CN100460452C - Preparing process of antiseptic graft polymer in micron and nanometer composite structure - Google Patents
Preparing process of antiseptic graft polymer in micron and nanometer composite structure Download PDFInfo
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- CN100460452C CN100460452C CNB2006101652417A CN200610165241A CN100460452C CN 100460452 C CN100460452 C CN 100460452C CN B2006101652417 A CNB2006101652417 A CN B2006101652417A CN 200610165241 A CN200610165241 A CN 200610165241A CN 100460452 C CN100460452 C CN 100460452C
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 230000002421 anti-septic effect Effects 0.000 title abstract description 5
- 229920000578 graft copolymer Polymers 0.000 title abstract 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 49
- -1 benzyl halide Chemical class 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 28
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 230000035484 reaction time Effects 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 239000004743 Polypropylene Substances 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 230000005059 dormancy Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012965 benzophenone Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 10
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 10
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 10
- 229940113124 polysorbate 60 Drugs 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 9
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 8
- 229940073608 benzyl chloride Drugs 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DSPKXCZGSQZMRS-UHFFFAOYSA-N C(C1=CC=CC=C1)Cl.[Cl] Chemical compound C(C1=CC=CC=C1)Cl.[Cl] DSPKXCZGSQZMRS-UHFFFAOYSA-N 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 239000002736 nonionic surfactant Substances 0.000 abstract description 11
- 230000003115 biocidal effect Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 14
- 125000004494 ethyl ester group Chemical group 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 125000005395 methacrylic acid group Chemical group 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- ZRNQYPVIKLEMCN-UHFFFAOYSA-N [benzyl(ethyl)amino] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON(CC)CC1=CC=CC=C1 ZRNQYPVIKLEMCN-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 239000007833 carbon precursor Substances 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
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 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
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000004745 nonwoven fabric Substances 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Treatments Of Macromolecular Shaped Articles (AREA)
- Cosmetics (AREA)
Abstract
The present invention is process of antiseptic graft polymer in micron and nanometer composite structure, and belongs to the field of polymer technology. The process includes adding solvent, triethylamine and acyl chloride with unsaturated C=C double bond into solution of tertiary amine with hydroxy radical to obtain product A; adding solvent and benzyl halide for reflux reaction to obtain product B; dissolving the product B separately in water and oily solvent; compounding water-in-oil microemulsion with the water solution, the oily solution and non-ionic surfactant and adding photoinitiator; irradiating with ultraviolet ray for reaction; extracting the grafted polymer with mixed solvent of water and acetone and drying. The antiseptic graft polymer in micron and nanometer composite structure has great specific surface area and specific antiseptic function and is used as antibiotic material for clothing, appliance, sanitary ceramic product, etc.
Description
Technical field
The present invention relates to the preparation method that a kind of surface has micron and nanometer composite structure grafted antibacterial polymkeric substance, belong to technical field of polymer materials.
Background technology
Antibiotic polymer material mainly can be by antiseptic-germicide and polymer blending, and antiseptic-germicide is coated in three kinds of methods such as polymer surfaces or the graft modification of employing polymer surfaces and obtains.Obviously, latter's economic and reliable more.Its major advantage has: sterilant utilising efficiency height.Sterilant is connected with covalent linkage with base material, stable performance.
The polymkeric substance of surface grafting quaternary ammonium salt is that a kind of antibacterial effect is good, cheap solid phase surface contact anti-biotic material.It is by electrostatic attraction and hydrophobic interaction absorption bacterium, but with kill bacteria after thalline directly contacts.Present existing technology has:
Use the monomer of hydrophilic radicals such as hydroxyl, alkoxyl group, amido, pyrrolidyl among the United States Patent (USP) U.S.5506188, contain the monomer of positively charged ion dissociation groups such as carboxyl, carboxymethyl, sulfonic group, sulfoethyl, phosphate, phosphorus methyl and contain the monomer of negatively charged ion dissociation groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt, radio polymerization becomes the macromonomer of polymerization degree 10-100, and add monose (as glucose), base material is carried out radiation grafting.Radiation ray has UV-light, α-ray, β-ray, γ-ray, eletron beam, and base material comprises Mierocrystalline cellulose, polyolefine, 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.
