CN103804549A - Silver halide based photoinitiator and application thereof to light-induction unsaturated olefin monomer polymerization - Google Patents
Silver halide based photoinitiator and application thereof to light-induction unsaturated olefin monomer polymerization Download PDFInfo
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- CN103804549A CN103804549A CN201410032384.5A CN201410032384A CN103804549A CN 103804549 A CN103804549 A CN 103804549A CN 201410032384 A CN201410032384 A CN 201410032384A CN 103804549 A CN103804549 A CN 103804549A
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Abstract
The invention belongs to the technical field of photo-initiation polymer polymerization and particularly relates to a silver halide based photoinitiator and application of the silver halide based photoinitiator to light-induction unsaturated olefin monomer polymerization. Active silver halide based material is used as a photoinitiator, and organic polymer material is prepared through induction polymerization under ultraviolet light. Firstly, surface active agent is added into halide salt water solution, then silver nitrate solution is added under a stirring condition to perform reaction, and the active silver halide based photoinitiator is obtained through dialysis, the silver halide based photoinitiator, the unsaturated olefin monomer and water are mixed to form stable dispersion liquid, active silver halide particles in the silver halide based photoinitiator absorb ultraviolet light to generate free radical under the irradiation of an ultraviolet lamp, unsaturated olefin monomer polymerization is initiated, and then the organic polymer material is prepared. The polymerization reaction can be carried out in water phase, the using range of suitable monomers and low polymers is wide, and the silver halide based photoinitiator has the characteristics of quick reaction speed, gentle reaction condition, environment protection and the like.
Description
Technical field
The invention belongs to light-initiated technical field of macromolecule polymerization, be specially a kind of halogenation money base light trigger and the application at photoinduction unsaturated olefin monomer polymerization thereof, adopt active halogenation silver-based material as light trigger, under UV-light, induced polymerization is prepared organic polymer material.
Background technology
Light trigger is the luminous energy that a class can absorb certain wavelength, generates active radical, and the two key reactions in initiator system form growing chain and the curing material of trigger monomer polymerization crosslinking.Visible light initiator, because insensitive to daylight and general lighting light source, is subject to certain restrictions in application, and therefore most of light trigger of application is ultraviolet initiator at present.According to the active intermediate difference producing, can be divided into free radical type and cationic photoinitiator.The history of radical polymerization light trigger research is longer; kind is more; can be divided into small molecules light trigger, macromolecular photoinitiator and high-molecular optical initiator etc.; mainly some compounds that contain chromophore; particularly contain the carbonyl compound being connected with phenyl ring, mainly comprise benzoin and its derivatives, acetophenones, fragrant ketone, acylphosphine oxide etc.It is several that Cationic photoinitiator mainly contains aromatic diazo salt, aromatic sulfonium salts and salt compounded of iodine, ferrocene salt etc.Free radical photo-initiation is easily subject to the inhibition of oxygen in initiated polymerization process, and after solidifying, volumetric shrinkage is larger, and cation light initiator general curing speed is slower, and applicable monomer and oligopolymer are less, and price is generally more expensive.
In order to adapt to the requirement such as safety and environmental protection, by introduce yin, yang radical ion or wetting ability nonionic base in former light trigger structure, exploitation water-soluble light trigger is the important development direction of light trigger, develop at present benzophenone carboxylic acid's salt, Michler's keton photoinitiator, and introduced some water-soluble light triggers such as water-soluble thioxanthones of quaternary ammonium salt and sulfonate.
Except a large amount of organic molecule light triggers, some semiconductor materials are also found to realize photoinduction polymerization.The people such as Stroyuk adopt CdS and CdZn nano particle to realize acrylamide and acrylic acid photopolymerization, and think to be adsorbed on the monomer absorption light induced electron of particle surface and the addition of atomic hydrogen, have formed initial free radical.Damm has reported the TiO that only has crystallization under illumination
2particle can cause vinylformic acid photopolymerization process, at TiO
2a certain amount of Fe adulterates in particle
3+can increase photopolymerization speed.Adopt TiO
2the polymethacrylate that nano particle colloidal sol is prepared as photoinduction agent and TiO
2the interface bond strength of matrix material organic-inorganic material is higher, glass transition temp and thermostability all increase [Journal of Photochemistry and Photobiology A:Chemistry2005,174,171].Kuriacose and Markha have studied ZnO polyreaction to methyl methacrylate in different solvents in great detail, and the oxygen that proposes ZnO surface adsorption is the key that chain causes.
