CN104815629A - Composite nano photocatalytic material and preparation method thereof by radiation grafting-embedment - Google Patents
Composite nano photocatalytic material and preparation method thereof by radiation grafting-embedment Download PDFInfo
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- CN104815629A CN104815629A CN201510242401.2A CN201510242401A CN104815629A CN 104815629 A CN104815629 A CN 104815629A CN 201510242401 A CN201510242401 A CN 201510242401A CN 104815629 A CN104815629 A CN 104815629A
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Abstract
The invention discloses a composite nano photocatalytic material and a preparation method thereof by radiation grafting-embedment. The method comprises the following steps: irradiating a high polymer substrate by ionizing radiation to generate active free radicals, carrying out graft polymerization reaction on the irradiated high polymer substrate and an intermediate monomer by precisely regulating the radiation technological parameters and reaction conditions, and effectively embedding an inorganic nano photocatalyst by a grafting monomer to effectively synthesize a serial novel composite nano photocatalytic material capable of substituting the traditional single inorganic nano photocatalytic material. The synthesis method has the advantages of high grafting ratio, high embedment ratio and simplified synthesis technique. The synthetic product has the advantages of high adsorption rate, high adsorption capacity, high photocatalytic degradation rate, lower use cost and obvious comprehensive economic benefits, and is especially suitable to be used as a high-speed high-efficiency adsorptive catalytic material for medium/low-concentration ambient organic pollutants. The composite nano photocatalytic material can be popularized as a high-speed high-efficiency adsorptive photocatalytic material for organic dyes, hormones, organic additives and other organic pollutants in water.
Description
Technical field
Invention belongs to field of material synthesis technology, relate to a kind of polymer base material and the effective composite photocatalyst material of inorganic nano material and preparation method thereof, especially for the radiation grafting embedding preparation method of a kind of high-speed and high-efficiency composite Nano catalysis material of organic pollutants.
Background technology
Along with the development of society, the improving constantly of the fast development of modern industry and living standards of the people, the difficult organic pollutant wastewater annual emissions decomposed sharply increases, and limited water resource is subject to serious pollution.National governments strengthen on the one hand working out measures the discharge quality of sewage and the standard of keeping under strict control, and drop into the research that huge fund is used for water resource scavenging material and technology of waste water control on the other hand.Exploitation wastewater processing technology, according to the difference of processing mode, can be divided three classes: physical treatment (active carbon, membrane technology), biodegradation (bacterium etc.) and chemical treatment.When processing the industrial or agricultural sewage of height organic contamination, physical method is helpless, often pays the utmost attention to some biological methods, although bioanalysis technology reaches its maturity and expense is lower, but this method is very responsive to noxious material, highly polluted waste water can cause organism waste water degraded tissue devitalization.And when adopting chemical method process, although the chemical property of pollutant can be changed by chemical reaction, make it be converted into harmless or separable material, method also exists inevitable secondary pollution problem and cost higher.
" high-level oxidation technology " that grow up gradually in recent years overcomes the weak point of said method.Extensively research and apply has photochemical degradating, photocatalysis and chemical oxidation of gold at present, and in this type of technology, heterogeneous nano-photo catalytic method, as abiotic technology, is used for destroying and mineralising Some Organic Pollutants.Its treatment cycle is short, degraded is comparatively complete, reaction condition is gentle, for the road made new advances is opened up in the process solving complicated macromolecule and poisonous and harmful organic pollution.
