CN101029113A - Reactive polymer antibacterial agent, its production and use - Google Patents
Reactive polymer antibacterial agent, its production and use Download PDFInfo
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- CN101029113A CN101029113A CN 200710027027 CN200710027027A CN101029113A CN 101029113 A CN101029113 A CN 101029113A CN 200710027027 CN200710027027 CN 200710027027 CN 200710027027 A CN200710027027 A CN 200710027027A CN 101029113 A CN101029113 A CN 101029113A
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- China
- Prior art keywords
- dimethylaminoethyl methacrylate
- antibacterial agent
- maleic anhydride
- polymer antibacterial
- alkyl halide
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229920013730 reactive polymer Polymers 0.000 title abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 54
- 239000004744 fabric Substances 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 32
- 238000007334 copolymerization reaction Methods 0.000 claims description 28
- -1 dimethylaminoethyl methacrylate alkyl halide Chemical class 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 239000004160 Ammonium persulphate Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- IVQJWIKDAPZNII-UHFFFAOYSA-N [Cl-].C(C1=CC=CC=C1)[NH3+].CN(C)CCOC(C(=C)C)=O Chemical compound [Cl-].C(C1=CC=CC=C1)[NH3+].CN(C)CCOC(C(=C)C)=O IVQJWIKDAPZNII-UHFFFAOYSA-N 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 239000004566 building material Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
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- 229920003023 plastic Polymers 0.000 claims description 3
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- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 26
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 22
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 22
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 20
- 230000003115 biocidal effect Effects 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 230000001954 sterilising effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 108010080698 Peptones Proteins 0.000 description 2
- 229920000289 Polyquaternium Polymers 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 231100000293 acute skin toxicity Toxicity 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000009988 textile finishing Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000283977 Oryctolagus Species 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A reactive polymer antibacterial agent, its production and use are disclosed. The process is carried out by adding solvent into any substance of methacrylic acid dimethylaminothoxy alkyl halide and maleic anhydride or acrylic amide or butyl acrylate or phenylethylene, agitating, inducing into nitrogen, raising temperature to 35-60degree, injecting into initiating agent, polymerization reacting for 6-11hrs, raising temperature to 50-70degree, reacting for 1-2hrs and cooling to obtain the final product. It's safe, efficient and non-toxic.
Description
Technical field
The present invention relates to a kind of reactable polymer antibacterial agent, more specifically be meant a kind of reactable polymer antibacterial agent that forms by antibacterial monomer and the copolymerization of reactable function monomer and preparation method thereof and method.
Background technology
Along with social development and human living standard's raising, healthy comfortable living environment becomes the target that people pursue day by day.People are by to the discovering of environmental microorganism, some invasive organisms produce very big harm to human beings'health.The cholera in 19th century, Japanese pathogenicity bo coli-infection in 1996 all brings very grave disaster to the mankind.The nineteen sixty-five cotton loss that causes because of mould corruption of Britain can reach more than millions of sterlings, and the same year, domestic certain industry internal statistical showed that the article that cause because of going mouldy then lose up to 5.6 hundred million yuan, is the same period 23 times of fire losses.Therefore, seeking the antiseptic-germicide of i.e. effect, wide spectrum, long-acting, stable and safety and attention that the durable antibiotic material just is being subjected to academia and industry member and human consumer's parent looks at.
Antiseptic-germicide comprises 4 big classes such as inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and polymer antibacterial agent.At present, inorganic antiseptic is research and uses a more class, particularly contains the nanometer grade inorganic antibacterial agent of metal ions such as silver, zinc and copper.Number of patent application is that patents such as 200410049653.5,200510029595.4,200510012945.6,200610050245.0 have all openly been reported multiple inorganic antiseptic and preparation method thereof.Nano inorganic antimicrobial agent have good anti-bacterial effect, high temperature resistant, toxicity is low, advantage such as tasteless, non-stimulated, non-volatile, its research and development has all obtained bigger achievement in theoretical and application, but still there is following outstanding problem at present: easily sulfuration or the oxidation of (1) silver, light stability is poor, should not be used for tinted material; (2) complicated process of preparation needs special equipment; (3) be difficult to controlling slow release speed, and in the use of material,, easily environment on every side polluted along with the heavy metal ion that discharges is more and more; (4) release of metal ion from material can influence the use properties of material itself to some extent; (5) large usage quantity, cost is higher.