Silver halide is a kind of important light receiving semiconductor material, has a wide range of applications at aspects such as photography, electrode materials, infrared spectra, radiation and heterodyne detections.It is generally acknowledged that silver halide is unstable under illumination, be easy to absorb luminous energy and decompose.Kakuta etc. find that research in 1999 AgBr part under UV-irradiation resolves into simple substance Ag, form the matrix material of Ag and AgBr, and this matrix material is continuing under UV-irradiation to keep stable, and can be used for as photocatalyst material the preparation [J.Phys.Chem.B. of hydrogen, 1999,103,5917].Wang Peng etc. have prepared stable Ag/AgCl photocatalyst in 2009, and find that its catalytic performance is 8 times of N doped Ti O2, are expected to be applied to the degraded of environmental pollutant and sterilization aspect [Angew.Chem.Int.Ed.2008,47,7931 to environmental microorganism; Chemistry-A European Journal, 2009,15,1821].Meanwhile, AgBr and AgI system are also proved to be successively and have excellent photocatalysis performance.
The activity of silver halide material under illumination is closely related with the preparation process of particle, size, pattern etc.Wang Peng etc. adopt Ag
2moO
4under HCl effect, reaction forms AgCl particle, grain diameter between 0.2-1.3mm, size inhomogeneous [Angew.Chem.Int.Ed.2008,47,7931].The method of the employing ionic liquid Hydrothermal Synthesiss such as golden cypress mark is prepared micron-sized cubes and subsphaeroidal silver chloride particle, and wherein subsphaeroidal particle performance has gone out higher photocatalytic activity [Dalton Trans., 2011,40,4104].Hu etc. adopt mesoporous Al
2o
3for carrier, prepare stable loading type silver chloride photocatalyst, under visible ray irradiation, Some Organic Pollutants is had to very strong degraded and mineralization ability [J.AM.CHEM.SOC.2010,132,857].
These researchs show, silver halide absorbs photon energy under ultraviolet light irradiation, produce electron-hole pair in inside, and first light induced electron makes part Ag on surface
+be reduced into simple substance Ag nano particle, be attached to silver halide particle surface.Silver nano-grain can absorb light induced electron, prevents the further reduction of negatively charged ion, thereby makes silver halide under illumination, keep stable.There is very strong absorption because the plasma resonance effect of silver nano-grain makes this catalyst body tie up to visible light part, can realize the photocatalytic degradation [Journal of Materials Chemistry.2011,21,11532] under visible ray.And photohole makes halogen ion-oxygen change into halogen atom, halogen atom has very strong oxygenizement, likely induces the polymerization of olefinic organic hydrocarbon monomer simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of halogenation money base light trigger and the application at photoinduction unsaturated olefin monomer polymerization, this silver halide sill light trigger preparation technology is simple, stable, nontoxic under UV-light, and catalytic efficiency is high.
Technical scheme of the present invention is:
A kind of halogenation money base light trigger first adds tensio-active agent in the halide salt aqueous solution, then under agitation condition, adds silver nitrate solution to react, and obtains active halogenation money base light trigger through dialysis; In halogenation money base light trigger, active silver halide grain diameter size is between 1～800 nanometer, and this activity silver halide particle is one or more mixture of silver chloride, Silver monobromide, Silver iodide.
Described active silver halide grain diameter size is preferably between 40～450 nanometers.
Preparation method's concrete steps of described halogenation money base light trigger are as follows:
(1) prepare respectively 0.2～1wt% water phase surfactant mixture, 0.1～1wt% halide salt aqueous solution, 0.1～1wt%AgNO
3the aqueous solution;
(2) by volume for 1:1:1 gets water phase surfactant mixture, the halide salt aqueous solution, AgNO
3, water phase surfactant mixture is preheating 3～10min in 20～90 ℃ of water-baths, adds halide salt aqueous solution stirring reaction 20～60min, adds AgNO
3aqueous solution lucifuge stirs 20～40min, obtains AgCl colloid, with ultrapure water dialysis 1～48 hour, obtains active halogenation money base light trigger.