United States Patent (USP) U.S.5561167 selects ion-exchange fiber (containing cation exchange group and anion exchange groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt such as carboxyl or sulfonic group) for use, pass through ion exchange reaction, make partial cation cation exchange groups (being less than 50%) connect antibacterial metal ions (as silver ions, cupric ion, zine ion etc.), make antibacterial fiber.Patent is also used it and activated carbon fiber with, makes water purifier, and has inquired into fibre array density (general 0.13g/cm
3) with the relation of water flow velocity.
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.Filtration medium has positive ξDian Wei when pH=7, strengthen adsorptive power.
Adopt radiation graft process to prepare antiseptic material of pyridine salt type polymer among the Chinese patent C.N.1223273, comprise pre-irradiation grafting and common radiation grafting, go through the radiation grafting pyridine monomer to polymeric matrix and two steps of quaterisation.The radiation grafting pyridine monomer is as follows to the polymer-based carbon precursor reactant, is solvent with the deionized water, and vinylpyridine is a monomer, and matrix is a polypropylene
(PP) non-woven fabrics, source of radiation are cobalt source (Co
60), and add a small amount of stopper.After graft reaction finishes, add ethanol swelling graft product, add excessive 100% long fatty carbon chain halohydrocarbon then, reacted 6～8 hours down at 70 ℃～80 ℃.
In the above-mentioned patented technology, the graftomer anti-biotic material all is simply the antibacterial monomer wiring solution-forming to be grafted to polymer surfaces, and the surface topography of material is not studied and selected.Because the entanglement of surface grafting chain in the graft reaction, these material surfaces are generally raised structures smooth or that have several microns sizes.
Summary of the invention
The objective of the invention is to propose the preparation method that a kind of surface has micron and nanometer composite structure grafted antibacterial polymkeric substance, adopt the method for ultraviolet light irradiation, directly grafting has the polymkeric substance of micron and nanometer composite structure on polymers for general use surface, to obtain a kind of anti-biotic material.
The surface that the present invention proposes has the preparation method of the grafted antibacterial polymkeric substance of micron and nanometer composite structure, may further comprise the steps:
(1) be solvent with toluene, benzene, methylene dichloride or tetrahydrofuran (THF), the volumetric molar concentration that makes the tertiary amine that has hydroxyl is 0.5～2mol/L, in the solution of the tertiary amine that has hydroxyl, add triethylamine and the acyl chlorides that contains the C=C unsaturated double-bond, obtain reaction product A, adding mol ratio is: acyl chlorides: hydroxyl: triethylamine=1～8:1:1～1.2, temperature of reaction is 0～5 ℃, and the reaction times is 8～24 hours;
(2) in above-mentioned reaction product A, add any in acetone, methylene dichloride or the acetonitrile as solvent, making the solution volumetric molar concentration is 0.5～2mol/L, add benzyl halogenide again and carry out back flow reaction, obtain reaction product B, adding mol ratio is: reaction product A: benzyl halogenide=1:0.9～1.1, and the reaction times is 6～8 hours;
(3) in reaction product B, add deionized water; obtain the aqueous solution; the volumetric molar concentration of the aqueous solution is 0.2～1.6mol/L; in reaction product B, add oil-based solvent; obtain oily solution; the volumetric molar concentration of oily solution is 0.05～0.6mol/L; with the aqueous solution; oily solution mixes mutually with nonionic surface active agent; be made into water in oil microemulsion; adding weight percent is: the aqueous solution: oil phase solvent: nonionic surface active agent=1:5～20:0.2～0.4; with light trigger with any ratio be coated in polymer surfaces after organic solvent mixes mutually; treat after the organic solvent volatilization polymkeric substance to be immersed in the microemulsion; under protection of inert gas, open UV-light and carry out irradiation reaction, irradiation intensity be 20～40 milliwatts/centimetre
2, the irradiation reaction temperature is 20 ℃～70 ℃, 5～40 minutes reaction times; Or polymkeric substance light dormancy base is immersed in the microemulsion, open UV-light and carry out irradiation reaction, irradiation intensity be 20～40 milliwatts/centimetre
2, the irradiation reaction temperature is 20 ℃～70 ℃, 5～40 minutes reaction times;
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 20～24 hours, be lower than 60 ℃ dry down.
Acyl chlorides in the aforesaid method can be acrylate chloride or methacrylic chloride.