Polymer antibacterial agent is with antibioticization of polymer itself, as with the antibacterial monomer copolymerization or be grafted in the macromolecular chain.Therefore plurality of advantages such as polymer antibacterial agent has efficiently, wide spectrum, safety non-toxic, non-volatile, and long service life is easy to processing, is easy to store, and can not infiltrate human or animal's epidermis, and is cheap will have bigger development space.At present, the research and development of polymer antibacterial agent also is in the stage at the early-stage.Its type mainly contains polyquaternium, poly-quaternary alkylphosphonium salt, polypyridine salt and chitosan etc.Compare with polyquaternium, poly-quaternary alkylphosphonium salt and polypyridine salt are owing to the cost of material height, and its range of application has been subjected to considerable restraint.Number of patent application is 200510037926.9,200510037927.3 reported chitosan antibacterial finishing agent etc. patent disclosure, because the chitosan anti-bacteria effect of non-modified is also bad, therefore must through complicated degradation technique and quaternized after, could improve its antibacterial effect.Mainly bond together by weak intermolecular forces between chitosan and the matrix in addition, antibacterial effect is not lasting, and particularly some fabrics are not through just having had antibacterial effect after the washing several times.
Summary of the invention
At above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to prepare a kind of reactable polymer antibacterial agent efficient, safe, long-acting, stable and easy to use by the raw material of cheapness and simple polymerization technique.
Another object of the present invention is to provide the preparation method of above-mentioned reactable polymer antibacterial agent.
A further object of the present invention is to provide the application of above-mentioned reactable polymer antibacterial agent, this antiseptic-germicide can be used for fields such as plastics, coating, fabric, paper, rubber, resin, timber, building materials, medical treatment, sanitary product and water treatment, method by chemical bonding antibiotic group introduce securely in the base material with provide contain in a kind of wide spectrum, efficient, the safe durable antibiotic material, particularly matrix can with the various base materials or the carrier of maleic anhydride reaction.
The objective of the invention is to realize: a kind of reactable polymer antibacterial agent by following technical proposals, it is to be formed by dimethylaminoethyl methacrylate alkyl halide and two kinds of monomer copolymerizations of maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 30～95mol%, shown in I; Perhaps form by any one material in acrylamide, butyl acrylate or the vinylbenzene and dimethylaminoethyl methacrylate alkyl halide and three kinds of monomer copolymerizations of maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 5～15mol%, the copolymerization ratio of any one material in acrylamide, butyl acrylate or the vinylbenzene is 15～90mol%, shown in II.
Wherein the dimethylaminoethyl methacrylate alkyl halide is the antibacterial monomer, and its substituted alkyl can be C
4～C
16X or benzyl chloride, X are CL or Br.Described acrylamide, butyl acrylate or vinylbenzene are for regulating the function monomer of antimicrobial macromolecule hydrophilic-lipophilic balance ratio.Maleic anhydride be can with the bridge formation function monomer of matrix generation covalent reaction.By containing weight percent at least is that 10% monomer component (total hybrid reaction monomer) carries out polymerization.
Formula I
Wherein, R
1Be C
4～C
16Alkyl or benzyl.
Formula II
Wherein, R
1Be meant C
4～C
16Alkyl or benzyl, R
2Be
In any one.
Reactable polymer antibacterial agent of the present invention does not produce any hormesis to skin.