Described halide salt is NaCl, KCl, CaCl
2, KBr or KI.
Described water soluble surfactant active is sorbitan monooleate Soxylat A 25-7, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene glycol, Xylo-Mucine, alkyl glycoside, lauric acid amide of ethanol, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate.
Described halogenation money base light trigger is in the application of photoinduction unsaturated olefin monomer polymerization, halogenation money base light trigger, ethylenic unsaturation hydrocarbon monomer and water are mixed to form to stable dispersion liquid, under ultra violet lamp, active silver halide particle in halogenation money base light trigger absorbs UV-light and produces free radical, cause the polymerization of ethylenic unsaturation hydrocarbon monomer, thereby prepare organic polymer material.
Described ethylenic unsaturation hydrocarbon monomer is water-soluble ethylenic unsaturation hydrocarbon monomer or oil soluble ethylenic unsaturation hydrocarbon monomer, and water-soluble ethylenic unsaturation hydrocarbon monomer is simple function group, bifunctional or multi-functional acrylic ester monomer.
Described water-soluble ethylenic unsaturation hydrocarbon monomer is one or more of acrylamide, NIPA, N-isopropyl methyl acrylamide, vinylformic acid, V-Pyrol RC; Oil soluble ethylenic unsaturation hydrocarbon monomer is one or more of esters of acrylic acid, vinylchlorid, vinyl cyanide, methyl-prop ketenes, vinyl acetate, vinylbenzene, divinyl, isoprene, chloroprene, Vinylstyrene.
By silver halide micro-nano granules under UV-light when the water-soluble unsaturated olefin of initiated polymerization, by directly soluble in water water-soluble ethylenic unsaturation hydrocarbon monomer, add again silver halide colloids mixing and stirring, reaction system is passed into the air in high pure nitrogen eliminating system, then by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization;
By silver halide micro-nano granules under UV-light when initiated polymerization oil soluble unsaturated olefin, adopt microemulsion polymerization method in O/W type microemulsion system, in the mixing solutions of organic solvent and silver halide colloids, add dispersion stabilizer, make oil soluble ethylenic unsaturation hydrocarbon monomer and water form microemulsion, initiator silver halide is dissolved in water, unsaturated olefin is present in oil phase, reaction forward reaction system passes into the air in high pure nitrogen eliminating system, by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization; Wherein, dispersion stabilizer is polyvinylpyrrolidone, polyvinyl alcohol, sodium lignosulfonate, ethyl cellulose, sodium lauryl sulphate, Xylo-Mucine, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate.
In described dispersion liquid, silver halide concentration is between 0.005～0.2mol/L.
Advantage of the present invention and beneficial effect are:
1, the tensio-active agent that first the present invention adds in the halide salt aqueous solution then adds silver nitrate solution to react under agitation condition, obtains active halogenation money base light trigger through dialysis.Halogenation money base light trigger of the present invention is forming free radical under certain wavelength light irradiation, can realize the even radical polymerization under lower temperature of room temperature.Polyreaction can be carried out in water, and applicable monomer and oligopolymer are more extensive, have speed of response fast, reaction conditions gentleness, the features such as environmental friendliness.
2, the invention provides simple silver halide sill light trigger preparation method, in the halide salt aqueous solution, add a certain amount of tensio-active agent, then under certain temperature and agitation condition, add silver nitrate solution, after reaction certain hour, can obtain active halogenation money base light trigger through dialysis.Tensio-active agent can be controlled the forming core growth process of silver halide particle on the one hand, prevents on the other hand the gathering of silver halide particle, makes the halogenation money base light trigger obtaining have very high activity and stability.
3, the present invention adds water-soluble ethylenic unsaturation hydrocarbon monomer in halogenation money base light trigger aqueous dispersion liquid, as: acrylamide, NIPA, N-isopropyl methyl acrylamide, vinylformic acid, V-Pyrol RC etc., under UV-irradiation, can induce the polymerization of water-soluble ethylenic unsaturation hydrocarbon monomer.