Nano-TiO
2there is colorless and odorless, do not burn, the advantage such as stable in physicochemical property, biocompatibility, high-light-fastness, environment compatibility, low cost and materials ' durability determines that it has been widely used at field tools such as biomedicine, antibiotic and sterilizing, the depollutions of environment.Fujishima etc. have found that water is at TiO
2the phenomenon that lower meeting is decomposed into oxygen and hydrogen is penetrated in the illumination of Single Crystalline Electrodes, and they also find that some micro-content organisms in water are also degraded simultaneously.The scientist Ollis of the U.S. etc. study TiO
2photocatalysis mineralising chlorinated hydrocarbon contaminants is clearly familiar with the earliest and starts to apply conductor photocatalysis as method for purifying water.Matthews, Barbeni and Okamoto use TiO respectively
2photochemical catalytic oxidation chlorobenzene, chlorophenol, phenol, confirm that conductor photocatalysis is not limited to aliphatic compound, be equally also applicable to aromatic compound.Utilize TiO
2the performance of photocatalytic pollutant degradation, carry out a kind of method that sewage disposal is effective environmental protect.Be widely used in the pollutant waste water of photographic industry and textile and dyeing industry at present, indusrial toxic solvent, dyestuff, pesticide, anticorrisive agent etc., as pollutant wastewater treatments such as halogenated hydrocarbon, benzene derivate class, phenols, organic acid, hydro carbons, surfactants.
But, traditional one-component nano-TiO
2material has weak point (particularly in absorption, catalysis and recovery, regeneration etc.), due to nano-TiO often in practical application
2mainly be present in carrier inside, organic pollution is slow in the diffusion velocity of carrier, affects its absorption, catalysis and desorption rate; Residual component in Catalyst Production technique is difficult to remove, and causes its leachable in water more, and its use in sewage treatment process is restricted; In addition, above-mentioned catalysis material is expensive, adsoption catalysis is limited in one's ability, uses these catalysis materials that cost recovery can be caused to improve.For the problems referred to above, above-mentioned defect can be overcome in the urgent need to researching and developing one, the NEW TYPE OF COMPOSITE photochemical catalyst of high-speed and high-efficiency adsoption catalysis can be carried out organic pollutants.
The main thought improving absorption adsoption catalysis performance is: as far as possible by nano-TiO
2etc. there being catalysis material to concentrate on polymer surface, shorten the diffusion process of absorption object in catalysis material as far as possible.According to this requirement, in catalyst structure design, Graft Method is utilized to import monomer on the surface and effectively the method for embedding inorganic nano catalysis material is used to prepare catalysis material in specific base material.The catalysis material of synthesis is particularly suitable for being carried out that is high speed adsorbed, high efficiency photocatalysis is degraded to being adsorbed with organic pollutants under middle low concentration environment; Ionising radiation crosslinking technology is also used as a kind of important means of material modification, for the synthesis of various catalysis material.Compared with other grafting method, radiation grafting technology has can be selected arbitrarily the kind of base material and monomer, substrate shapes is not limited, without advantages, particularly electron beam emulsion pre-irradiation grafting method such as excessive residual compositions in grafting intermediate product, the radiative process of base material and monomer-grafted course of reaction can be separated, be not easy in course of reaction to produce homopolymers, reaction efficiency is high, and controllability is strong, is adapted at the nano-TiO that material surface high density imports specific monomer and effectively embeds high dispersive
2.This kind of method is conducive to nano-TiO
2be incorporated in the polymer base material surface texture of grafted monomers, can TiO be made
2the energy of effective absorption natural daylight, excites hydrone to produce living radical, can improve nano-TiO again
2absorption property and catalytic degradation performance, also improve stability and the mechanical property of high molecular nanometer composite catalyst simultaneously, and be conducive to reclaiming recycling technique, achieve the cooperative synergism effect that advantageous property combines, mechanical property improves and adsoption catalysis function strengthens.
Summary of the invention
The object of the invention is to overcome the defect existed in prior art, provide a kind of adopt ionising radiation, emulsion graft investment preparation for the high-speed and high-efficiency composite Nano catalysis material of organic pollutants radiation grafting embedding preparation method.
