CN1394999A - Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface - Google Patents
Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface Download PDFInfo
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- CN1394999A CN1394999A CN 02128949 CN02128949A CN1394999A CN 1394999 A CN1394999 A CN 1394999A CN 02128949 CN02128949 CN 02128949 CN 02128949 A CN02128949 A CN 02128949A CN 1394999 A CN1394999 A CN 1394999A
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- fibre
- acyl chlorides
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- 239000000835 fiber Substances 0.000 title claims abstract description 44
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 150000001263 acyl chlorides Chemical class 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 229920003043 Cellulose fiber Polymers 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 5
- 238000002329 infrared spectrum Methods 0.000 abstract description 2
- 238000002411 thermogravimetry Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 abstract description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002671 adjuvant Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000003899 bactericide agent Substances 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XQBXGCKZZNVZEC-UHFFFAOYSA-N (dipropylamino) 2-methylprop-2-enoate Chemical compound C(CC)N(CCC)OC(C(=C)C)=O XQBXGCKZZNVZEC-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- -1 sulfonic group Chemical group 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000029052 metamorphosis Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- KBGBDGQCRFNDLU-UHFFFAOYSA-N benzyl(diethyl)azanium;chloride Chemical compound Cl.CCN(CC)CC1=CC=CC=C1 KBGBDGQCRFNDLU-UHFFFAOYSA-N 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The preparation method of macromolecular anti-bacterial fibre with surface high-grafting ratio belongs to the field of macromolecular material, and includes the following steps: firstly, making acryl chloride containing C equal to C unsaturated double bond and tertiary amine monomer matter with OH group produce reaction, adding triethylamine as adjuvant to obtain tertiary amine with C equal to C bond, adding benzyl chloride, making reflux reactino, adding macromolecular fibre and initiator, after reaction is completed, using solution to stir and rinse reaction product, suction filtering and drying so as to obtain the invented product. By means of infrared spectrum analysis, TGA analysis and weighing analysis these analysises show that the monomer is grafted and polymerized on the surface of fibre, and grafting ratio range is 50%-150%.
Description
Technical field
The present invention relates to a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface, belong to technical field of polymer materials.
Background technology
In use generally there is the problem of excess residual in the micromolecule bactericidal agent, can cause the secondary pollution of water and to the harm of health.Compare with low molecule bactericide, that the macromolecule bactericide has is non-volatile, chemically stable good, generally can not infiltrate advantages such as human or animal's skin, toxicity is little, thereby has good application prospects.Because fiber has very big specific area, be filled into easily in the various bactericidal units simultaneously and go, so fiber product is one of most important kind of macromolecule sterilization material.Sterilization fibre can or adopt the method for surface graft modification to obtain by bactericide and polyblend spinning.Obviously, latter's economic and reliable more.Its major advantage has: (1) bactericide utilization ratio height.And the bactericide of the fibrous inside that co-blended spinning obtains can not contact with bacterium, and a large amount of bactericide do not have sterilization functions.(2) bactericide is connected with covalent bond with base material, stable performance.The mode of co-blended spinning then exists problems such as bactericide migration, can lose efficacy after use a period of time.(3) surface grafting can be selected different monomers and base material, structure that can be different according to Application Design.
Quaternary ammonium salt is one of the most frequently used micromolecule antiseptic, with the method for polymerisable quaternary ammonium salt monomer by surface grafting, is linked at the macromolecular fibre surface, can be used for application fields such as water treatment.Present existing technology has
Use the monomer of hydrophilic radicals such as hydroxyl, alkoxyl, amido, pyrrolidinyl among the United States Patent (USP) U.S.5506188, contain the monomer of CATION dissociation groups such as carboxyl, carboxymethyl, sulfonic group, sulfoethyl, phosphate, phosphorus methyl and contain the monomer of anion dissociation groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt, radiation polymerization becomes the macromonomer of degree of polymerization 10-100, and add monose (as glucose), base material is carried out radiation grafting.Radiation ray has ultraviolet light, α-ray, β-ray, γ-ray, eletron beam, and base material comprises cellulose, polyolefin, animal hair, leather and the synthetic leather etc. of various forms such as fiber, diaphragm, powder.Monose can quicken the speed that macromonomer is impregnated into base material, thereby can obviously improve the grafting efficiency of macromonomer.The sorbing material that makes is used for removing stink from gas, liquid.