A kind of preparation method of reactable polymer antibacterial agent, comprise the steps: in dimethylaminoethyl methacrylate alkyl halide and maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, and the copolymerization ratio of maleic anhydride is 30～95mol%; Perhaps at acrylamide, any one material in butyl acrylate or the vinylbenzene, in dimethylaminoethyl methacrylate alkyl halide and the maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 5～15mol%, acrylamide, the copolymerization ratio of any one material in butyl acrylate or the vinylbenzene is 15～90mol%, add solvent, begin then to stir, behind the logical nitrogen, temperature is increased to 35～60 ℃, inject initiator, described initiator amount is 0.2～1.0mol%, under same temperature, continue polyreaction 6～11h, for residual monomer is reacted completely as far as possible, be warming up to 50～70 ℃ then, continue reaction 1～2h, cooling promptly gets the reactable polymer antibacterial agent.
In order to realize the present invention better, described dimethylaminoethyl methacrylate alkyl halide is the antibacterial monomer, and its substituted alkyl can be C
4～C
16X or benzyl chloride, X are CL or Br.Described dimethylaminoethyl methacrylate alkyl halide comprises dimethylaminoethyl methacrylate benzyl ammonium chloride, dimethylaminoethyl methacrylate butyl brometo de amonio, dimethylaminoethyl methacrylate hexadecyl brometo de amonio or dimethylaminoethyl methacrylate dodecyl bromination ammonium etc.
Described solvent comprises water, 1,4-dioxane, N, and any one in dinethylformamide or the dimethyl sulfoxide (DMSO) or two kinds of solvents carry out solution polymerization; Special preferred solvent is 1,4-dioxane and N, and dinethylformamide, 1,4-dioxane: N, the volume ratio of dinethylformamide is 1: 2～2: 1.
Wherein during polymerization, used initiator is ammonium persulphate or azo-initiator (being Diisopropyl azodicarboxylate); Initiator amount is 0.2～1.0mol%.Also to use a kind of reductive agent (Tetramethyl Ethylene Diamine) when adopting ammonium persulphate to make initiator, mole such as described Tetramethyl Ethylene Diamine consumption and ammonium persulphate.
The application of above-mentioned reactable polymer antibacterial agent, can be used for fields such as plastics, coating, fabric, paper, rubber, resin, timber, building materials or water treatment, method by chemical bonding antibiotic group introduce securely in the base material with provide contain in a kind of wide spectrum, efficient, the safe durable antibiotic material, particularly matrix can with the various base materials or the carrier of maleic anhydride reaction.
Key problem in technology of the present invention is rationally to control content and maleic anhydride the content in copolymerization component of antibacterial monomer in the copolymerization component.Because when multipolymer reaches the best antimicrobial effect, the ratio of the antibacterial monomer of different alkyl chain lengths in multipolymer is different, and their content in multipolymer is having a strong impact on the antibacterial effect of multipolymer.Simultaneously the proportion of composing of maleic anhydride in the multipolymer anti-microbial property that not only affects polymkeric substance also affects the level of response with base material.
Principle of the present invention is at first by the quaternary ammonium salt antibacterial monomer, maleic anhydride reactable monomer and hydrophilic or hydrophobic monomer carries out binary or terpolymer prepares the reactable polymer antibacterial agent, but utilize the maleic anhydride group in this antiseptic-germicide and the reactive group of substrate surface to react then, on matrix, introduce the antibiotic group of quaternary ammonium salt by the covalent attachment mode and prepare the durable antibiotic material.
The present invention compared with prior art has following advantage and beneficial effect:
(1) polymer antibacterial agent of the present invention belongs to green product, to skin without any hormesis.
(2) use polymer antibacterial agent of the present invention, improved the service efficiency of antiseptic-germicide, reduce the antiseptic-germicide in the relief liquor and therefore reduce toxic action to ecotope, security and stability is better.