Tertiary amine in the aforesaid method has one or two hydroxyl, for example can be N, N-dimethylethanolamine, N, any in N-diethylethanolamine, N-dimethyl n Propanolamine, N-dimethylisopro panolamine or the N methyldiethanol amine.
Halogenide in the aforesaid method can be in muriate, bromide or the iodide any, for example can be for Benzyl Chloride, to nitro Benzyl Chloride, 2,5-dimethyl chlorination benzyl, any in a benzyl chloride chlorine or the benzyl chloride chlorine.
Oil phase solvent in the aforesaid method can be chloroform or methylene dichloride.
Nonionic surface active agent in the aforesaid method can be the mixture of class of department 80 or class 80 of department and polysorbate60, and the mixing quality ratio is: class of department 80: polysorbate60=1:0.15.
The preparation method of the polymkeric substance light dormancy base in the aforesaid method is: polymkeric substance is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, irradiation intensity be 20～40 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 1～6 minute.
Polymkeric substance in the aforesaid method can be in polyethylene, polypropylene, polyacrylonitrile or the polyester any.
The surface that the present invention proposes has the preparation method of the grafted antibacterial polymkeric substance of micron and nanometer composite structure, because polymerizable quaternary ammonium salt solubilized all in water and oil phase, behind monomer-grafted in the oil phase, because grafted chain tangles, obtain micrometer structure, and microemulsion aqueous phase monomer grafted chain in the graft polymerization process is compressed by interfacial tension always, forms nanostructure.By the photo-grafting polyreaction grafting efficiency height that UV-light causes, can more strictly control graft reaction and carry out on the surface of base material, can not damage the material main body performance.The surface for preparing has the micron and nanometer composite structure anti-biotic material, has bigger specific surface area, bigger with the contact area of bacterium, and nanostructure has special antibacterial, therefore the surface have the anti-microbial property of the anti-biotic material of micron and nanometer composite structure will be more outstanding.Prepared modify and graft polymkeric substance can be used as anti-biotic material, is widely used in the fiber garment that wears from daily, to every field such as household household electrical appliance commonly used, sanitary ware, plastics films.
Embodiment
Embodiment 1
(1) be solvent with 100ml benzene, with the N of 0.1mol, the N-dimethylethanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 2:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) ethyl ester.
(2) adding the 100ml methylene dichloride in methacrylic acid 2-(N, N-dimethyl amido) ethyl ester of 0.1mol is solvent, and the Benzyl Chloride that adds 0.1mol again carries out back flow reaction, reacts 6 hours; Obtaining product is methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in reaction product methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride is solvent; the volumetric molar concentration that makes solution is 0.8mol/L; in another part reaction product methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, add chloroform; the volumetric molar concentration that makes solution is 0.05mol/L; with the aqueous solution; oily solution and non-ionic surfactant span 80 mix; be made into water in oil microemulsion; adding weight percent is: the aqueous solution: oil-phase solution: the 80=1:10:0.2 of class of department; with benzophenone be coated in polypropylene surface after acetone mixes mutually; treat after the acetone volatilization polypropylene to be immersed in the microemulsion; under protection of inert gas; open UV-light and carry out irradiation reaction, irradiation intensity be 20 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 20 minutes reaction times.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 2
(1) be solvent with 100ml benzene, be mixed with liquid with the N methyldiethanol amine of 0.05mol, add triethylamine and methacrylic chloride, the mol ratio of acyl chlorides and hydroxyl and triethylamine is 8:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N-ethyl amido) diethyl ester.
(2) adding the 100ml methylene dichloride in methacrylic acid 2-(N-ethyl amido) diethyl ester of 0.05mol is solvent, and the Benzyl Chloride that adds 0.05mol again carries out back flow reaction, and the reaction times is 8 hours; Obtaining product is dimethyl allene acyl-oxygen ethyl-benzyl-ammonio methacrylate.
(3) adding deionized water in reaction product dimethyl allene acyl-oxygen ethyl-benzyl-ammonio methacrylate is solvent, the volumetric molar concentration that makes solution is 0.6mol/L, in another part reaction product dimethyl allene acyl-oxygen ethyl-benzyl-ammonio methacrylate, add chloroform, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix, be made into water in oil microemulsion, the weight percent of adding is: the aqueous solution: oil-phase solution: the 80=1:10:0.3 of class of department; Polypropylene film light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 30 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 40 minutes reaction times.Wherein the preparation method of polypropylene film light dormancy base is: polypropylene film is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, irradiation intensity be 20 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 3 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 3
(1) be solvent with the 100ml tetrahydrofuran (THF), be mixed with liquid with the N methyldiethanol amine of 0.05mol, add triethylamine and acrylate chloride, the mol ratio of acyl chlorides and hydroxyl and triethylamine is 4:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is vinylformic acid 2-(N-methyl amido) diethyl ester.
