CN115233333A - Antibacterial modified polyamide composite fiber and synthetic method thereof - Google Patents
Antibacterial modified polyamide composite fiber and synthetic method thereof Download PDFInfo
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- CN115233333A CN115233333A CN202211016954.2A CN202211016954A CN115233333A CN 115233333 A CN115233333 A CN 115233333A CN 202211016954 A CN202211016954 A CN 202211016954A CN 115233333 A CN115233333 A CN 115233333A
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- chitosan
- polyamide
- composite fiber
- quaternary ammonium
- ammonium salt
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- 239000000835 fiber Substances 0.000 title claims abstract description 59
- 239000004952 Polyamide Substances 0.000 title claims abstract description 34
- 229920002647 polyamide Polymers 0.000 title claims abstract description 34
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title description 2
- 229920001661 Chitosan Polymers 0.000 claims abstract description 77
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 57
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 triethanolamine quaternary ammonium salt Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 23
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical compound OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002262 Schiff base Substances 0.000 claims description 16
- 150000004753 Schiff bases Chemical class 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 238000010511 deprotection reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000001914 filtration Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
The invention relates to the technical field of polyamide fibers and discloses an antibacterial modified polyamide composite fiber and a synthesis method thereof, wherein polyhydroxy of triethanolamine quaternary ammonium salt is subjected to esterification reaction with carboxyl of chitosan and carboxyl of acrylic acid grafted polyamide 6 respectively to obtain chitosan quaternary ammonium salt grafted polyamide 6 with high grafting rate, the chitosan quaternary ammonium salt grafted polyamide 6 is used as an antibacterial agent and is blended with the polyamide 6 to obtain the antibacterial modified polyamide composite fiber, the compatibility and interface acting force of chitosan and a polyamide 6 matrix are improved, the phenomenon of phase separation of the composite fiber after spinning is favorably overcome, the composite fiber shows higher breaking strength and mechanical property, and meanwhile, the chitosan quaternary ammonium salt biological antibacterial agent is endowed with excellent antibacterial property of the polyamide fiber.
Description
Technical Field
The invention relates to the technical field of polyamide fibers, in particular to an antibacterial modified polyamide composite fiber.
Background
The polyamide 6 (PA 6) fiber has high wear resistance, good heat resistance and excellent chemical resistance, can be made into long fiber or short fiber, and is important to be applied to textile fiber, clothing, rope screen and the like; and can be blended with natural fibers, silk, chitosan and the like to improve the comprehensive performance of the polyamide 6 fibers, for example, the fiber membrane obtained by blending chitosan and PA6 has excellent adsorption performance in the research on the preparation and adsorption performance of porous chitosan fiber membranes.
In recent years, the antibacterial performance of polyamide 6 fibers is improved, and the application of the antibacterial polyamide fiber in the aspects of medical health, antibacterial fiber and the like is developed to become a research trend, for example, the antibacterial performance of PA6 composite fiber is passed by synthesizing a guanidino polymer antibacterial agent in preparation, structure and performance of antibacterial polyamide fiber; the antibacterial agent mainly comprises a guanidine antibacterial agent, a chitosan-based antibacterial agent and the like, wherein the chitosan quaternary ammonium salt antibacterial agent has good biocompatibility, is nontoxic and pollution-free, and is an antibacterial agent with wide application.
Disclosure of Invention
Technical problem to be solved
The invention provides an antibacterial modified polyamide composite fiber, which improves the antibacterial property and strength of a polyamide 6 fiber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an antibacterial modified polyamide composite fiber is synthesized by the following method: adding the chitosan quaternary ammonium salt grafted polyamide 6 and the polyamide 6 into a formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.3-0.6mL/h, the spinning voltage is 20-25kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Preferably, the mass ratio of the chitosan quaternary ammonium salt grafted polyamide 6 to the polyamide 6 is 0.1-0.4.
Preferably, the chitosan quaternary ammonium salt grafted polyamide 6 is synthesized by the following method:
s1, dissolving chitosan into an acetic acid solution, adding benzaldehyde, and reacting to obtain Schiff base protective chitosan; then adding the mixture into a sodium hydroxide solution, adding epoxy chloropropane after uniformly stirring, and reacting to obtain the epoxidized Schiff base chitosan.
S2, adding the epoxy Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding DL-aspartic acid, stirring for reaction, adding the product into a hydrochloric acid solution for deprotection, and washing the product with acetone to obtain the polycarboxyl hydrophilic modified chitosan.
