CN105732918A - Organic-silicon-modified acrylate/silver nano composite material and preparation method thereof - Google Patents
Organic-silicon-modified acrylate/silver nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an organic-silicon-modified acrylate/silver nano composite material which is prepared with polydimethylsiloxane-b-polymethyl methacrylate as a stabilizer. A preparation method includes a step of: 1) mixing the polydimethylsiloxane-b-polymethyl methacrylate with an organic solvent according to the mass ratio of 1:35-350 for 30-60 min, sealing the container, and allowing the mixture to stand at 10-50 DEG C for 2-4 h to prepare a solution (I); 2) mixing silver nitrate, dimethyl formamide and water according to the mass ratio of 1:30-230:0.1 in a sealed container for 3-20 min at 10-50 DEG C in a sealed container to prepare a solution (II); 3) according to mass ratio, moving 1 part of the solution (II) to 1-3 parts of the solution (I) at 10-50 DEG C, and stirring the solutions for 8-40 h under a shading condition to obtain a homogeneous sol liquid; and 4) concentrating the sol liquid, removing solvents, and separating the mixture to obtain the organic-silicon-modified acrylate/silver nano composite material.
Description
Technical field
The present invention relates to a kind of Organic/Inorganic Composite Nanomaterials and preparation method thereof, particularly relate to a kind of organic-silicon-modified acrylate/argentum nano composite material and preparation method thereof.
Background technology
At present, along with the development of science and technology, people are also more and more higher to the material performance requirement of field of coating, and the Coating Market with the combination property such as heat-resisting, antifouling, antibacterial has a extensive future.Heat-proof macromolecule material mainly has aromatic ring polymer class, heterocycle polymer class, ladder polymer class, elemento-organic polymer class；The resin that can be used for preparing low surface energy anti-fouling paint mainly has fluorocarbon resin, organic siliconresin and fluorine silicon resin three major types；And can be used for the ion-type anti-biotic material of the antibacterial ion such as mainly argentiferous, copper, zinc of inorganic antibacterial material and photocatalytic activity anti-biotic material and containing metal oxide anti-biotic material three kinds.
It is known that Organic/Inorganic Composite Nanomaterials can integrate the excellent properties of each component.It is understood that polyacrylate has good biocompatibility, have that film is plentiful and mechanical strength advantages of higher, but weatherability and stain resistant are not enough；And organosilicon material has very low surface energy, having well hydrophobic, stain resistant performance, and in such material, Si-O bond energy is high, interior Rotation energy barrier is low so that it is have the high-low temperature resistant of excellence, physiology and chemical inertness.Therefore, this kind of composite can be made to be combined by the excellent properties of acrylate and organosilicon through organic-silicon-modified acrylate so that this kind of material has good heat-resisting, antifouling property.
Current organosilicon-modified acrylate can adopt the method (GraiverD of radical polymerization, DeckerGT, KimY, HamiltonFJ, HarwoodHJ.Graftandblockcopolymerswithpolysiloxaneandviny lpolymersegments [J] .Silicon.Chem, 2002,1 (12): 107-120.).Before realizing modifiying, generally first prepare the polydimethylsiloxane (PDMS) of functionalization, utilize the polydimethylsiloxane (PDMS) of functionalization to be used as macromole evocating agent, macromonomer and transfer agent acceptor.If Minami et al. is under nitrogen atmosphere is protected; in triethylamine, reaction it is stirred with 2-bromine isobutyryl for initiation material with the polydimethylsiloxane that end contains hydroxyl; reaction is filtered after terminating; it is dissolved in dichloromethane after filtrate decompression is distilled off inert organic solvents; wash at least 1 time with cold sodium bicarbonate solution; separatory; organic layer desiccant dryness; refilter, finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow.According to atom transfer radical polymerization mechanism, carrying out polyreaction under the protection of inert atmosphere, with Cu-lyt. for catalyst, with 1, Isosorbide-5-Nitrae, 7,7-PMDETAs are part, carry out atom transfer radical polymerization in atent solvent toluene.According to mol ratio, methyl methacrylate: initiator: catalyst: part=10～100:1:1:3 feeds in raw material, after freezing-evacuation-defrosting 3 times circulation, heated solution, 80-90 DEG C starts reaction.After reacting 5 hours, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after again product being dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.null(HidetoMinami,YasuyukiKagawa,ShintaroKuwahara,JunjiShigematsu,SyujiFujii&MasayoshiOkubo.Dispersionatomtransferradicalpolymerizationofmethylmethacrylatewithbromo-terminatedpoly(dimethylsiloxane)insupercriticalcarbondioxide.DesignedMonomersandPolymers.2004,796): 553-562).