(2) adding the 100ml methylene dichloride in vinylformic acid 2-(N-methyl amido) diethyl ester of 0.05mol is solvent, and the Benzyl Chloride that adds 0.05mol again carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is two acrylyl oxy-ethyls-benzyl-ammonio methacrylate.
(3) adding deionized water in reaction product two acrylyl oxy-ethyls-benzyl-ammonio methacrylate is solvent; the volumetric molar concentration that makes solution is 0.8mol/L; in another part reaction product two acrylyl oxy-ethyls-benzyl-ammonio methacrylate, add methylene dichloride; the volumetric molar concentration that makes solution is 0.05mol/L; with the aqueous solution; oily solution and non-ionic surfactant span 80 mix; be made into water in oil microemulsion; adding weight percent is: the aqueous solution: oil phase solvent: the 80=1:5:0.3 of class of department; with benzophenone be coated in polyethylene surface after acetone mixes mutually; treat after the acetone volatilization polyethylene to be immersed in the microemulsion; under nitrogen protection; open UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 20 minutes reaction times.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 20 hours, be lower than 60 ℃ dry down.
Embodiment 4
(1) be solvent with 100ml benzene, with the N of 0.05mol, N-dimethyl n Propanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 4:1:1.2,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) n-propyl.
(2) adding the 100ml methylene dichloride in methacrylic acid 2-(N, N-dimethyl amido) n-propyl of 0.1mol is solvent, and what add 0.11mol again carries out back flow reaction to the nitro Benzyl Chloride, and the reaction times is 8 hours; Obtain product and be methacryloxypropyl n-propyl-to nitrobenzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in reaction product methacryloxypropyl n-propyl-to nitrobenzyl-alkyl dimethyl ammonium chloride is solvent; the volumetric molar concentration that makes solution is 0.4mol/L; in another part reaction product methacryloxypropyl n-propyl-, add methylene dichloride to nitrobenzyl-alkyl dimethyl ammonium chloride; the volumetric molar concentration that makes solution is 0.05mol/L; with the aqueous solution; oily solution and non-ionic surfactant span 80 mix; be made into water in oil microemulsion; adding weight percent is: the aqueous solution: oil phase solvent: the 80=1:5:0.2 of class of department; with benzophenone be coated in polypropylene surface after acetone mixes mutually; treat after the acetone volatilization polypropylene to be immersed in the microemulsion; under protection of inert gas; open UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 40 minutes reaction times.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 5
1) be solvent with 100ml benzene, with the N of 0.05mol, the N-dimethylethanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 8:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) ethyl ester.
(2) adding the 100ml methylene dichloride in the methacrylic acid 2 of 0.2mol-(N, N-dimethyl amido) ethyl ester is solvent, and the Benzyl Chloride that adds 0.22mol again carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 0.4mol/L, in another part reaction product methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, add chloroform, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix with polysorbate60, are made into water in oil microemulsion, class of department 80: polysorbate60=1:0.15.Additional proportion is: the aqueous solution: the oil phase solvent: class 80 of department and polysorbate60 mixture=1:5:0.2; Then polypropylene film light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 5 minutes reaction times.Wherein the preparation method of polypropylene film light dormancy base is: add in polymer surfaces and sprawl the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, make the polymer surfaces acetone soln reach 0.4 * 10
2Ml/m
2, open UV-light, irradiation intensity be 20 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 2 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 6
(1) be solvent with 100ml benzene, with the N of 0.05mol, N-dimethyl n Propanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 4:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) isopropyl ester.