4, halogenation money base light trigger of the present invention also can be induced the polymerization of oil soluble ethylenic unsaturation hydrocarbon monomer, in halogenation money base light trigger aqueous dispersion liquid, add oil soluble ethylenic unsaturation hydrocarbon monomer, as: esters of acrylic acid, vinylchlorid, vinyl cyanide, methyl-prop ketenes, vinyl acetate, vinylbenzene, divinyl, isoprene, chloroprene, Vinylstyrene etc.In order to improve polymerization efficiency, in solution, add dispersion stabilizer, make oil soluble ethylenic unsaturation hydrocarbon monomer and water form microemulsion, under ultraviolet light irradiation, can cause the polymerization of oil soluble ethylenic unsaturation hydrocarbon monomer.
5, halogenation money base light trigger of the present invention forms stable dispersion liquid in solvent, adds ethylenic unsaturation hydrocarbon monomer in this dispersion liquid; Under ultra violet lamp, the active silver halide particle in halogenation money base light trigger absorbs UV-light and produces free radical, causes the polymerization of ethylenic unsaturation hydrocarbon monomer, thereby prepares organic polymer material.
6, the active silver halide particle of halogenation money base light trigger of the present invention can be dispersed in water and form stable dispersion liquid, water-soluble ethylenic unsaturation hydrocarbon monomer is directly soluble in water, to oil soluble ethylenic unsaturation hydrocarbon monomer, can add certain emulsifying agent, form the O/w emulsion take oil soluble unsaturated olefin as oil phase, thereby improve speed of response and transformation efficiency.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the poly N-isopropyl acrylamide prepared of embodiment 1.
Fig. 2 is the infrared spectrogram (FTIR) of the poly N-isopropyl acrylamide prepared of embodiment 1.Wherein, (a) NIPA monomer; (b) poly N-isopropyl acrylamide that prepared by embodiment 1.
Fig. 3 is the XRD figure spectrum of the polystyrene prepared of embodiment 3.
Fig. 4 is the infrared spectrogram (FTIR) of the polystyrene prepared of embodiment 3.
Fig. 5 is the infrared spectrogram (FTIR) of the polymethylmethacrylate prepared of embodiment 6.
Embodiment
The present invention is by volume for 1:1:1 gets water phase surfactant mixture, the halide salt aqueous solution, AgNO
3the aqueous solution, water phase surfactant mixture is preheating 3～10min in 20～90 ℃ of water-baths, adds halide salt aqueous solution stirring reaction 20～60min, adds AgNO
3aqueous solution lucifuge stirs 20～40min, obtain AgCl colloid, in 20～50 ℃ of ultrapure waters, dialyse 1～48 hour, to remove the too much tensio-active agent in silver halide colloids surface, make it have the strongest UV-resistance, obtain active halogenation money base light trigger.
Water soluble surfactant active can be sorbitan monooleate Soxylat A 25-7 (Tween80), sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene glycol, Xylo-Mucine, alkyl glycoside, lauric acid amide of ethanol, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate etc.
Ethylenic unsaturation hydrocarbon monomer comprises water-soluble unsaturated olefin and oil soluble unsaturated olefin two classes, water-soluble ethylenic unsaturation hydrocarbon monomer is simple function group, bifunctional or multi-functional acrylic ester monomer, as: acrylamide, NIPA, N-isopropyl methyl acrylamide, vinylformic acid, V-Pyrol RC etc. one or more; Oil soluble unsaturated olefin mainly contain esters of acrylic acid, vinylchlorid, vinyl cyanide, methyl-prop ketenes, vinyl acetate, vinylbenzene, divinyl, isoprene, chloroprene, Vinylstyrene etc. one or more.
By silver halide micro-nano granules under UV-light when the water-soluble unsaturated olefin of initiated polymerization, by directly soluble in water water-soluble ethylenic unsaturation hydrocarbon monomer, add again silver halide colloids mixing and stirring, reaction system is passed into the air in high pure nitrogen eliminating system, then by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization.Specific as follows:
The water-soluble ethylenic unsaturation hydrocarbon monomer that takes 0.5～1mmol is dissolved in 0.5～5ml deionized water, adds the above-mentioned silver halide colloids 1～15ml preparing, and mixing and stirring, passes into high pure nitrogen N
2(bulk purity is more than 99.999%) 20～40min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 30～100W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 1～300min, obtains high molecular polymer; Close ultraviolet lamp, finish reaction.