Ketonic oxygen in polyacrylate has good complexing power for metal ion, thus this characteristic has vouchsafed again organic-silicon-modified acrylate another performance of this kind of material, namely it can as the stabilizer in metal nanoparticle preparation process so that the Organic/Inorganic Composite Nanomaterials obtained after separating-purifying has more special performance.
Summary of the invention
The present invention provides a kind of organic-silicon-modified acrylate/argentum nano composite material.The present invention also provides for a kind of adopting organic-silicon-modified acrylate (PDMS-b-PMMA) for the stabilizer method to prepare organic-silicon-modified acrylate/argentum nano composite material.This composite, namely polydimethylsiloxane-b-polymethyl methacrylate/silver nano-grain (PDMS-b-PMMA/Ag), has the bulk properties of organic material and inorganic material concurrently, has well heat-resisting, antifouling and anti-microbial property.
Acrylate/argentum nano composite material (PDMS-b-PMMA/Ag) that the present invention is organic-silicon-modified, with PDMS-b-PMMA for stabilizer, in the mixed solvent that organic solvent and dimethylformamide form, add a small amount of silver nitrate as metal inorganic salt presoma, add minor amount of water, when without additionally adding reducing agent, in-situ reducing silver nitrate, finally being concentrated by mixed solution, precipitate, be centrifuged, obtain Organic/Inorganic Composite Nanomaterials after drying, its concrete preparation method is as follows:
(1) synthesis PDMS-b-PMMA
PDMS-b-PMMA can be synthesized according to the method disclosed in prior art.nullSuch as: under inert gas shielding，In triethylamine, reaction it is stirred with 2-bromine isobutyl acylbromide for initiation material with the polydimethylsiloxane that end contains hydroxyl，End contains the polydimethylsiloxane of hydroxyl: 2-bromine isobutyl acylbromide: triethylamine is 1:(1.5-4.2): (2.7-6.6)，Reaction is filtered after terminating，It is dissolved in dichloromethane after filtrate decompression is distilled off triethylamine，Wash at least 1 time with cold sodium bicarbonate solution，Separatory，Organic layer desiccant dryness，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent toluene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part=10～100:1:1:3 feeds in raw material, after freezing-evacuation-defrosting 3 times circulation, heated solution, 80-90 DEG C starts reaction.After reaction 5h, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after again product being dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) organic-silicon-modified acrylate/argentum nano composite material is prepared with PDMS-b-PMMA for stabilizer
1) after PDMS-b-PMMA being mixed 30～60 minutes with organic solvent 1:35～350 in mass ratio, seal container and at 10～50 DEG C place within 2～4 hours, prepare into solution first, described organic solvent includes toluene, dimethylbenzene, hexamethylene, chlorobenzene, ethanol, ether, ethyl acetate, methyl acetate, acetone, butanone etc.；
2) it is that 1:30～230:0.1 mixes 3-20 minute wiring solution-forming second in 10～50 DEG C in sealing container by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 10～50 DEG C, in mass ratio 1 part of solution second is transferred in 1～3 part of solution first, when lucifuge, stir 8～40 hours, obtain homogeneous sol solution；
4) concentration sol solution, after removing major part solvent, with the alcohol for sedimentation reactant liquor of 1-4 carbon, is finally separating to obtain organic-silicon-modified acrylate/argentum nano composite material.
Organosilicon-modified acrylate/argentum nano composite material of the present invention, its heat resistance can be tested by thermal gravimetric analyzer, heating rate is 10 DEG C/min, under nitrogen atmosphere from room temperature to 800 DEG C, as can be seen from Figure 1, comparing simple acrylate material through organic-silicon-modified acrylate/argentum nano composite material and have better heat resistance, complete heat decomposition temperature is brought up to 650 DEG C by 550 DEG C.Composite material film hydrophobic properties of the surface utilize KRUSS (ContactAngleMeasuringInstrumentDSA30) contact angle instrument to test, and take the meansigma methods of 5 some tests as Static water contact angle value.Static water contact angle value is more than 90 °, and just for hydrophobic surface, in Fig. 2, Static water contact angle value is 118.4 °, has good hydrophobicity.It is finally introducing Escherichia coli bacteria liquid, utilizes Agar Plating to carry out Bactericidal test, can be used to judge qualitatively the antibacterial effect of material by the presence or absence and size thereof observing inhibition zone.The anti-microbial property of sample is evaluated by the size of inhibition zone, and the diameter of inhibition zone is more big, it was shown that the antibacterial effect of this material is more good, otherwise, then show that the antibacterial effect of this material is more poor.General antibacterial circle diameter just has good antibacterial effect more than 25mm.The antibacterial circle diameter showing the organic-silicon-modified acrylate/argentum nano composite material of the present invention in Fig. 3 is 34mm.