(2) adding the 100ml methylene dichloride in the methacrylic acid 2 of 0.1mol-(N, N-dimethyl amido) isopropyl ester is solvent, and the Benzyl Chloride that adds 0.1mol again carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is methacryloxypropyl sec.-propyl-benzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in reaction product methacryloxypropyl sec.-propyl-benzyl-alkyl dimethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 0.4mol/L, in another part reaction product methacryloxypropyl sec.-propyl-benzyl-alkyl dimethyl ammonium chloride, add methylene dichloride, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix, be made into water in oil microemulsion, additional proportion is: the aqueous solution: the oil phase solvent: the 80=1:5:0.2 of class of department; Then PET polyester film light dormancy base is immersed in the microemulsion under nitrogen protection, opens UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 40 minutes reaction times.Wherein the preparation method of PET polyester film light dormancy base is: the PET polyester film is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, irradiation intensity be 25 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 3 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 7
(1) be solvent with 100ml benzene, with the N of 0.1mol, the N-dimethylethanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 8:1:1,0 ℃ of temperature of reaction, and the reaction times is 24 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) ethyl ester.
(2) adding the 100ml methylene dichloride in the methacrylic acid 2 of 0.1mol-(N, N-dimethyl amido) ethyl ester is solvent, and the Benzyl Chloride that adds 0.1mol again carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 0.4mol/L, in another part reaction product methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, add chloroform, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oil-based solvent and non-ionic surfactant span 80 mix, and are made into water in oil microemulsion, and additional proportion is: the aqueous solution: oil-phase solution: the 80=1:5:0.2 of class of department; Polyacrylonitrile fibre light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 40 ℃, 20 minutes reaction times.Wherein the preparation method of polyacrylonitrile fibre light dormancy base is: polyacrylonitrile fibre is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, irradiation intensity be 25 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 3 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 8
(1) be solvent with 100ml toluene, with the N of 0.1mol, the N-diethylethanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 8:1:1.2,5 ℃ of temperature of reaction, and the reaction times is 8 hours.Obtaining product is methacrylic acid 2-(N, N-diethyl amido) ethyl ester.
(2) adding the 100ml methylene dichloride in the methacrylic acid 2 of 0.05mol-(N, N-diethyl amido) ethyl ester is solvent, adds 2 of 0.045mol again, and 5-dimethyl chlorination benzyl carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is methylacryoyloxyethyl-benzyl-diethyl ammonium chloride.
(3) at methylacryoyloxyethyl-2, adding deionized water in 5-dimethyl benzyl-diethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 0.4mol/L, at another part reaction product methylacryoyloxyethyl-2, add methylene dichloride in 5-dimethyl benzyl-diethyl ammonium chloride, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix, be made into water in oil microemulsion, additional proportion is: the aqueous solution: oil-phase solution: the 80=1:10:0.2 of class of department; Polypropylene fibre light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 20 ℃, 20 minutes reaction times.Wherein the preparation method of polypropylene fibre light dormancy base is: polypropylene fibre is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, irradiation intensity be 25 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 3 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 24 hours, be lower than 60 ℃ dry down.
Embodiment 9
(1) be solvent with the 100ml methylene dichloride, with the N of 0.1mol, the N-dimethylethanolamine is mixed with liquid, adds triethylamine and methacrylic chloride, and the mol ratio of acyl chlorides and hydroxyl and triethylamine is 8:1:1,0 ℃ of temperature of reaction, and the reaction times is 16 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) ethyl ester.
(2) adding 100ml acetone in the methacrylic acid 2 of 0.05mol-(N, N-dimethyl amido) ethyl ester is solvent, and the p-chlorobenzyl chlorine that adds 0.055mol again carries out back flow reaction, and the reaction times is 6 hours; Obtaining product is methylacryoyloxyethyl-p-chlorobenzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in methylacryoyloxyethyl-p-chlorobenzyl-alkyl dimethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 1.6mol/L, in another part reaction product methylacryoyloxyethyl-p-chlorobenzyl-alkyl dimethyl ammonium chloride, add methylene dichloride, the volumetric molar concentration that makes solution is 0.6mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix, be made into water in oil microemulsion, additional proportion is: the aqueous solution: oil-phase solution: the 80=1:20:0.4 of class of department; Polypropylene film light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 35 milliwatts/centimetre
2, the irradiation reaction temperature is 70 ℃, 30 minutes reaction times.Wherein the preparation method of polypropylene film light dormancy base is: polypropylene film is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, opens UV-light, illumination 3 minutes, irradiation intensity be 35 milliwatts/centimetre
2, carry out the graft polymerization preformer reaction.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 20 hours, be lower than 60 ℃ dry down.
