from the substrate.
[0024] In the present invention, in the step (1), the cation of the nitrogen-containing ionic liquid comprises an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation, a quaternary phosphonium salt cation, a pyridine cation, a pyrrole cation or a piperidine cation, and the anion comprises a fluoride ion, a chloride ion, a bromide ion, a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a phosphate ion, a toluenesulfonate ion, a dihydrogen phosphate ion, a diethyl phosphate, a dihydrogen phosphate ion, a nitrate ion, a methylsulfate ion, a methylsulfonate ion, a chloroaluminate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a trifluoromethylsulfonate ion, a thiocyanate ion, an acetate ion, a di(2,4, 4-trimethylpentyl)phosphinate, bis(malonato)borate, borate, dicyanamide, chloroaluminate, bis(oxalato)borate, bis(trifluoromethyl)imide, bis(trifluoromethanesulfonyl)imide, bis(phthalato)borate, bromochlorate, decylbenzenesulfonate, dichlorocuprate, bis(pentafluoroethyl)phosphinate, bis(salicylate)borate, bis(trifluoromethanesulfonyl)methane, (dodecyl)benzenesulfonate, diethylphosphonate, ethyl sulfate, ethyl sulfonate, tetracyanoborate, tetrakis(hydrogensulfate)borate, tetrakis(methylsulfate)borate, tris(pentafluoroethyl)trifluorophosphate or trifluoroacetate.
[0025] In the present invention, the nitrogen-containing ionic liquid is preferably 1-vinyl-3-butylimidazolium chloride, tetrabutylammonium dihydrogen phosphate, polyhexamethyleneguanidine hydrochloride, poly (p-vinylbenzyl-trimethylphosphine hexafluorophosphate), 1-hexyl-3-methylpyridine methyl sulfate, N,N-di(propyl)pyrrole dihydrogen phosphate or N,N-di(n-butyl)piperidinium hexafluorophosphate.
[0026] In the present invention, the mass ratio of the nitrogen-containing ionic liquid to the bio-based nylon salt is 0.0001 to 0.99:100, preferably 0.01 to 0.2:100, and more preferably 0.05 to 0.1:100.
[0027] In the present invention, the bio-based nylon salt comprises nylon 56 salt, nylon 54 salt, nylon 510 salt, nylon 512 salt or nylon 513 salt, preferably nylon 510 salt.
[0028] In the present invention, in the step (1), the polymerization includes prepolymerization and final polymerization.
[0029] In the present invention, the prepolymerization temperature is 200-270°C, preferably 210-260°C; the rotation speed is 10-30rpm, preferably 15-25rpm, more preferably 20rpm; the time is 5-15min, preferably 8-12min, more preferably 10min.
[0030] In the present invention, the final polymerization temperature is 200-270°C, preferably 210-260°C; the rotation speed is 50-70rpm, preferably 55-65rpm, more preferably 60rpm; the time is 15-25min, preferably 18-22min, more preferably 20min.
[0031] In the present invention, in the step (1), the nitrogen-containing ionic liquid and the bio-based nylon salt are placed in a polymerization reactor, and the temperature is increased for prepolymerization and final polymerization. During the prepolymerization and final polymerization, the bio-based nylon salt undergoes polymerization reaction by itself. During the prepolymerization, the state of the reactant changes from liquid to polymer, and the rotation speed is low at this time. During the final polymerization, the reactant has become a viscous polymer. The rotation speed is increased to fully evaporate the water in the polymer, increase the viscosity of the polymer, and form a high polymer. During the entire polymerization process, the nitrogen-containing ionic liquid is wrapped in the polymer through the self-polymerization process of the bio-based nylon salt, so that the nitrogen-containing ionic liquid is evenly distributed in the entire system.
[0032] In the present invention, in the step (2), the dose of electron beam irradiation is 1 to 800 kGy, preferably 10 to 100 kGy, and more preferably 25 to 45 kGy; the time is 8 to 18 h, and preferably 8 h, 10 h, 12 h, or 15 h.
[0033] In the present invention, in the step (2), melt spinning is carried out in a protective atmosphere, the melt spinning temperature is 250-290° C., the pressure is 500-1200 kPa, and the spinneret aperture is 0.3×0.75 mm.
[0034] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0035] Example 1
[0036] Nylon 510 salt (PA510 salt) was placed in a vacuum drying oven at 100° C. for 12 h, and 1-vinyl-3-butylimidazole chloride was placed in a vacuum drying oven at 80° C. for 12 h to completely remove moisture.