S3, adding triethanolamine and benzyl chloride into an ethanol solvent, and carrying out heating reflux reaction to obtain triethanolamine quaternary ammonium salt; and dissolving triethanolamine quaternary ammonium salt into a xylene solvent, adding polycarboxyl hydrophilic modified chitosan, acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, dropwise adding p-toluenesulfonic acid, stirring for grafting reaction, cooling after reaction, adding deionized water for precipitation, filtering the solvent, and washing with deionized water and ethanol to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
Preferably, the mass ratio of the epoxidized chitosan to the DL-aspartic acid in S2 is 1.
Preferably, the reaction temperature in the S2 is 70-90 ℃ and the reaction time is 12-36h.
Preferably, the mass ratio of the triethanolamine quaternary ammonium salt, the polycarboxyl hydrophilic modified chitosan, the acrylic acid grafted polyamide 6 and the p-toluenesulfonic acid in the S3 is 0.1-0.6.
Preferably, the temperature of the grafting reaction in the S3 is 110-140 ℃ and the time is 24-48h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
protecting chitosan amino with benzaldehyde, reacting with epoxy chloropropane to obtain epoxidized Schiff base chitosan, further performing ring opening addition reaction on an epoxy group and DL-aspartic acid, and performing deprotection with hydrochloric acid to obtain polycarboxyl hydrophilic modified chitosan, so that abundant carboxyl is introduced into a chitosan side chain, and under the catalysis of p-toluenesulfonic acid, the polyhydroxy of triethanolamine quaternary ammonium salt is subjected to esterification reaction with the carboxyl of chitosan and the carboxyl of acrylic acid grafted polyamide 6 respectively to obtain chitosan quaternary ammonium salt grafted polyamide 6 with high grafting rate, and abundant quaternary ammonium salt functional groups and polyamide 6 molecular chains are introduced into a chitosan matrix.
The chitosan quaternary ammonium salt grafted polyamide 6 is used as an antibacterial agent and is blended with the polyamide 6 to obtain the antibacterial modified polyamide composite fiber, a chitosan grafted polyamide 6 molecular chain can be used as a compatilizer, the compatibility and the interface acting force of chitosan and a polyamide 6 matrix are improved, the phenomenon that the composite fiber is separated after spinning is favorably overcome, the composite fiber shows higher breaking strength and mechanical property, meanwhile, the chitosan quaternary ammonium salt biological antibacterial agent is endowed with the excellent antibacterial property of the polyamide fiber, and the application of the polyamide fiber in the aspects of antibacterial fiber materials, medical sanitation and the like is expanded.
Detailed Description
Example 1
(1) Dissolving 0.5g of chitosan into 1% acetic acid solution, then adding 3g of benzaldehyde, reacting for 24 hours at room temperature, dropwise adding sodium hydroxide solution after reaction to separate out a precipitate, filtering the solvent, and washing with ethanol and deionized water to obtain Schiff base protective chitosan; and then adding 0.5g of Schiff base protective chitosan into a 1.5% sodium hydroxide solution, uniformly stirring, adding 0.7g of epoxy chloropropane, stirring and reacting at 60 ℃ for 4 hours, filtering the solvent after the reaction, and washing with ethanol and deionized water to obtain the epoxidized Schiff base chitosan.
(2) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.2g of DL-aspartic acid, stirring and reacting at 90 ℃ for 24 hours, adding the product into 2% hydrochloric acid solution after the reaction, stirring and reacting at room temperature for 36 hours, filtering the solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(3) Adding polyamide 6 into 20% formic acid to swell uniformly, then dropwise adding acrylic acid (5 mg/mL), and reacting at 60 ℃ for 3h by using ceric ammonium nitrate (6 mg/mL) and sulfuric acid as initiators to obtain the acrylic acid grafted polyamide 6.
(4) 0.2g of triethanolamine and 0.15g of benzyl chloride are added to ethanolHeating and refluxing in solvent to obtain triethanolamine quaternary ammonium salt
And then dissolving 0.2g of triethanolamine quaternary ammonium salt into a xylene solvent, adding 2g of polycarboxylic hydrophilic modified chitosan, 1g of acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, dropwise adding 0.02g of p-toluenesulfonic acid, stirring for grafting reaction at 110 ℃ for 36 hours, cooling after reaction, adding deionized water for precipitation, filtering the solvent, and washing with deionized water and ethanol to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
(5) Adding 0.5g of chitosan quaternary ammonium salt grafted polyamide 6 and 5g of polyamide 6 into 80% formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.3mL/h, the spinning voltage is 25kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Example 2
(1) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.4g of DL-aspartic acid, stirring and reacting at 90 ℃ for 24h, adding a product into a 2% hydrochloric acid solution after reaction, stirring and reacting at room temperature for 24h, filtering a solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(2) Dissolving 0.5g of triethanolamine quaternary ammonium salt into a xylene solvent, adding 2g of polycarboxylic hydrophilic modified chitosan, 1.5g of acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, then dropwise adding 0.06g of p-toluenesulfonic acid, stirring for grafting reaction for 48 hours at 120 ℃, cooling after reaction, adding deionized water for precipitation, filtering the solvent, washing with deionized water and ethanol, and obtaining the chitosan quaternary ammonium salt grafted polyamide 6.