Embodiment 10
(1) with benzene be solvent, add triethylamine in the rare acyl chlorides of methyl-prop and 2-(N, N-dimethyl amido) alcoholic acid mixed solution, the mol ratio of acyl chlorides and hydroxyl and triethylamine is 2:1:1,5 ℃ of temperature of reaction, and the reaction times is 8 hours.Obtaining product is methacrylic acid 2-(N, N-dimethyl amido) ethyl ester.
(2) adding the 100ml acetonitrile in methacrylic acid 2-(N, N-dimethyl amido) ethyl ester of 0.05mol is solvent, add again 0.05mol between benzyl chloride chlorine carry out back flow reaction, the reaction times is 8 hours; Obtaining product is methylacryoyloxyethyl-m-chloro benzyl-alkyl dimethyl ammonium chloride.
(3) adding deionized water in methylacryoyloxyethyl-m-chloro benzyl-alkyl dimethyl ammonium chloride is solvent, the volumetric molar concentration that makes solution is 0.8mol/L, in another part reaction product methylacryoyloxyethyl-m-chloro benzyl-alkyl dimethyl ammonium chloride, add methylene dichloride, the volumetric molar concentration that makes solution is 0.05mol/L, with the aqueous solution, oily solution and non-ionic surfactant span 80 mix with polysorbate60, class of department 80: polysorbate60=1:0.15, be made into water in oil microemulsion, additional proportion is: the aqueous solution: oil-phase solution: class 80 of department and polysorbate60 mixture=1:10:0.2; Then polypropylene film light dormancy base is immersed in the microemulsion, under protection of inert gas, opens UV-light and carry out irradiation reaction, irradiation intensity be 30 milliwatts/centimetre
2, the irradiation reaction temperature is 30 ℃, 30 minutes reaction times.Wherein the preparation method of polypropylene film light dormancy base is: will be immersed in the polypropylene film in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, open UV-light, irradiation intensity be 25 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 3 minutes.
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 22 hours, be lower than 60 ℃ dry down.
Claims (9)
1. a surface has the preparation method of the grafted antibacterial polymkeric substance of micron and nanometer composite structure, it is characterized in that this method may further comprise the steps:
(1) be solvent with toluene, benzene, methylene dichloride or tetrahydrofuran (THF), the volumetric molar concentration that makes the tertiary amine that has hydroxyl is 0.5～2mol/L, in the solution of the tertiary amine that has hydroxyl, add triethylamine and the acyl chlorides that contains the C=C unsaturated double-bond, obtain reaction product A, adding mol ratio is: acyl chlorides: hydroxyl: triethylamine=1～8:1:1～1.2, temperature of reaction is 0～5 ℃, and the reaction times is 8～24 hours;
(2) in above-mentioned reaction product A, add any in acetone, methylene dichloride or the acetonitrile as solvent, making the solution volumetric molar concentration is 0.5～2mol/L, add benzyl halogenide again and carry out back flow reaction, obtain reaction product B, adding mol ratio is: reaction product A: benzyl halogenide=1:0.9～1.1, and the reaction times is 6～8 hours;
(3) in reaction product B, add deionized water; obtain the aqueous solution; the volumetric molar concentration of the aqueous solution is 0.2～1.6mol/L; in reaction product B, add oil-based solvent; obtain oily solution; the volumetric molar concentration of oily solution is 0.05～0.6mol/L; with the aqueous solution; oily solution mixes mutually with nonionic surface active agent; be made into water in oil microemulsion; adding weight percent is: the aqueous solution: oil phase solvent: nonionic surface active agent=1:5～20:0.2～0.4; with light trigger with any ratio be coated in polymer surfaces after organic solvent mixes mutually; treat after the organic solvent volatilization polymkeric substance to be immersed in the microemulsion; under protection of inert gas, open UV-light and carry out irradiation reaction, irradiation intensity be 20～40 milliwatts/centimetre
2, the irradiation reaction temperature is 20 ℃～70 ℃, 5～40 minutes reaction times; Or polymkeric substance light dormancy base is immersed in the microemulsion, open UV-light and carry out irradiation reaction, irradiation intensity be 20～40 milliwatts/centimetre
2The irradiation reaction temperature is 20 ℃～70 ℃, and in 5～40 minutes reaction times, the preparation method of wherein said polymkeric substance light dormancy base is: polymkeric substance is immersed in the acetone soln that contains 2mol/L vinylformic acid and 0.2mol/L benzophenone, open UV-light, irradiation intensity be 20～40 milliwatts/centimetre
2, the graft polymerization preformer reaction is carried out in illumination 1～6 minute;
(4) with the mixed solvent of water and acetone to above-mentioned graftomer extracting 20～24 hours, be lower than 60 ℃ dry down.