By silver halide micro-nano granules under UV-light when initiated polymerization oil soluble unsaturated olefin, adopt microemulsion polymerization method in certain O/W type microemulsion system, in the mixing solutions of organic solvent and silver halide colloids, add dispersion stabilizer, make oil soluble ethylenic unsaturation hydrocarbon monomer and water form microemulsion, initiator silver halide is dissolved in water, unsaturated olefin is present in oil phase, reaction forward reaction system passes into the air in high pure nitrogen eliminating system, by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization.In order to improve polymerization efficiency, in solution, add dispersion stabilizer, make oil soluble ethylenic unsaturation hydrocarbon monomer and water form microemulsion, under ultraviolet light irradiation, can cause the polymerization of oil soluble ethylenic unsaturation hydrocarbon monomer.Wherein, dispersion stabilizer can be polyvinylpyrrolidone (PVP), polyvinyl alcohol, sodium lignosulfonate, ethyl cellulose, sodium lauryl sulphate, Xylo-Mucine, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate etc.Organic solvent is conventional ethanol, acetone, dimethylbenzene, methylene dichloride etc.Specific as follows:
Get the silver halide colloids of above-mentioned preparation and the mixing solutions 10～20mL(V of organic solvent
organic solvent: V
silver halide colloids=2～6:1), add 0.05～0.2g dispersion stabilizer magnetic agitation to abundant dissolving, add 0.5～3mL oil soluble ethylenic unsaturation hydrocarbon monomer, magnetic agitation forms O/W type transparent micro emulsion, passes into high-purity N
2(bulk purity is more than 99.999%) 20～40min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 30～100W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 30～90min, obtains high molecular polymer; Close ultraviolet lamp, finish reaction.
Below in conjunction with specific embodiment, to further detailed introduction of the present invention, but content of the present invention is not limited only to content related in embodiment.
Embodiment 1:
Join 1wt% sorbitan monooleate Soxylat A 25-7 (Tween80) aqueous solution, 0.067wt%CaCl
2the aqueous solution, 0.25wt%AgNO
3the aqueous solution is stand-by.
Getting concentration is Tween80 aqueous solution 20ml preheating 5min in 50 ℃ of water-baths of 1wt%, and adding 20ml concentration is the CaCl of 0.067wt%
2aqueous solution stirring reaction 30min, adding rapidly concentration is the AgNO of 0.25wt%
3aqueous solution 20ml lucifuge stirs 30min, obtains AgCl colloid, and with ultrapure water dialysis, 1.5h is for subsequent use, and in AgCl colloid, active A gCl grain diameter size is in 50～800 nanometers.The NIPA that takes 0.7mmol is dissolved in 1ml deionized water, adds the above-mentioned AgCl colloid 10ml preparing, and mixing and stirring, passes into high pure nitrogen N
230min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 36W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 25min, obtains poly N-isopropyl acrylamide; Close ultraviolet lamp, finish reaction.After reaction finishes, by reaction solution lyophilize, with the product of ether washing freeze-drying, after suction filtration, under room temperature, naturally dry, weigh, transformation efficiency reaches 100%.
As shown in Figure 1, on the product X RD spectrogram of above-mentioned preparation, 5 °～25 ° have shown the unformed peak of obvious polymkeric substance, have the characteristic peak of a small amount of argent and the characteristic peak of undecomposed silver chloride on product simultaneously.
As shown in Figure 2, the product infrared spectra of above-mentioned preparation is compared with monomer NIPA infrared spectra, 1620cm on monomer
-1the characteristic peak of the C=C of place disappears in polymkeric substance infrared spectrogram, 1540cm in polymkeric substance infrared spectra
-1, 1457cm
-1be respectively acid amides II key in poly N-isopropyl acrylamide and the characteristic peak of acid amides III key.Infrared spectra shows, the silver chloride that monomer NIPA is prepared in the present invention, as under light trigger, ultraviolet light irradiation condition, polyreaction has occurred really.
Embodiment 2:
With embodiment 1 method, wherein NIPA replaces with N-isopropyl methyl acrylamide, and its quality is 0.1g, obtains poly-N-isopropyl Methacrylamide, and transformation efficiency is 100%.