(3) fabric through polymer antibacterial agent of the present invention arrangement still has antibiotic and germicidal action for a long time through washing, can reduce and avoid fabric store and use in the going mouldy and damage by worms of generation.
(4) compare with existing chitosan antibacterial finishing agent, this reactive polymer antibacterial agent synthesis technique is simple, easy to use, and contains the group that reacts with matrix, can prepare the durable antibiotic material.
(5) be that the antibacterial finish technology is compared with existing inorganic nano-silver, this method process operations is simple, and Material Cost is cheap, and the reaction conditions gentleness can be handled light fabric.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
In the reactor of 500mL, add 110.9g (70mol%) dimethylaminoethyl methacrylate benzyl ammonium chloride and 16.5g (30mol%) maleic anhydride successively, then add 1 of 200mL, the N of 4-dioxane and 100mL, dinethylformamide, (500～1000 change/min) feed simultaneously water of condensation to begin stirring, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, inject 2mL with sampler and contain 1 of 0.18g (0.2%mol) Diisopropyl azodicarboxylate (AIBN), the 4-dioxane solution under same temperature, continues polyreaction 10h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 2h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 2
In the reactor of 500mL, add 110.9g (70mol%) dimethylaminoethyl methacrylate benzyl ammonium chloride and 16.5g (30mol%) maleic anhydride successively, then add 300mL water, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, temperature is increased to 35 ℃, injects the aqueous solution and the 0.83mL Tetramethyl Ethylene Diamine (reductive agent) that 2mL contains 1.3g (1wt%) ammonium persulphate (APS) with sampler by thermostatic water-circulator bath, under same temperature, continue polyreaction 6h.For residual monomer is reacted completely as far as possible, temperature is increased to 50 ℃ at last, continue reaction 2h, cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 3
In the reactor of 500mL, add 115.0g (70mol%) dimethylaminoethyl methacrylate butyl brometo de amonio and 16.5g (30mol%) maleic anhydride successively, then add 300mL water, begin to stir and feed the water of condensation temperature control simultaneously, behind the logical nitrogen 30min, temperature is increased to 35 ℃, injects the aqueous solution and the 0.83mL Tetramethyl Ethylene Diamine that 2mL contains 1.3g (1wt%) ammonium persulphate (APS) with sampler by thermostatic water-circulator bath, under same temperature, continue polyreaction 6h.For residual monomer is reacted completely as far as possible, temperature is increased to 60 ℃ at last, continue reaction 2h, cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 4
In the reactor of 500mL, add 12.9g (5mol%) dimethylaminoethyl methacrylate hexadecyl brometo de amonio and 52.3g (95mol%) maleic anhydride successively, then add 1 of 200mL, the N of 4-dioxane and 100mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, inject 2mL with sampler and contain 1 of 0.18g (0.2%mol) Diisopropyl azodicarboxylate (AIBN), the 4-dioxane solution under same temperature, continues polyreaction 10h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 2h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 5
In the reactor of 500mL, add 22.6g (10mol%) dimethylaminoethyl methacrylate dodecyl bromination ammonium successively, 8.2g (15mol%) maleic anhydride and 29.8g (85mol%) acrylamide, then add 1 of 100mL, the N of 4-dioxane and 200mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, injects 2mL with sampler and contain 1 of 0.18g (0.2%mol) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 11h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 6
In the reactor of 500mL, add 45.4g (20mol%) dimethylaminoethyl methacrylate dodecyl bromination ammonium successively, 2.7g (5mol%) maleic anhydride and 29.8g (75mol%) acrylamide, then add 1 of 100mL, the N of 4-dioxane and 200mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, injects 2mL with sampler and contain 1 of 0.18g (1.0%mol) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 11h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 7