(3) Adding 1g of chitosan quaternary ammonium salt grafted polyamide 6 and 5g of polyamide 6 into 85% formic acid solution in mass ratio, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.6mL/h, the spinning voltage is 20kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Example 3
(1) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.5g of DL-aspartic acid, stirring and reacting at 70 ℃ for 36h, adding the product into 2% hydrochloric acid solution after the reaction, stirring and reacting at room temperature for 24h, filtering the solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(2) Dissolving 0.6g of triethanolamine quaternary ammonium salt into a xylene solvent, adding 2g of polycarboxylic hydrophilic modified chitosan, 2g of acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, then dropwise adding 0.08g of p-toluenesulfonic acid, stirring and grafting for reaction for 48 hours at 140 ℃, cooling after reaction, adding deionized water for precipitation, filtering the solvent, and washing with deionized water and ethanol to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
(3) Adding 1.6g of chitosan quaternary ammonium salt grafted polyamide 6 and 5g of polyamide 6 into 70% formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.6mL/h, the spinning voltage is 25kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Example 4
(1) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.6g of DL-aspartic acid, stirring and reacting at 90 ℃ for 12h, adding the product into 2% hydrochloric acid solution after the reaction, stirring and reacting at room temperature for 24h, filtering the solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(2) Dissolving 1g of triethanolamine quaternary ammonium salt into a xylene solvent, adding 2g of polycarboxylic hydrophilic modified chitosan, 2.5g of acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, then dropwise adding 0.13g of p-toluenesulfonic acid, stirring and grafting for 24 hours at 140 ℃, cooling after reaction, adding deionized water for precipitation, filtering the solvent, and washing with deionized water and ethanol to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
(3) Adding 1.6g of chitosan quaternary ammonium salt grafted polyamide 6 and 5g of polyamide 6 into 80% formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.6mL/h, the spinning voltage is 22kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Example 5
(2) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.8g of DL-aspartic acid, stirring and reacting at 80 ℃ for 24h, adding the product into 2% hydrochloric acid solution after reaction, stirring and reacting at room temperature for 36h, filtering the solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(2) Dissolving 1.2g of triethanolamine quaternary ammonium salt into a xylene solvent, adding 2g of polycarboxylic hydrophilic modified chitosan, 3g of acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, then dropwise adding 0.16g of p-toluenesulfonic acid, stirring and grafting for reaction for 48 hours at 130 ℃, cooling after reaction, adding deionized water for precipitation, filtering the solvent, and washing with deionized water and ethanol to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
(3) Adding 2g of chitosan quaternary ammonium salt grafted polyamide 6 and 5g of polyamide 6 into 85% formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.6mL/h, the spinning voltage is 20kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
Comparative example 1
(1) Adding 1g of epoxidized Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding 0.2g of DL-aspartic acid, stirring and reacting at 90 ℃ for 24 hours, adding a product into 2% hydrochloric acid solution after the reaction, stirring and reacting at room temperature for 24 hours, filtering the solvent, and washing the product with ethanol and deionized water to obtain polycarboxyl hydrophilic modified chitosan;
(2) Adding 1g of polycarboxyl hydrophilic modified chitosan and 5g of polyamide 6 into 85% formic acid solution in mass ratio, stirring and dissolving, then performing electrostatic spinning, wherein the flow rate of a spinning solution is 0.6mL/h, the spinning voltage is 20kV, and after spinning, soaking and washing the fiber in deionized water to obtain the polyamide composite fiber.
The polyamide composite fibers obtained in examples and comparative examples were prepared into a specimen of 10cm × 3cm × 0.4cm, and the breaking strength and the drawing rate were measured by an electronic single fiber strength tester and 1cm/min.
Escherichia coli was used as a test strain, and polyamide composite fiber membrane samples were each plated in 24-well plates and 1X 10 8 Inoculating CFU/mL Escherichia coli stock solution on the sample to culture, and taking the sample as an experimental sample; culturing a non-polyamide composite fiber membrane sample by using a stock solution to obtain a blank sample; and then, diluting the bacterial liquid cultured in the experimental sample and the blank sample in an equal gradient manner, transferring 0.1mL of bacterial suspension, dropwise adding the bacterial suspension into a culture dish containing a peptone culture medium, culturing at the constant temperature of 37 ℃ for 24h, respectively determining the number of bacterial colonies, and calculating the bacteriostasis rate.