The fibrous filter media of European patent E.P.433661A3, surface grafting one deck overlie polymer is by the unsaturated vinyl monomer that contains quaternary ammonium or amido.Filter medium has positive ξDian Wei when pH=7, strengthen adsorption capacity.
But in above-mentioned two patented technologies, the high-molecular anti-bacteria material of grafting quaternary ammonium salt all is to utilize its surperficial positive charge, and absorption has the bacterium of negative electricity.And the bacterium of handling through anti-biotic material, its physiologically active and metamorphosis are not observed variation.Just ineffective after anti-bacterial fibre adsorbs a certain amount of bacterium, even because the anti-bacterial fibre surface aggregation a large amount of bacteriums and become pollution sources.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface, prepare a series of high percent grafting quaternary ammonium salt grafting polymer anti-bacterial fibres.The fiber that obtains not only has quick absorption bacterium from water, thereby reaches the function of removing the middle bacterium of anhydrating, also really has the inhibition bacterial activity, further the effect of kill bacteria.Macromolecular sterilization fibre through surface grafting preparation is a kind of portable above, does not need specific operation condition, cheap macromolecule water treatment agent.Processing target mainly concentrates on the removal to pathogenetic bacteria.This sterilization fibre can also be used as hospital gauze, artificial skin and take lining.
The preparation method of the high-molecular anti-bacterial fibre with high grafting rate in surface that the present invention proposes may further comprise the steps:
(1) acyl chlorides that contains the C=C unsaturated double-bond and the reaction that has the tertiary amine monomers material of OH group: with toluene, benzene, carrene or oxolane is solvent, the adding triethylamine is an auxiliary agent, the mol ratio of hydroxyl and acyl chlorides and auxiliary agent is 1: 1～8: 1～1.2, the molar concentration that has the tertiary amine monomers material of OH group is 0.5～2mol/L, reaction temperature is 0～20 ℃, and the reaction time is 8～24 hours.Acyl chlorides can be third rare acyl chlorides, the rare acyl chlorides of methyl-prop; Tertiary amine can have one or two-OH, can be N, N-dimethylethanolamine, N, and N-diethyl ethylene diamine, N methyldiethanol amine, N-ethyldiethanolamine, reaction makes the tertiary amine that has the C=C key.
(2) above-mentioned product is a solvent with acetone, carrene, and concentration is 0.5～2mol/L, adds benzyl chloride, and containing the tertiary amine of C=C unsaturated double-bond and the mol ratio of benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6～18 hours.
(3) add above-mentioned second step product and the macromolecular fibre in reactor, macromolecular fibre can be cellulose fibre, chitin fiber etc.Add solvent, the molar concentration of the second step product in solvent is 0.6～1.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～1: 25.Solvent can be water and rare nitric acid, dilute sulfuric acid, watery hydrochloric acid.
(4) inflated with nitrogen adds initator to drain air in reactor, and making the concentration of initator in above-mentioned solution is 0.01～0.03mol/L, and initator can be ammonium ceric nitrate, Cericammoniumsulfate.Under agitation continue to fill nitrogen, reaction temperature is 20 ℃～60 ℃, reacts 0.5～4 hour.
(5) after reaction finished, with solution stirring, flushing reactant, suction filtration, the aqueous solution with acetone carried out extracting about 6～24 hours to the good fiber of grafting then, and was dry under being lower than 60 ℃ then.
The preparation method of the high-molecular anti-bacterial fibre with high grafting rate in surface that the present invention proposes, anti-bacterial fibre prepared therefrom, by infrared spectrum analysis, TGA analysis and the analysis etc. of weighing, the proof monomer is by the surface of glycerol polymerization to fiber, by weight between the percent grafting scope 50%～150% that method is measured.
Escherichia coli E.coli and staphylococcus aureus were cultivated through 18 hours, with the mixed of sterilized water with 1: 4.The anti-bacterial fibre of above-mentioned bacterium liquid 100ml and the present invention preparation is mixed in shaking bottle, under 37 ℃, 150rpm, cultivate, regularly take out certain amount of mixed solution, survey viable count with dull and stereotyped progression dilution method.The order of magnitude of number of bacteria decline 3～8 in the bacterium liquid.To mix the anti-bacterial fibre of certain hour in bacterium liquid directly observes under environmental scanning electron microscope, can observe the metamorphosis of bacterium under the anti-bacterial fibre effect of the present invention's preparation, bacterium on the high percent grafting anti-bacterial fibre over time, form generation distortion breaks until thalline.And the morphosis that the bacterium on the low percent grafting anti-bacterial fibre of prior art still is kept perfectly.