In the reactor of 500mL, add 110.9g (70mol%) dimethylaminoethyl methacrylate benzyl ammonium chloride successively, 8.2g (15mol%) maleic anhydride and 7.4g (15mol%) vinylbenzene, then add 1 of 200mL, the N of 4-dioxane and 100mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 55 ℃, injects 2mL with sampler and contain 1 of 0.18g (0.2mol%) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 7h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 8
In the reactor of 500mL, add 31.6g (20mol%) dimethylaminoethyl methacrylate benzyl ammonium chloride successively, 2.7g (5mol%) maleic anhydride and 29.8g (75mol%) acrylamide, then add 1 of 100mL, the N of 4-dioxane and 200mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, injects 2mL with sampler and contain 1 of 0.18g (1.0mol%) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 7h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 9
In the reactor of 500mL, add 32.8g (20mol%) dimethylaminoethyl methacrylate butyl brometo de amonio successively, 2.7g (5mol%) maleic anhydride and 29.8g (75mol%) acrylamide, then add 1 of 100mL, the N of 4-dioxane and 200mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, injects 2mL with sampler and contain 1 of 0.18g (1.0%mol) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 11h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 10
In the reactor of 500mL, add 115.0g (70mol%) dimethylaminoethyl methacrylate butyl brometo de amonio successively, 5.4g (10mol%) maleic anhydride and 12.1g (20mol%) butyl acrylate, then add 1 of 100mL, the N of 4-dioxane and 200mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, injects 2mL with sampler and contain 1 of 0.18g (1.0mol%) Diisopropyl azodicarboxylate (AIBN), 4-dioxane solution, under same temperature, continue polyreaction 7h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 11
In the reactor of 500mL, add 25.8g (10mol%) dimethylaminoethyl methacrylate hexadecyl brometo de amonio successively, 5.4g (10mol%) maleic anhydride and 31.8g (80mol%) acrylamide, the N that then adds 300mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, inject 2mL with sampler and contain 1 of 0.18g (1.0%mol) Diisopropyl azodicarboxylate (AIBN), the 4-dioxane solution under same temperature, continues polyreaction 11h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 1h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 12
In the reactor of 500mL, add 12.9g (5mol%) dimethylaminoethyl methacrylate hexadecyl brometo de amonio successively, 2.7g (5mol%) maleic anhydride and 35.8g (90mol%) acrylamide, the N that then adds 300mL, dinethylformamide, begin to stir and feed water of condensation simultaneously, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, inject 2mL with sampler and contain 1 of 0.18g (1.0mol%) Diisopropyl azodicarboxylate (AIBN), the 4-dioxane solution under same temperature, continues polyreaction 6h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 2h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 13
In the reactor of 500mL, add 79.2g (50mol%) dimethylaminoethyl methacrylate benzyl ammonium chloride and 27.5g (50mol%) maleic anhydride successively, then add 1 of 200mL, the N of 4-dioxane and 100mL, dinethylformamide, (500～1000 change/min) feed simultaneously water of condensation to begin stirring, behind the logical nitrogen 30min, by thermostatic water-circulator bath temperature is increased to 60 ℃, inject 2mL with sampler and contain 1 of 0.18g (0.2%mol) Diisopropyl azodicarboxylate (AIBN), the 4-dioxane solution under same temperature, continues polyreaction 10h.For residual monomer is reacted completely as far as possible, the 0.5mL that reinjects at last contains the dioxane solution of 0.04g AIBN, is warming up to 70 ℃, continues reaction 2h, and cooling promptly gets the reactable polymer antibacterial agent.
Embodiment 14
Cotton fabric is washed in 50 ℃ water, in 70 ℃ convection oven, dry then.Subsequently the fabric of oven dry is immersed bath raio (solid-liquid weight ratio) by embodiment 2 preparations and is 30min in 30: 1 the high-molecular anti-bacteria agent solution of 10g/L, two soak two pricks the back taking-up, in 80～90 ℃ convection oven, bake 3min, then at 160～170 ℃ of reaction 2min, washing is dried the fabric of arrangement at last in 70 ℃ convection oven.Promptly obtain antibiotic fabric.