Accompanying drawing explanation
Fig. 1 is acrylate/argentum nano composite material thermogravimetric curve figure that the present invention is organic-silicon-modified.
Fig. 2 is the Static water contact angles (118.4 °) of the organic-silicon-modified acrylate/argentum nano composite material of the present invention
Fig. 3 is the Bactericidal test (antibacterial circle diameter is 34mm) of the organic-silicon-modified acrylate/argentum nano composite material of the present invention
Composite of the present invention combines the optical transparence of organosilicon material, heat stability, chemical inertness, nontoxic, high hydrophobicity, the bacteriostasis property of the biocompatibility of polymethyl methacrylate, higher mechanical strength and silver nano-grain, product is made to have heat-resisting, antifouling, anti-microbial property concurrently in one, preparation method uses a small amount of silver nitrate, without additionally adding reducing agent, can in the mixed solvent of solvent polymerization thing, reduced by direct in-situ, and the polymer added serves good Stabilization so that nano-particle manifests without gathering.
Detailed description of the invention
Embodiment 1
(1) synthesis PDMS-b-PMMA
nullUnder nitrogen atmosphere is protected，1 part of end is contained the polydimethylsiloxane of hydroxyl、1.8 parts of 2-bromine isobutyryls and 3 parts of triethylamines are stirred reaction 30h at 0 DEG C，After reaction terminates,Filter，It is dissolved in dichloromethane after filtrate decompression is distilled off solvent，Wash 3 times with cold sodium bicarbonate solution，Separatory，Organic over anhydrous magnesium sulfate dries and dewaters，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent toluene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part=10:1:1:3 feeds in raw material, after freezing-evacuation-defrostings 3 times circulation, heated solution, start to react.After reaction terminates, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after product is dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) PDMS-b-PMMA obtained with (1) prepares silver nano-grain for stabilizer, obtains organic-silicon-modified acrylate/argentum nano composite material
1) by PDMS-b-PMMA with after toluene in mass ratio 1:35 mixing 30min, seal container and at 35 DEG C place 2h prepare into first solution；
2) it is that 1:30:0.1 mixes 5min in 35 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 35 DEG C, in mass ratio 1 part of second solution is transferred in 1 part of first solution, when lucifuge, after stirring 14h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 215 °, and 600 ° are decomposed completely, and its Static water contact angles can reach 100.2 °, and antibacterial circle diameter is 27mm.
Comparative example 1
1) by PMMA with after toluene in mass ratio 1:35 mixing 30min, seal container and at 35 DEG C place 2h prepare into first solution；
2) it is that 1:30:0.1 mixes 5min in 35 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 35 DEG C, in mass ratio 1 part of second solution is transferred in 1 part of first solution, when lucifuge, after stirring 14h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 200 °, and 550 ° are decomposed completely, and its Static water contact angles can reach 98 °, and antibacterial circle diameter is 29mm.
Embodiment 2
(1) synthesis PDMS-b-PMMA
nullUnder nitrogen atmosphere is protected，1 part of end is contained the polydimethylsiloxane of hydroxyl、1.8 parts of 2-bromine isobutyryls and 3 parts of triethylamines are stirred reaction 18h at 15 DEG C，After reaction terminates,Filter，It is dissolved in dichloromethane after filtrate decompression is distilled off solvent，Wash 2 times with cold sodium bicarbonate solution，Separatory，Organic over anhydrous magnesium sulfate dries and dewaters，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent dimethylbenzene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part is that 20:1:1:3 feeds in raw material, after freezing-evacuation-defrostings 3 times circulation, heated solution, start to react.After reaction terminates, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after product is dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) PDMS-b-PMMA obtained with (1) prepares silver nano-grain for stabilizer, obtains organic-silicon-modified acrylate/argentum nano composite material
1) by PDMS-b-PMMA with after toluene in mass ratio 1:100 mixing 50min, seal container and at 35 DEG C place 2h prepare into first solution；
2) it is that 1:100:0.1 mixes 20min in 10 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 10 DEG C, in mass ratio 1 part of second solution is transferred in 2 parts of first solution, when lucifuge, after stirring 12h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 208 °, and 600 ° are decomposed completely, and its Static water contact angles can reach 108.3 °, and antibacterial circle diameter is 28.5mm.