Embodiment 3
Join the 1wt%Tween-80 aqueous solution, 0.067wt%CaCl
2the aqueous solution, 0.25wt%AgNO
3the aqueous solution is stand-by.
Getting concentration is Tween-80 aqueous solution 20ml preheating 5min in 50 ℃ of water-baths of 1wt%, and adding 20ml concentration is the CaCl of 0.067wt%
2aqueous solution stirring reaction 30min, adding rapidly concentration is the AgNO of 0.25wt%
3aqueous solution 20ml lucifuge stirs 30min, obtains AgCl colloid, and with ultrapure water dialysis, 2h is for subsequent use, and in AgCl colloid, active A gCl grain diameter size is at 50～800nm.Get the AgCl colloid of above-mentioned preparation and the mixing solutions 14mL(V of dehydrated alcohol
ethanol: V
agCl colloid=5:1), add 0.15g polyvinylpyrrolidone (PVP) as dispersion stabilizer, magnetic agitation, to abundant dissolving, adds 2mL vinylbenzene, and magnetic agitation forms O/W type transparent micro emulsion, passes into high-purity N
230min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 36W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 1h, obtains polystyrene; Close ultraviolet lamp, finish reaction.By reacted emulsion on Rotary Evaporators at 60 ℃ evaporated under reduced pressure, then use ultrapure water washed twice, centrifugation, finally, by product freeze-drying, weighs, transformation efficiency reaches 30%.
As shown in Figure 3, on product X RD spectrogram, 5 °～25 ° have shown the unformed peak of obvious polymkeric substance, have the characteristic peak of a small amount of argent and the characteristic peak of undecomposed silver chloride on product simultaneously.
As shown in Figure 4,3024cm in the polystyrene infrared spectra of above-mentioned preparation
-1, 754cm
-1, 697cm
-1place is the proton key band of the monosubstituted phenyl ring of vinylbenzene; 1600cm
-1, 1492cm
-1, 1453cm
-1place is phenyl ring skeletal vibration bands of a spectrum; 2920cm
-1place corresponds to the asymmetric stretching vibration of C-H, 2848cm
-1place corresponds to C-H symmetrical stretching vibration.Infrared spectra shows, the silver chloride that monomer styrene is prepared in the present invention, as under light trigger, ultraviolet light irradiation condition, polyreaction has occurred really.
Embodiment 4:
Join the 1wt%Tween80 aqueous solution, the 0.17wt%KBr aqueous solution, 0.25wt%AgNO
3the aqueous solution is stand-by.
Getting concentration is Tween80 aqueous solution 20ml preheating 5min in 50 ℃ of water-baths of 1wt%, and adding 20ml concentration is the KBr aqueous solution stirring reaction 30min of 0.17wt%, and adding rapidly concentration is the AgNO of 0.25wt%
3aqueous solution 20ml lucifuge stirs 30min, obtains AgBr colloid, and with ultrapure water dialysis, 2h is for subsequent use, and in AgBr colloid, active A gBr grain diameter size is in 20～800 nanometers.Take 0.7mmol vinylformic acid and be dissolved in 1ml deionized water, add the above-mentioned AgBr colloid 10ml preparing, mixing and stirring, passes into high-purity N
230min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 36W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 25min, obtains polyacrylic acid; Close ultraviolet lamp, finish reaction.After reaction finishes, by reaction solution lyophilize, with the product of ether washing freeze-drying, after suction filtration, under room temperature, naturally dry, weigh, transformation efficiency reaches 100%.
Embodiment 5:
Join the 1wt%Tween80 aqueous solution, the 0.25wt%KI aqueous solution, 0.25wt%AgNO
3the aqueous solution is stand-by.
Getting concentration is Tween80 aqueous solution 20ml preheating 5min in 50 ℃ of water-baths of 1wt%, and adding 20ml concentration is the KI aqueous solution stirring reaction 30min of 0.25wt%, and adding rapidly concentration is the AgNO of 0.25wt%
3aqueous solution 20ml lucifuge stirs 30min, obtains AgI colloid, and with ultrapure water dialysis, 2h is for subsequent use, and in AgI colloid, active A gI grain diameter size is in 10～800 nanometers.Take 0.7mmol acrylamide and be dissolved in 1ml deionized water, add the above-mentioned AgI colloid 10ml preparing, mixing and stirring, passes into high-purity N
230min gets rid of inner air tube, then, by reaction tubes sealing, is placed under 36W ultraviolet lamp and magnetic agitation, and under uv light irradiation, direct initiated polymerization 25min, obtains polyacrylamide; Close ultraviolet lamp, finish reaction.After reaction finishes, by reaction solution lyophilize, with the product of ether washing freeze-drying, after suction filtration, under room temperature, naturally dry, weigh, transformation efficiency reaches 100%.