Embodiment 15
Cotton fabric is washed in 60 ℃ water, in 70 ℃ convection oven, dry then.Subsequently the fabric of oven dry is immersed bath raio by embodiment 6 preparations and is 30min in 30: 1 the high-molecular anti-bacteria agent solution of 2g/L, two soak two pricks the back taking-up, in 80～90 ℃ convection oven, bake 3min, then at 160～170 ℃ of reaction 2min, washing is dried the fabric of arrangement at last in 70 ℃ convection oven.Promptly obtain antibiotic fabric.
Embodiment 16
Cotton fabric is washed in 70 ℃ water, in 50 ℃ convection oven, dry then.Subsequently the fabric of oven dry is immersed bath raio by embodiment 11 preparations and is 30min in 30: 1 the high-molecular anti-bacteria agent solution of 5g/L, two soak two pricks the back taking-up, in 80～90 ℃ convection oven, bake 3min, then at 160～170 ℃ of reaction 2min, washing is dried the fabric of arrangement at last in 70 ℃ convection oven.Promptly obtain antibiotic fabric.
Embodiment 17
The antibiotic fabric that embodiment 14 is made carries out carrying out antibacterial tests respectively after 50,100,150,200 washings.
Embodiment 18
The antibiotic fabric that embodiment 15 is made carries out carrying out antibacterial tests respectively after 50,100,150,200 washings.
Embodiment 19
3 new zealand rabbits that body weight is about 2.5 kilograms after quarantining 7 days, in test backbone both sides, preceding 24 hours places to go dorsal body setae, scope is 3cm * 3cm.The antimicrobial 0.5mL (5g/L) that gets embodiment 1 preparation is applied to animal one side intact skin, scope is 2.5cm * 2.5cm, cover with two layers of gauze and one deck glassine paper, use the nonirritant immobilization with adhesive tape, opposite side is as blank, seal and remove the residual thing that tried with warm water after 4 hours, observations and other poisoning sign.It the results are shown in Table 4.
The test method that the present invention adopts is as follows:
Nutrient agar medium (composition: peptone 10g, extractum carnis powder 3g, sodium-chlor 5g, agar 15g); Nutrient broth (composition: peptone 10g, extractum carnis powder 3g, sodium-chlor 5g); Intestinal bacteria (ATCC 25922).
The dull and stereotyped dilution method of counting is adopted in the test of polymer antibacterial agent anti-microbial property.The antiseptic-germicide of embodiment 1 to embodiment 6 preparation is mixed with the solution of 0.5g/L respectively.Take out the antimicrobial of 18ml then respectively and put into the test tube of the bacterium of going out, then add 2mL 10
6The bacteria suspension of individual/ml, mixed bacteria liquid is cultivated down at 37 ℃, the shaking culture liquid that takes out 1ml behind the 6h is put into the sterilized physiological saline of 9ml, do 10 times of gradient stepwise dilutions, get the 0.1ml diluent and put into the culture dish of the bacterium of going out, each extent of dilution is made three plates, cultivates 24～48h counting at 36～37 ℃, multiply by the colony number that extension rate is every ml mixed solution with the bacterium colony mean number of dilution three plates.
The antibacterial fabric performance test is tested with reference to FZ/T01021-92 antibacterial fabric method for testing performance.
Sterilizing rate=(A/B-A) * 100%; A is the colony number after the antiseptic-germicide effect, and B is the colony number without the antiseptic-germicide effect.
Percentage of grafting=(X-Y/Y) * 100%; X is the weight after the textile finishing, and Y is the weight before the textile finishing.
The mensuration of cationic degree adopts the JIS method.