[0037] 100 g of nylon 510 salt and 0.05 g of 1-vinyl-3-butyl imidazole chloride were placed in a polymerization reactor, the temperature was raised to 260°C, prepolymerization was carried out at a rotation speed of 20 rpm for 10 min, the temperature was kept constant, final polymerization was carried out at a rotation speed of 60 rpm for 20 min, and the material was cooled and shaped after discharge to obtain an ionic liquid-doped prepolymer.
[0038] The ionic liquid-doped prepolymer was placed in a polyethylene ziplock bag and irradiated at a dose of 25 kGy for 8 hours. Finally, it was added to a melt spinning machine and melt-spun in a nitrogen atmosphere with a spinning temperature of 255°C, a pressure of 1000 kPa, and a spinneret aperture of 0.3×0.75 mm to obtain bio-based nylon fibers modified with nitrogen-containing ionic liquids.
[0039] Example 2
[0040] The difference from Example 1 is that the irradiation dose is 35 kGy, and other conditions are the same.
[0041] Example 3
[0042] The difference from Example 1 is that the irradiation dose is 45 kGy, and other conditions are the same.
[0043] Example 4
[0044] The difference from Example 2 is that the nitrogen-containing ionic liquid is tetrabutylammonium dihydrogen phosphate, and other conditions are the same.
[0045] Example 5
[0046] The difference from Example 2 is that the nitrogen-containing ionic liquid is polyhexamethyleneguanidine hydrochloride, and other conditions are the same.
[0047] Example 6
[0048] The difference from Example 2 is that the nitrogen-containing ionic liquid is poly (p-vinylbenzyl-trimethyl quaternary phosphine hexafluorophosphate), and other conditions are the same.
[0049] Example 7
[0050] The difference from Example 2 is that the nitrogen-containing ionic liquid is 1-hexyl-3-methylpyridinium methyl sulfate, and other conditions are the same.
[0051] Example 8
[0052] The difference from Example 2 is that the nitrogen-containing ionic liquid is N,N-di(propyl)pyrrole dihydrogen phosphate, and other conditions are the same.
[0053] Example 9
[0054] The difference from Example 2 is that the nitrogen-containing ionic liquid is N,N-di(n-butyl)piperidinium hexafluorophosphate, and other conditions are the same.
[0055] Comparative Example 1
[0056] Nylon 510 salt (PA510 salt) was placed in a vacuum drying oven at 100° C. for 12 h to completely remove moisture.
[0057] 100 g of nylon 510 salt was placed in a polymerization reactor, the temperature was raised to 260°C, prepolymerized at a rotation speed of 20 rpm for 10 min, the temperature was kept constant, final polymerized at a rotation speed of 60 rpm for 20 min, and cooled after discharge to obtain a nylon 510 salt polymer.
[0058] The above nylon 510 salt polymer was added into a melt spinning machine and melt-spinning was carried out under a nitrogen atmosphere with a spinning temperature of 255° C., a pressure of 1000 kPa, and a spinneret aperture of 0.3×0.75 mm to obtain bio-based nylon fibers.
[0059] Comparative Example 2
[0060] Nylon 510 salt (PA510 salt) was placed in a vacuum drying oven at 100° C. for 12 h, and 1-vinyl-3-butylimidazole chloride was placed in a vacuum drying oven at 80° C. for 12 h to completely remove moisture.
[0061] 100 g of nylon 510 salt and 0.05 g of 1-vinyl-3-butyl imidazole chloride were placed in a polymerization reactor, the temperature was raised to 260°C, prepolymerization was carried out at a rotation speed of 20 rpm for 10 min, the temperature was kept constant, final polymerization was carried out at a rotation speed of 60 rpm for 20 min, and the material was cooled and shaped after discharge to obtain an ionic liquid-doped prepolymer.
[0062] The ionic liquid-doped prepolymer was added into a melt spinning machine and melt-spinning was carried out in a nitrogen atmosphere with a spinning temperature of 255° C., a pressure of 1000 kPa, and a spinneret aperture of 0.3×0.75 mm to obtain nitrogen-containing ionic liquid-doped bio-based nylon fibers.
[0063] The bio-based nylon fibers modified by nitrogen-containing ionic liquids in Examples 1 to 9, the bio-based nylon fibers in Comparative Example 1, and the bio-based nylon fibers doped with nitrogen-containing ionic liquids in Comparative Example 2 were woven into antibacterial cloths, and then subjected to antibacterial tests. The specific test method is as follows: 25 mL of agar medium was poured into sterile culture dishes in a clean bench, and cooled and solidified naturally. A pipette was used to take a 1×10 8 100 μL of CFU / mL Escherichia coli suspension was inoculated onto the culture medium and evenly spread on the surface of the agar culture medium with a smear stick. The antibacterial cloth was then cut into a circular sample with a diameter of 20 mm and placed on the center surface of the agar culture medium. The culture dish was covered with a lid, inverted, and cultured in an incubator at 37°C for 24 hours. The results were observed and are shown in Table 1.