Embodiment 6:
With embodiment 3 methods, wherein vinylbenzene replaces with methyl methacrylate, obtains polymethylmethacrylate, and transformation efficiency is 90%.
As shown in Figure 5, can find out 1732cm from the infrared spectrogram (FTIR) of polymethylmethacrylate
-1place is ester carbonyl group C-O stretching vibration peak, 1444cm
-1place is O (CH
3) asymmetric bending vibrational band, 1195cm
-1place is-O-CH
3stretching vibration key band, 1062cm
-1place is the strong and weak key band that interacts in polymethylmethacrylate molecular chain, does not have the two key key bands of obvious C=C on infrared spectra.Showing, as under light trigger, ultraviolet light irradiation condition, there is polyreaction in the silver chloride that monomers methyl methacrylate is prepared in the present invention really.
Embodiment result shows, the active halogenation silver-based material of the present invention silver halide particle under illumination can be induced polymerization and the copolymerization of multiple olefinic organic hydrocarbon monomer effectively, and have very high photocatalysis efficiency, this activity halogenation silver-based material have not been reported as a kind of new light trigger.
Claims (10)
1. a halogenation money base light trigger, is characterized in that: first in the halide salt aqueous solution, add tensio-active agent, then under agitation condition, add silver nitrate solution to react, obtain active halogenation money base light trigger through dialysis; In halogenation money base light trigger, active silver halide grain diameter size is between 1～800 nanometer, and this activity silver halide particle is one or more mixture of silver chloride, Silver monobromide, Silver iodide.
2. according to halogenation money base light trigger claimed in claim 1, it is characterized in that: active silver halide grain diameter size is preferably between 40～450 nanometers.
3. according to halogenation money base light trigger claimed in claim 1, it is characterized in that, preparation method's concrete steps of halogenation money base light trigger are as follows:
(1) prepare respectively 0.2～1wt% water phase surfactant mixture, 0.1～1wt% halide salt aqueous solution, 0.1～1wt%AgNO
3the aqueous solution;
(2) by volume for 1:1:1 gets water phase surfactant mixture, the halide salt aqueous solution, AgNO
3, water phase surfactant mixture is preheating 3～10min in 20～90 ℃ of water-baths, adds halide salt aqueous solution stirring reaction 20～60min, adds AgNO
3aqueous solution lucifuge stirs 20～40min, obtains AgCl colloid, with ultrapure water dialysis 1～48 hour, obtains active halogenation money base light trigger.
4. according to halogenation money base light trigger claimed in claim 1, it is characterized in that: halide salt is NaCl, KCl, CaCl
2, KBr or KI.
5. according to halogenation money base light trigger claimed in claim 1, it is characterized in that: water soluble surfactant active is sorbitan monooleate Soxylat A 25-7, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene glycol, Xylo-Mucine, alkyl glycoside, lauric acid amide of ethanol, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate.
6. a halogenation money base light trigger claimed in claim 1 is in the application of photoinduction unsaturated olefin monomer polymerization, it is characterized in that, halogenation money base light trigger, ethylenic unsaturation hydrocarbon monomer and water are mixed to form to stable dispersion liquid, under ultra violet lamp, active silver halide particle in halogenation money base light trigger absorbs UV-light and produces free radical, cause the polymerization of ethylenic unsaturation hydrocarbon monomer, thereby prepare organic polymer material.
7. the application at photoinduction unsaturated olefin monomer polymerization according to halogenation money base light trigger claimed in claim 6, it is characterized in that, ethylenic unsaturation hydrocarbon monomer is water-soluble ethylenic unsaturation hydrocarbon monomer or oil soluble ethylenic unsaturation hydrocarbon monomer, and water-soluble ethylenic unsaturation hydrocarbon monomer is simple function group, bifunctional or multi-functional acrylic ester monomer.