The structural characterization and the sterilization effect of the polymer antibacterial agent that table 1 embodiment 1 to embodiment 12 is prepared
| Embodiment | Intrinsic viscosity mL/mg | Acid number (KOHmg/g) | CD (％) | Sterilizing rate (%) |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 | 426.1 378.2 269.4 298.1 428.2 492.3 726.1 306.5 298.3 236.8 216.3 359.6 | 146.8 138.1 138.1 351.9 89.1 40.5 89.1 37.2 37.2 54.2 54.2 37.0 | 50.4 51.6 57.6 2.1 4.8 13.8 60.5 13.2 12.9 57.6 4.0 1.5 | 100 100 100 100 100 100 100 100 100 100 100 100 |
Table 1 is the structural characterization and the sterilization effect of the prepared polymer antibacterial agent of embodiment 1 to embodiment 12.
As can be seen from Table 1, the intrinsic viscosity of 1 to embodiment 12 synthetic antimicrobial macromolecule of embodiment shows that the various embodiments described above synthetic polymkeric substance all has higher molecular weight between 216.3～716.1mL/mg.It can also be seen that in these multipolymers simultaneously and not only contain antibiotic group but also contain the reactable group, be the synthetic reactable polymer antibacterial agent of wanting according to the acid number of polymkeric substance and cationic degree.Institute of the present invention synthetic reactable polymer antibacterial agent has the good sterilization effect simultaneously, can both kill 100% intestinal bacteria in the action time of 6h.
The percentage of grafting of the fabric after table 2 antibacterial finish and sterilizing rate
| Embodiment | Percentage of grafting (%) | Sterilizing rate (%) |
| Embodiment 14 embodiment 15 embodiment 16 | 7.9 11.8 10.7 | 100 100 100 |
Table 2 is percentage of grafting and sterilizing rates of embodiment 2, embodiment 6, the embodiment 11 synthetic reactable polymer antibacterial agents fabric after to the cotton fabric antibacterial finish.Cotton fabric is after embodiment 2, embodiment 6, embodiment 11 synthetic reactable polymer antibacterial agents are handled as can be seen from Table 2, percentage of grafting reaches 7.9～11.8%, has 100% sterilization effect simultaneously, illustrate to combine a large amount of antibacterial polymers on the fabric securely, and the polymkeric substance on the fabric has still showed good antibacterial effect.
The washing fastness result of variations of table 3 fabric percentage of grafting and antibacterial effect
| Embodiment | Washing times | Percentage of grafting (%) | Sterilizing rate (%) |
| Embodiment 17 | 0 50 100 150 200 | 7.5 5.2 4.8 4.5 4.4 | 100 99.9 90.7 90.7 90.0 |
| Embodiment 18 | 0 50 100 150 200 | 11.8 10.2 9.7 9.4 9.4 | 100 100 100 100 100 |
Table 3 is after embodiment 6 and embodiment 8 synthetic reactable polymer antibacterial agents are handled cotton fabric, the percentage of grafting and the washing fastness sterilization effect of antibiotic fabrics after washing through 50,100,150,200 times respectively.Fabric is through repeatedly still having higher percentage of grafting and sterilization effect after the washing as can be seen from Table 3.Particularly fabric percentage of grafting after 200 washings of handling through embodiment 8 still reaches 9.4%, and still has 100% sterilization effect.Illustrate that synthetic reactable polymer antibacterial agent of the present invention can be securely fixed in by the mode of covalent bonding on the fabric, therefore still have higher antibacterial effect after 200 washings of fabric through antimicrobial treatment.