[0064] Table 1 Antibacterial test results
[0065]
[0066]
[0067] It can be seen from Table 1 that the bio-based nylon fiber modified with the nitrogen-containing ionic liquid prepared in the present invention has a good antibacterial effect.
[0068] As can be seen from the above embodiments, the present invention provides a method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid, and the specific steps are as follows: polymerizing nitrogen-containing ionic liquid and bio-based nylon salt to obtain ionic liquid-doped prepolymer; subjecting the ionic liquid-doped prepolymer to electron beam irradiation and melt spinning to obtain nitrogen-containing ionic liquid-modified bio-based nylon fiber. The present invention copolymerizes nitrogen-containing ionic liquid and bio-based nylon salt and then irradiates with electron beam, so that the nitrogen-containing ionic liquid small molecules can fully contact with the bio-based nylon salt, thereby being grafted onto the polymer molecular chain, and the connection between the ionic liquid and the polymer molecule is achieved through chemical bonds, thereby avoiding the loss of ionic liquid due to migration and other reasons during long-term use, and the obtained nitrogen-containing ionic liquid-modified bio-based nylon fiber has good antibacterial effect.
[0069] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid, characterized in that: The steps include: (1) polymerizing a nitrogen-containing ionic liquid and a bio-based nylon salt to obtain an ionic liquid-doped prepolymer; (2) The ionic liquid-doped prepolymer is subjected to electron beam irradiation and melt spinning to produce bio-based nylon fibers modified with nitrogen-containing ionic liquid.
2. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 1, characterized in that: In the step (1), the cation of the nitrogen-containing ionic liquid comprises an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation, a quaternary phosphonium salt cation, a pyridine cation, a pyrrole cation or a piperidine cation, and the anion comprises a fluoride ion, a chloride ion, a bromide ion, a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a phosphate ion, a toluenesulfonate ion, a dihydrogen phosphate ion, a diethyl phosphate, a dihydrogen phosphate ion, a nitrate ion, a methylsulfate ion, a methylsulfonate ion, a chloroaluminate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a trifluoromethylsulfonate ion, a thiocyanate ion, an acetate ion, a di(2,4,4-trifluoromethyl)sulfonate ion, a tetrafluoroborate ion, a trifluoromethylsulfonate ion, a thiocyanate ion, a ... methylpentyl)phosphinate, bis(malonato)borate, borate, dicyanamide, chloroaluminate, bis(oxalato)borate, bis(trifluoromethyl)imide, bis(trifluoromethanesulfonyl)imide, bis(phthalato)borate, bromochlorate, decylbenzenesulfonate, dichlorocuprate, bis(pentafluoroethyl)phosphinate, bis(salicylate)borate, bis(trifluoromethanesulfonyl)methane, (dodecyl)benzenesulfonate, diethylphosphonate, ethyl sulfate, ethyl sulfonate, tetracyanoborate, tetrakis(hydrogensulfate)borate, tetrakis(methylsulfate)borate, tris(pentafluoroethyl)trifluorophosphate or trifluoroacetate.
3. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 1 or 2, characterized in that: The mass ratio of the nitrogen-containing ionic liquid to the bio-based nylon salt is 0.0001-0.99:
100.
4. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 3, characterized in that: The bio-based nylon salt comprises nylon 56 salt, nylon 54 salt, nylon 510 salt, nylon 512 salt or nylon 513 salt.
5. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 2 or 4, characterized in that: In the step (1), the polymerization includes prepolymerization and final polymerization.
6. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 5, characterized in that: The prepolymerization temperature is 200-270° C., the rotation speed is 10-30 rpm, and the time is 5-15 minutes.
7. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 6, characterized in that: The temperature during the final polymerization is 200-270° C., the rotation speed is 50-70 rpm, and the second polymerization time is 15-25 minutes.
8. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 6 or 7, characterized in that: In the step (2), the dose of electron beam irradiation is 1 to 800 kGy and the time is 8 to 18 hours.
9. The method for preparing bio-based nylon fiber modified by nitrogen-containing ionic liquid according to claim 9, characterized in that: In the step (2), melt spinning is carried out in a protective atmosphere, the temperature of the melt spinning is 250 to 290° C., and the pressure is 500 to 1200 kPa.