8. the application at photoinduction unsaturated olefin monomer polymerization according to halogenation money base light trigger claimed in claim 7, it is characterized in that, water-soluble ethylenic unsaturation hydrocarbon monomer is one or more of acrylamide, NIPA, N-isopropyl methyl acrylamide, vinylformic acid, V-Pyrol RC; Oil soluble ethylenic unsaturation hydrocarbon monomer is one or more of esters of acrylic acid, vinylchlorid, vinyl cyanide, methyl-prop ketenes, vinyl acetate, vinylbenzene, divinyl, isoprene, chloroprene, Vinylstyrene.
9. the application at photoinduction unsaturated olefin monomer polymerization according to halogenation money base light trigger claimed in claim 7, is characterized in that,
By silver halide micro-nano granules under UV-light when the water-soluble unsaturated olefin of initiated polymerization, by directly soluble in water water-soluble ethylenic unsaturation hydrocarbon monomer, add again silver halide colloids mixing and stirring, reaction system is passed into the air in high pure nitrogen eliminating system, then by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization;
By silver halide micro-nano granules under UV-light when initiated polymerization oil soluble unsaturated olefin, adopt microemulsion polymerization method in O/W type microemulsion system, in the mixing solutions of organic solvent and silver halide colloids, add dispersion stabilizer, make oil soluble ethylenic unsaturation hydrocarbon monomer and water form microemulsion, initiator silver halide is dissolved in water, unsaturated olefin is present in oil phase, reaction forward reaction system passes into the air in high pure nitrogen eliminating system, by reaction system sealing, under magnetic agitation condition under uv light irradiation direct initiated polymerization; Wherein, dispersion stabilizer is polyvinylpyrrolidone, polyvinyl alcohol, sodium lignosulfonate, ethyl cellulose, sodium lauryl sulphate, Xylo-Mucine, polyoxyethylene laurel ether, polyoxyethylene stearic acid ester or polyoxyethylene oleate.
10. the application at photoinduction unsaturated olefin monomer polymerization according to halogenation money base light trigger claimed in claim 6, is characterized in that, in dispersion liquid, silver halide concentration is between 0.005～0.2mol/L.
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| CN104259478A (en) * | 2014-09-28 | 2015-01-07 | 南京欣益浩化学科技有限公司 | Preparation method of silver nanowire |
| CN112673030A (en) * | 2018-08-16 | 2021-04-16 | 西锐斯材料科技有限公司 | Method for preparing polymer and metal-polymer composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337687A (en) * | 2008-08-07 | 2009-01-07 | 中国人民解放军海军工程大学 | Process for preparing nano-grade AgCl powder by semisolid method |
| CN101774630A (en) * | 2010-01-29 | 2010-07-14 | 浙江大学 | Preparation method of water-soluble silver halide nanoparticle |
| CN101816943A (en) * | 2010-04-30 | 2010-09-01 | 安徽师范大学 | High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof |
| CN101962205A (en) * | 2009-07-24 | 2011-02-02 | 烟台海岸带可持续发展研究所 | Halogenated silver nano-particles and synthesis method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337687A (en) * | 2008-08-07 | 2009-01-07 | 中国人民解放军海军工程大学 | Process for preparing nano-grade AgCl powder by semisolid method |
| CN101962205A (en) * | 2009-07-24 | 2011-02-02 | 烟台海岸带可持续发展研究所 | Halogenated silver nano-particles and synthesis method and application thereof |
| CN101774630A (en) * | 2010-01-29 | 2010-07-14 | 浙江大学 | Preparation method of water-soluble silver halide nanoparticle |
| CN101816943A (en) * | 2010-04-30 | 2010-09-01 | 安徽师范大学 | High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104259478A (en) * | 2014-09-28 | 2015-01-07 | 南京欣益浩化学科技有限公司 | Preparation method of silver nanowire |
| CN112673030A (en) * | 2018-08-16 | 2021-04-16 | 西锐斯材料科技有限公司 | Method for preparing polymer and metal-polymer composite material |
| CN112673030B (en) * | 2018-08-16 | 2023-08-01 | 西锐斯材料科技有限公司 | Method for producing polymer and metal-polymer composite |
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