The object of the invention is to be achieved through the following technical solutions:
A kind of radiation grafting embedding preparation method of composite Nano catalysis material, it is characterized in that: comprise make polymer base material produce living radical ionising radiation process, on described living radical grafted monomers graft polymerization and inorganic nano photochemical catalyst is introduced the embedding process of graft product
Wherein, ionising radiation process is: enclosed by polymer base material in the PE bag containing nitrogen, at low temperatures, uses high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction to polymer base material,
Glycerol polymerization embedding process is: the described polymer base material creating living radical is put into modulate in advance be blown in the water system emulsified solution of nitrogen, glycerol polymerization embedding reaction is carried out in heating, cleaning after reaction is also dry, obtains end product composite Nano catalysis material
By mass fraction, its water system emulsified solution comprise 10 ~ 80% acrylates or benzene alkene salt intermediate monomer and 4 ~ 10% inorganic nano catalyst.
Preferably: described polymer base material shape to be average diameter the be spheroidal particle of 20-800 μm, or diameter be 5-300 μm, length is the microfibrous or laminated structure of 50-10000 μm.
Why selecting this size range, is the processing in order to be conducive to product and packaging, also facilitates filling and the loading of later stage adsorption column.
Preferably: described ionising radiation is by gamma ray, and electron ray, the ionizing ray that X-ray produces, dose of radiation is 10-250kGy.
Preferably: it is make them be formed in water system in stable emulsification system at interfacial agent to carry out that described polymer base material and acrylates or benzene alkene salt intermediate monomer carry out graft polymerization reaction, and emulsion grafting polymerization reaction temperature is 40-80 DEG C, emulsion grafting polymerization reaction time 2-4h.Guarantee that monomer fully can be grafted on base material and to have higher rate of vaccination, for the ring-opening reaction of intermediate product provides precondition.
Why selecting acrylates or benzene alkene salt intermediate monomer, is because their easy radiation graftings and can guarantee there is higher rate of vaccination.
Preferably: the percent grafting of described intermediate monomer is more than 85%, the density of grafted monomers is more than 0.8mmol/g.
Preferably: described polymer base material is one or more in microcrystalline cellulose, PP, LDPE, HDPE, PVC, PVDF, PET.
Preferably: described inorganic nano photochemical catalyst is TiO
2, ZnO, Cu
2o, InVO
4, Fe
2o
3, CdSe, CdS, POM, SrTiO
3, WO
3, the complex of bipyridyl-iron, ferriporphyrin, iron-phthalocyanine, one or more in rare-earth oxide.
Why select these inorganic nano photochemical catalysts, be because they have good energy gap coupling and good photoelectricity transfer performance, and there is comparatively high stable photocatalysis performance.
Preferably: described monomer is one or more in GMA, acrylic acid, PAA, chloroethene olefin(e) acid, chloroethene olefin(e) acid sodium, styrene acid sodium, chlorostyrene acid sodium.
Preferably: the embedding rate of the inorganic nano photochemical catalyst of described embedding is more than 80%.
The invention also discloses the composite photocatalyst material adopting above preparation method to obtain.
The beneficial effect that the present invention has:
1. ionising radiation grafting method of the present invention is compared with other grafting methods, radiation grafting technology has can be selected arbitrarily the kind of base material and monomer, substrate shapes is not limited, the advantages such as the residual component of production technology are not remained in grafting intermediate product, particularly electron beam irradiation emulsion pre-irradiation grafting method, the radiative process of base material and monomer-grafted course of reaction can be separated, be not easy in course of reaction to produce homopolymers, reaction efficiency is high, controllability is strong, be adapted at the inorganic nano catalysis material that material surface high density imports specific monomer and polymolecularity.
2. synthetic method of the present invention uses the water serial emulsion of acrylates or benzene alkene salt/polymer base material as monomer reaction liquid, (it is more than 85% that the inventive method can obtain percent grafting can to obtain exceeding the percent grafting of several times than conventional organic solvents reactant liquor, the density of grafted monomers is more than 0.8mmol/g), and can Reaction time shorten greatly, to avoid in building-up process a large amount of with an organic solvent, reduce the carrying capacity of environment of synthesis technique.