Bacteriostasis rate = (number of blank sample colonies-number of experimental sample colonies)/number of blank sample colonies.
Claims (7)
1. An antibacterial modified polyamide composite fiber is characterized in that: the antibacterial modified polyamide composite fiber is synthesized by the following method: adding the chitosan quaternary ammonium salt grafted polyamide 6 and the polyamide 6 into a formic acid solution, stirring and dissolving, then carrying out electrostatic spinning, wherein the flow rate of a spinning solution is 0.3-0.6mL/h, the spinning voltage is 20-25kV, and after spinning, dipping and washing the fiber in deionized water to obtain the antibacterial modified polyamide composite fiber.
2. The antibacterial modified polyamide composite fiber according to claim 1, characterized in that: the mass ratio of the chitosan quaternary ammonium salt grafted polyamide 6 to the polyamide 6 is 0.1-0.4.
3. The antibacterial modified polyamide composite fiber according to claim 1, characterized in that: the chitosan quaternary ammonium salt grafted polyamide 6 is synthesized by the following method:
s1, dissolving chitosan into an acetic acid solution, adding benzaldehyde, and reacting to obtain Schiff base protective chitosan; then adding the mixture into a sodium hydroxide solution, uniformly stirring, adding epoxy chloropropane, and reacting to obtain epoxidized Schiff base chitosan;
s2, adding the epoxy Schiff base chitosan into dimethyl sulfoxide, heating and stirring uniformly, adding DL-aspartic acid, stirring for reaction, adding a product into a hydrochloric acid solution, and performing deprotection to obtain the polycarboxyl hydrophilic modified chitosan;
s3, adding triethanolamine and benzyl chloride into an ethanol solvent, and carrying out heating reflux reaction to obtain triethanolamine quaternary ammonium salt; and dissolving triethanolamine quaternary ammonium salt into a xylene solvent, adding polycarboxyl hydrophilic modified chitosan, acrylic acid grafted polyamide 6 and an N, N-dimethylformamide solvent, uniformly stirring, dropwise adding p-toluenesulfonic acid, and stirring for grafting reaction to obtain the chitosan quaternary ammonium salt grafted polyamide 6.
4. The antibacterial modified polyamide composite fiber according to claim 3, characterized in that: the mass ratio of the epoxidized chitosan to the DL-aspartic acid in S2 is 1.2-0.8.
5. The antibacterial modified polyamide composite fiber according to claim 3, characterized in that: the reaction temperature in the S2 is 70-90 ℃, and the reaction time is 12-36h.
6. The antibacterial modified polyamide composite fiber according to claim 3, characterized in that: the mass ratio of triethanolamine quaternary ammonium salt, polycarboxyl hydrophilic modified chitosan, acrylic acid grafted polyamide 6 and p-toluenesulfonic acid in S3 is (weight ratio) 0.1-0.6.
7. The antibacterial modified polyamide composite fiber according to claim 3, characterized in that: the temperature of the grafting reaction in the S3 is 110-140 ℃, and the time is 24-48h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116410440A (en) * | 2023-04-03 | 2023-07-11 | 佛山市惠安家居用品有限公司 | Hydrophilic antibacterial sponge and preparation method thereof |
| CN116442615A (en) * | 2023-06-14 | 2023-07-18 | 汕头市兴裕泰纺织有限公司 | Cool antibacterial fabric containing inorganic composite nylon, and preparation method and application thereof |
| CN117618624A (en) * | 2023-11-15 | 2024-03-01 | 扬州景怡医疗科技有限公司 | Medical polymer bandage convenient for biodegradation and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116410440A (en) * | 2023-04-03 | 2023-07-11 | 佛山市惠安家居用品有限公司 | Hydrophilic antibacterial sponge and preparation method thereof |
| CN116410440B (en) * | 2023-04-03 | 2024-04-19 | 佛山市惠安家居用品有限公司 | Hydrophilic antibacterial sponge and preparation method thereof |
| CN116442615A (en) * | 2023-06-14 | 2023-07-18 | 汕头市兴裕泰纺织有限公司 | Cool antibacterial fabric containing inorganic composite nylon, and preparation method and application thereof |
| CN117618624A (en) * | 2023-11-15 | 2024-03-01 | 扬州景怡医疗科技有限公司 | Medical polymer bandage convenient for biodegradation and preparation method thereof |
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