Comparative example 2
1) by PMMA with after toluene in mass ratio 1:100 mixing 50min, seal container and at 35 DEG C place 2h prepare into first solution；
2) it is that 1:100:0.1 mixes 20min in 10 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 10 DEG C, in mass ratio 1 part of second solution is transferred in 2 parts of first solution, when lucifuge, after stirring 12h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 201 °, and 552 ° are decomposed completely.Its Static water contact angles can reach 100.2 °, and inhibition zone is sized to 25mm.
Embodiment 3
(1) synthesis PDMS-b-PMMA
nullUnder nitrogen atmosphere is protected，1 part of end is contained the polydimethylsiloxane of hydroxyl、2.5 parts of 2-bromine isobutyryls and 4 parts of triethylamines are stirred reaction 15h at 20 DEG C，After reaction terminates,Filter，It is dissolved in dichloromethane after filtrate decompression is distilled off solvent，Wash 2 times with cold sodium bicarbonate solution，Separatory，Organic over anhydrous magnesium sulfate dries and dewaters，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent dimethylbenzene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part changes 40:1:1:3 into and feeds in raw material, after freezing-evacuation-defrostings 3 times circulation, heated solution, start to react.After reaction terminates, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after product is dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) PDMS-b-PMMA obtained with (1) prepares silver nano-grain for stabilizer, obtains organic-silicon-modified acrylate/argentum nano composite material
1) by PDMS-b-PMMA with after toluene in mass ratio 1:200 mixing 60min, seal container and at 25 DEG C place 3h prepare into first solution；
2) it is that 1:200:0.1 mixes 5min in 50 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 50 DEG C, in mass ratio 1 part of second solution is transferred in 3 parts of first solution, when lucifuge, after stirring 20h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, within dry 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 204 °, and 600 ° are decomposed completely, and its Static water contact angles can reach 118.4 °, and antibacterial circle diameter is 32mm.
Comparative example 3
1) by PMMA with after toluene in mass ratio 1:200 mixing 60min, seal container and at 25 DEG C place 3h prepare into first solution；
2) it is that 1:200:0.1 mixes 5min in 50 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 50 DEG C, in mass ratio 1 part of second solution is transferred in 3 parts of first solution, when lucifuge, after stirring 20h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, within dry 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 198 °, and 550 ° are decomposed completely.Its Static water contact angles can reach 108.4 °, and inhibition zone is sized to 23mm.
Embodiment 4
(1) synthesis PDMS-b-PMMA
nullUnder nitrogen atmosphere is protected，1 part of end is contained the polydimethylsiloxane of hydroxyl、2.8 parts of 2-bromine isobutyryls and 3.5 parts of triethylamines are stirred reaction 14h at 25 DEG C，After reaction terminates,Filter，It is dissolved in dichloromethane after filtrate decompression is distilled off solvent，Wash 2 times with cold sodium bicarbonate solution，Separatory，Organic over anhydrous magnesium sulfate dries and dewaters，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent dimethylbenzene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part changes 40:1:1:3 into and feeds in raw material, after freezing-evacuation-defrostings 3 times circulation, heated solution, start to react.After reaction terminates, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after product is dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) PDMS-b-PMMA obtained with (1) prepares silver nano-grain for stabilizer, obtains organic-silicon-modified acrylate/argentum nano composite material
1) by PDMS-b-PMMA with after toluene in mass ratio 1:350 mixing 30min, seal container and at 50 DEG C place 3h prepare into first solution；
2) it is that 1:230:0.1 mixes 10min in 45 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 45 DEG C, in mass ratio 1 part of second solution is transferred in 1 part of first solution, when lucifuge, after stirring 40h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 204 °, and 600 ° are decomposed completely, and its Static water contact angles can reach 118.2 °, and antibacterial circle diameter is 34mm.