Table 4 is acute dermal toxicity test-results, from the result as can be seen, synthetic reactable polymer antibacterial agent of the present invention to rabbit skin without any hormesis.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Table 4 acute dermal toxicity test-results (embodiment 19)
| Observing time | 1h | 24h | 48h | 72h | 4d | 5d | 6d | 7d | ||||||||||
| Sex | Body weight kg | Grade | A | B | A | B | A | B | A | B | A | B | A | B | A | B | A | B |
| Female robust | 2.4 2.5 2.5 2.6 | Red and swollen | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 |
A: tried thing B: contrast is blank
Claims (9)
1, a kind of reactable polymer antibacterial agent, it is characterized in that: form by dimethylaminoethyl methacrylate alkyl halide and two kinds of monomer copolymerizations of maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 30～95mol%, shown in I; Perhaps form by any one material in acrylamide, butyl acrylate or the vinylbenzene and dimethylaminoethyl methacrylate alkyl halide and three kinds of monomer copolymerizations of maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 5～15mol%, the copolymerization ratio of any one material in acrylamide, butyl acrylate or the vinylbenzene is 15～90mol%, shown in II; The substituted alkyl of described dimethylaminoethyl methacrylate alkyl halide is C
4～C
16X or benzyl chloride, X are CL or Br;
Formula I
Wherein, R
1Be C
4～C
16Alkyl or benzyl;
Formula II
Wherein, R
1Be C
4～C
16Alkyl or benzyl, R
2Be
Or
In any one.
2, the preparation method of the described a kind of reactable polymer antibacterial agent of claim 1, it is characterized in that comprising the steps: in dimethylaminoethyl methacrylate alkyl halide and maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, and the copolymerization ratio of maleic anhydride is 30～95mol%; Perhaps at acrylamide, any one material in butyl acrylate or the vinylbenzene, in dimethylaminoethyl methacrylate alkyl halide and the maleic anhydride, the copolymerization ratio of described dimethylaminoethyl methacrylate alkyl halide is 5～70mol%, the copolymerization ratio of maleic anhydride is 5～15mol%, acrylamide, the copolymerization ratio of any one material in butyl acrylate or the vinylbenzene is 15～90mol%, add solvent, begin then to stir, behind the logical nitrogen, temperature is increased to 35～60 ℃, inject initiator, described initiator amount is 0.2～1.0mol%, under same temperature, continues polyreaction 6～11h, be warming up to 50～70 ℃ then, continue reaction 1～2h, cooling promptly gets the reactable polymer antibacterial agent.
3, the preparation method of a kind of reactable polymer antibacterial agent according to claim 2 is characterized in that: the substituted alkyl of described dimethylaminoethyl methacrylate alkyl halide is C
4～C
16X or benzyl chloride, X are CL or Br.
4, the preparation method of a kind of reactable polymer antibacterial agent according to claim 2 is characterized in that: described dimethylaminoethyl methacrylate alkyl halide comprises dimethylaminoethyl methacrylate benzyl ammonium chloride, dimethylaminoethyl methacrylate butyl brometo de amonio, dimethylaminoethyl methacrylate hexadecyl brometo de amonio or dimethylaminoethyl methacrylate dodecyl bromination ammonium.
5, the preparation method of a kind of reactable polymer antibacterial agent according to claim 2 is characterized in that: described solvent comprises water, 1,4-dioxane, N, any one in dinethylformamide or the dimethyl sulfoxide (DMSO) or two kinds of solvents.
6, the preparation method of a kind of reactable polymer antibacterial agent according to claim 2 is characterized in that: described solvent is 1,4-dioxane and N, dinethylformamide, 1,4-dioxane: N, the volume ratio of dinethylformamide is 1: 2～2: 1.
7, the preparation method of a kind of reactable polymer antibacterial agent according to claim 2 is characterized in that: described initiator is ammonium persulphate or Diisopropyl azodicarboxylate.
8, the preparation method of a kind of reactable polymer antibacterial agent according to claim 7 is characterized in that: described initiator will add the reductive agent Tetramethyl Ethylene Diamine during for ammonium persulphate, mole such as described Tetramethyl Ethylene Diamine consumption and ammonium persulphate.
9, the application of the described a kind of reactable polymer antibacterial agent of claim 1 in plastics, coating, fabric, paper, rubber, resin, timber, building materials or water treatment field.
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