2. the method for claim 1 is characterized in that wherein said acyl chlorides is acrylate chloride or methacrylic chloride.
3. the method for claim 1 is characterized in that wherein said tertiary amine has one or two hydroxyl.
4. method as claimed in claim 3 is characterized in that wherein said tertiary amine is N, N-dimethylethanolamine, N, any in N-diethylethanolamine, N-dimethyl n Propanolamine, N-dimethylisopro panolamine or the N methyldiethanol amine.
5. the method for claim 1 is characterized in that wherein said benzyl halogenide is any in muriate, bromide or the iodide.
6. method as claimed in claim 5, it is characterized in that wherein said muriate be Benzyl Chloride, to nitro Benzyl Chloride, 2,5-dimethyl chlorination benzyl, any in a benzyl chloride chlorine or the benzyl chloride chlorine.
7. the method for claim 1 is characterized in that wherein said oil phase solvent is chloroform or methylene dichloride.
8. the method for claim 1 is characterized in that wherein said nonionic surface active agent is the mixture of class of department 80 or class 80 of department and polysorbate60, and the mass ratio of mixture is: class of department 80: polysorbate60=1:0.15.
9. the method for claim 1 is characterized in that wherein said polymkeric substance is any in polyethylene, polypropylene, polyacrylonitrile or the polyester.
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| CN101168586B (en) * | 2007-09-28 | 2010-09-15 | 东南大学 | Antibacterial macromolecule polymer and preparation method thereof |
| WO2010018792A1 (en) * | 2008-08-11 | 2010-02-18 | 倉敷紡績株式会社 | Sliver for spinning, process for producing same, and spun yarn and textile product both using same |
| CN103130662A (en) * | 2011-11-24 | 2013-06-05 | 中国科学院理化技术研究所 | Cationic water cosolvent with V-type configuration, polymer thereof, synthetic method and application thereof |
| CN103910996A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | Antibacterial masterbatch, nano antibacterial super-tough plastic added with antibacterial masterbatch and preparation and application of plastic |
| CN105771687B (en) * | 2016-03-29 | 2019-09-03 | 天津工业大学 | A kind of preparation method of antibacterial PVC ultrafiltration membrane |
| CN107638612B (en) * | 2017-11-08 | 2020-09-25 | 中国科学院长春应用化学研究所 | Anticoagulation antibacterial indwelling needle cannula and preparation method thereof |
| CN108774759A (en) * | 2018-05-24 | 2018-11-09 | 江阴市华思诚无纺布有限公司 | A kind of antibacterial polyester non-woven fabrics and preparation method thereof |
| CN108690390B (en) * | 2018-05-29 | 2020-04-21 | 中深建业建设集团有限公司 | Environment-friendly paint additive with antibacterial function and preparation method thereof |
| CN111519432B (en) * | 2020-05-12 | 2022-09-27 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5056188A (en) * | 1988-08-03 | 1991-10-15 | Schott Glaswerke | Process and apparatus for securing a grip element to crockery or pottery |
| US5561167A (en) * | 1992-12-28 | 1996-10-01 | Suntory Limited | Antibacterial fiber, textile and water-treating element using the fiber and method of producing the same |
| CN1223273A (en) * | 1998-11-02 | 1999-07-21 | 华南理工大学 | Radiation graft process for preparing antiseptic material of pyridine salt type polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5056188A (en) * | 1988-08-03 | 1991-10-15 | Schott Glaswerke | Process and apparatus for securing a grip element to crockery or pottery |
| US5561167A (en) * | 1992-12-28 | 1996-10-01 | Suntory Limited | Antibacterial fiber, textile and water-treating element using the fiber and method of producing the same |
| CN1223273A (en) * | 1998-11-02 | 1999-07-21 | 华南理工大学 | Radiation graft process for preparing antiseptic material of pyridine salt type polymer |
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