The specific embodiment
Embodiment 1
(1) N of rare acyl chlorides of methyl-prop and 0.1mol, the reaction of N-dimethylethanolamine is a solvent with 100ml benzene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-dimethylethanolamine and acyl chlorides and auxiliary agent is 1: 2: 1,0 ℃ of reaction temperature, the reaction time is 16 hours.Obtaining product is methacrylic acid 2-(N, N dimethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of methacrylic acid 2-(N, N dimethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of methyl-prop-alkyl dimethyl ammonium chloride.
(3) in reactor, add the rare acyl-oxygen ethyl-benzyl of 1g cellulose fiber peacekeeping 0.02mol methyl-prop-alkyl dimethyl ammonium chloride, add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 30 ℃, reacts 1 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 67%.
Embodiment 2
The reaction of the N methyldiethanol amine of (1) third rare acyl chlorides and 0.1ml is a solvent with 200ml benzene, and the adding triethylamine is an auxiliary agent, and the mol ratio of N methyldiethanol amine and acyl chlorides and auxiliary agent is 1: 8: 1,5 ℃ of reaction temperatures, and the reaction time is 24 hours.Obtaining product is acrylic acid 2-(N methyl amido) diethylester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N methyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate.
(3) add the 1.5g cellulose fibre in reactor, the rare acyl-oxygen ethyl-benzyl of 0.02mol methyl-prop-alkyl dimethyl ammonium chloride and the rare acyl-oxygen ethyl-benzyl of 0.002mol dipropyl-ammonio methacrylate add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 40 ℃, reacts 0.5 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 50 ℃ then.Weigh percent grafting 79%.
Embodiment 3
(1) reaction of the N-ethyldiethanolamine of rare acyl chlorides of methyl-prop and 0.1ml is a solvent with 200ml benzene, and the adding triethylamine is an auxiliary agent, and the mol ratio of N-ethyldiethanolamine and acyl chlorides and auxiliary agent is 1: 16: 1,5 ℃ of reaction temperatures, and the reaction time is 24 hours.Obtaining product is methacrylic acid 2-(N ethyl amido) diethylester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of methacrylic acid 2-(N ethyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate.
(3) add the 1.5g cellulose fibre in reactor, the rare acyl-oxygen ethyl-benzyl of 0.02mol methyl-prop-alkyl dimethyl ammonium chloride and 0.004mol dimethyl propylene acyl-oxygen ethyl-benzyl-ethyl ammonium chloride add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 40 ℃, reacts 0.5 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 89%.
Embodiment 4
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-dimethylethanolamine is a solvent with the 50ml carrene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-dimethylethanolamine and acyl chlorides and auxiliary agent is 1: 4: 1.2,10 ℃ of reaction temperatures, and the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N methyl amido) diethylester.
(2) above-mentioned product is a solvent with the 50ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N methyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-alkyl dimethyl ammonium chloride.
(3) add 2g chitin fiber and the rare acyl-oxygen ethyl-benzyl of 0.015mol methyl-prop-alkyl dimethyl ammonium chloride in reactor, the rare nitric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen adds initator 0.000251mol Cericammoniumsulfate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 50 ℃, reacts 1 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 12 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 62%.
Embodiment 5
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-diethyl ethylene diamine is a solvent with the 50ml oxolane, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-diethyl ethylene diamine and acyl chlorides and auxiliary agent is 1: 4: 1.1,10 ℃ of reaction temperatures, and the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N, N diethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with 50ml acetone, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N, N diethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride.
(3) add 1g cellulose fiber peacekeeping 0.025mol third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride in reactor, the dilute sulfuric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen is to drain air in reactor, and adding the 0.000501mol ammonium ceric nitrate is initator, under agitation continues to fill nitrogen, and reaction temperature is 50 ℃, reacts 2 hours.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 18 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 69%.
Embodiment 6
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-diethyl ethylene diamine is a solvent with 50ml toluene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-diethyl ethylene diamine and acyl chlorides and auxiliary agent is 1: 4: 1.2,10 ℃ of reaction temperatures, the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N, N diethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with the 50ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N, N diethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride.