Embodiment 5
(1) synthesis PDMS-b-PMMA
nullUnder nitrogen atmosphere is protected，1 part of end is contained the polydimethylsiloxane of hydroxyl、3.8 parts of 2-bromine isobutyryls and 4.5 parts of triethylamines are stirred reaction 12h at 25 DEG C，After reaction terminates,Filter，It is dissolved in dichloromethane after filtrate decompression is distilled off solvent，Wash 2 times with cold sodium bicarbonate solution，Separatory，Organic over anhydrous magnesium sulfate dries and dewaters，Refilter，Finally filtrate decompression is distilled off the polydimethylsiloxane macromer initiator that dichloromethane solvent obtains the bromine atoms end-blocking of oily yellow，Again with the polydimethylsiloxane macromer of the bromine atoms end-blocking of preparation for initiator，According to atom transfer radical polymerization mechanism，Polyreaction is carried out under the protection of inert atmosphere，With Cu-lyt. for catalyst，With 1,1,4,7,7-PMDETA is part，Atent solvent dimethylbenzene carries out atom transfer radical polymerization.According to mol ratio, methyl methacrylate: initiator: catalyst: part changes 40:1:1:3 into and feeds in raw material, after freezing-evacuation-defrostings 3 times circulation, heated solution, start to react.After reaction terminates, gained solution oxolane is diluted, again the solution after dilution is passed through alkali alumina post to remove catalyst, after filtrate is removed major part solvent with Rotary Evaporators, product is obtained with methanol extraction, after product is dissolved-precipitate at least 3 times repeatedly, finally it is placed in vacuum drying oven dry, obtains end-product polydimethylsiloxane-b-polymethyl methacrylate.
(2) PDMS-b-PMMA obtained with (1) prepares silver nano-grain for stabilizer, obtains organic-silicon-modified acrylate/argentum nano composite material
1) by PDMS-b-PMMA with after acetone in mass ratio 1:250 mixing 30min, seal container and at 40 DEG C place 4h prepare into first solution；
2) it is that 1:230:0.1 mixes 20min in 10 DEG C in sealing container and is made into second solution by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 10 DEG C, in mass ratio 1 part of second solution is transferred in 3 parts of first solution, when lucifuge, after stirring 40h, obtain homogeneous sol solution；
4) concentration sol solution, after utilizing Rotary Evaporators to remove major part solvent, use methanol extraction reactant liquor, then being centrifuged by this mixed solution, rotating speed is 15000r/min, and centrifugation time is 15min, take off a layer precipitate, being put in vacuum drying oven to be dried, drying baker temperature is set to 60 DEG C, dries and within 24 hours, finally obtains organic-silicon-modified acrylate/argentum nano composite material.This material starts thermal decomposition in 204 °, and 600 ° are decomposed completely, and its Static water contact angles can reach 118.2 °, and antibacterial circle diameter is 31mm.
Claims (1)
1. acrylate/argentum nano composite material one kind organic-silicon-modified, it is characterized in that described composite is polydimethylsiloxane-b-polymethyl methacrylate/silver nano-grain, with polydimethylsiloxane-b-polymethyl methacrylate for stabilizer, in the mixed solvent that organic solvent and dimethylformamide form, add a small amount of silver nitrate as metal inorganic salt presoma, add minor amount of water, when without additionally adding reducing agent, in-situ reducing silver nitrate, finally mixed solution is concentrated, precipitation, centrifugal, obtain Organic/Inorganic Composite Nanomaterials after drying, wherein, described stabilizer polydimethylsiloxane-b-polymethyl methacrylate adopts prior art synthesis,
1) after polydimethylsiloxane-b-polymethyl methacrylate mixes 30～60 minutes with organic solvent 1:35～350 in mass ratio, seal container and at 10～50 DEG C place within 2～4 hours, prepare into solution first, described organic solvent be selected from toluene, dimethylbenzene, hexamethylene, chlorobenzene, ethanol, ether, ethyl acetate, methyl acetate, acetone, butanone；
2) it is that 1:30～230:0.1 mixes 3-20 minute wiring solution-forming second in 10～50 DEG C in sealing container by silver nitrate, dimethylformamide and water according to mass ratio；
3) at 10～50 DEG C, in mass ratio 1 part of solution second is transferred in 1～3 part of solution first, when lucifuge, stir 8～40 hours, obtain homogeneous sol solution.
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| CN116120750A (en) * | 2023-04-04 | 2023-05-16 | 中国海洋大学 | Composite elastomer integrating resistance and killing, preparation method and antifouling application |
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| CN116120750A (en) * | 2023-04-04 | 2023-05-16 | 中国海洋大学 | Composite elastomer integrating resistance and killing, preparation method and antifouling application |
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