(3) add 1g cellulose fiber peacekeeping 0.035mol third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride in reactor, the watery hydrochloric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen is to drain air in reactor, and adding the 0.000752mol ammonium ceric nitrate is initator, under agitation continues to fill nitrogen, and reaction temperature is 60 ℃, reacts 4 hours.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 24 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 71%.
Claims (7)
1, a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface is characterized in that this method may further comprise the steps:
(1) making the molar concentration of the tertiary amine monomers material that has the OH group with solvent is 0.5～2mol/L, in having the tertiary amine monomers material of OH group, add acyl chlorides and the triethylamine auxiliary agent that contains the C=C unsaturated double-bond, wherein the mol ratio of tertiary amine monomers material, acyl chlorides, auxiliary agent is 1: 1～8: 1～1.2, reaction temperature is 0～20 ℃, reaction time is 8～24 hours, and reaction makes the tertiary amine that has the C=C key;
(2) adding benzyl chloride in above-mentioned product, is solvent with acetone, carrene, and the concentration that makes the tertiary amine of the above-mentioned C=C of having key is 0.5～2mol/L, and the mol ratio of tertiary amine and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6～18 hours;
(3) add macromolecular fibre in the above-mentioned second step product, add solvent, making the molar concentration of above-mentioned product in solvent is 0.6～1.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～25;
(4) add initator in above-mentioned solution, making the concentration of initator in above-mentioned solution is 0.01～0.03mol/L, and inflated with nitrogen under agitation continues to fill nitrogen to drain air, and reaction temperature is 20 ℃～60 ℃, reacts 0.5～4 hour;
(5) after reaction finishes, stir, wash reactant with reactant liquor, suction filtration, the aqueous solution with acetone carried out extracting about 6～24 hours to the good fiber of grafting then, and is dry under being lower than 60 ℃ then.
2, the method for claim 1 is characterized in that used solvent in the first step wherein is any in toluene, benzene, carrene or the oxolane.
3, the method for claim 1 is characterized in that wherein acyl chlorides is third rare acyl chlorides or the rare acyl chlorides of methyl-prop in the first step.
4, the method for claim 1 is characterized in that the tertiary amine in the first step wherein has one or two OH group, is N, N-dimethylethanolamine, N, any in N-diethyl ethylene diamine, N methyldiethanol amine or the N-ethyldiethanolamine.
5, the method for claim 1 is characterized in that wherein the macromolecular fibre in the 3rd step is cellulose fibre or chitin fiber.
6, the method for claim 1 is characterized in that wherein solvent in the 3rd step is any in water, rare nitric acid, dilute sulfuric acid or the watery hydrochloric acid.
7, the method for claim 1 is characterized in that wherein the initator in the 4th step is ammonium ceric nitrate or Cericammoniumsulfate.
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| CN100465215C (en) * | 2006-12-15 | 2009-03-04 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| US8258235B2 (en) * | 2004-10-04 | 2012-09-04 | Nitto Denko Corporation | Biodegradable cationic polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8258235B2 (en) * | 2004-10-04 | 2012-09-04 | Nitto Denko Corporation | Biodegradable cationic polymers |
| CN100465215C (en) * | 2006-12-15 | 2009-03-04 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| CN102119246B (en) * | 2008-08-11 | 2012-09-26 | 仓敷纺绩株式会社 | Sliver for spinning, process for producing same, and spun yarn and textile product both using same |
| CN103015160A (en) * | 2012-12-18 | 2013-04-03 | 武汉纺织大学 | Method for producing bacteriostatic sole, lining or insole by using bacteriostatic agent |
| CN103015160B (en) * | 2012-12-18 | 2015-06-03 | 武汉纺织大学 | Method for producing bacteriostatic sole, lining or insole by using bacteriostatic agent |
| CN104892842A (en) * | 2015-05-15 | 2015-09-09 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose, preparation method and application thereof |
| CN111519432A (en) * | 2020-05-12 | 2020-08-11 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN114232336A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Hemp diphenol modified viscose fiber and preparation method thereof |
| CN114686733A (en) * | 2022-04-12 | 2022-07-01 | 江苏中基复合材料有限公司 | Cast-rolled aluminum foil for aseptic packaging and preparation method thereof |
| CN114686733B (en) * | 2022-04-12 | 2022-11-18 | 江苏中基复合材料有限公司 | Cast-rolling aluminum foil for aseptic packaging and preparation method thereof |
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