3. the present invention selects the macromolecular material of microspheroidal, threadiness or sheet as base material, by controlling radiation grafting and screening plan importing monomer and inorganic nano catalysis material and configure, realization, for the MOLECULE DESIGN of Adsorption of Organic photocatalytic degradation material, has been synthesized a series of alternative traditional catalysis material, has been had the NEW TYPE OF COMPOSITE catalysis material of high speed absorption feature, high absorption capacity and high efficiency photocatalysis degraded.This sorbing material based on the synthesis of microspheroidal, threadiness or flat substrates, can replace existing business photochemical catalyst to use in catalysis post/tower more easily.
4. with the composite photocatalyst material that synthetic method of the present invention is synthesized, there is the degraded of high speed absorption feature, high absorption capacity and high efficiency photocatalysis, use cost can be reduced, overall economic efficiency is remarkable, carries out high-speed and high-efficiency adsorption photochemical catalysis degradation reaction under being particularly suitable for middle low concentration environment to organic pollutants.
The high-speed and high-efficiency adsorption photochemical catalysis material prepared by the inventive method extensively can promote the use the high-speed and high-efficiency adsorption photochemical catalysis composite done for organic pollutants.
Accompanying drawing explanation
Fig. 1 two kinds of photocatalyst for degrading dynamics comparison diagrams.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
Embodiment 1:
With microcrystalline cellulose crude granule (MCC, average diameter about 100 μm) be polymer base material, 10g above-mentioned material is put into the PE bag containing nitrogen, within the scope of-79 DEG C to-60 DEG C, use high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction; Illuminate condition is irradiation voltage 1MeV, and exposure dose is 30kGy, close rate 10kGy/pass, and postradiation above-mentioned particle drops into by 20% GMA (GMA), 2% Tween 80,4% nano-TiO at once
2with in the emulsion reaction system of 74% water composition, GMA monomer and nano-TiO
2emulsion reaction system be blown into continuously before use 30min nitrogen, to discharge the oxygen in water.Glycerol polymerization embedding reaction carries out 4h at 60 DEG C.Obtain the polymer of grafting embedding reaction under these conditions: the percent grafting of microcrystalline cellulose base material is 120%, and embedding rate is 110%.The monomer-grafted embedding product of above-mentioned GMA, can obtain the final product of the present invention after clean dry.Get basis weight products to drop in the aqueous solution of methylene blue of 250mL, 4mg/L, dark place leaves standstill 2h, and recording saturated adsorption capacity is 2.4mg/g, under room temperature visible light-inducing, carry out photocatalytic degradation experiment, after reaction 3h, records degradation rate and reaches 98%.After the grafting embedding reaction of above-mentioned condition, the composite photocatalyst material diameter obtained is about 290 μm.
Embodiment 2:
With sheet shaped polyethylene (LDPE, average diameter about 300 μm) be polymer base material, 10g above-mentioned material is put into the PE bag containing nitrogen, within the scope of-50 DEG C to-40 DEG C, use high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction; Illuminate condition is irradiation voltage 1MeV, and exposure dose is 60kGy, close rate 30kGy/pass, and postradiation above-mentioned sheet-like particle drops into by 30% styrene acid sodium, 3% Tween 80,5%SrTiO at once
3with in the emulsion reaction system of 62% water composition, styrene acid sodium monomer and SrTiO
3emulsion reaction system be blown into continuously before use 30min nitrogen, to discharge the oxygen in water.Glycerol polymerization embedding reaction carries out 4h at 50 DEG C.Obtain the polymer of grafting embedding reaction under these conditions: the percent grafting of sheet polyethylene base material is 95%, and embedding rate is 80%.The above-mentioned monomer-grafted embedding product of styrene acid sodium, can obtain the final product of the present invention after clean dry.Get basis weight products to drop in the aqueous solution of methylene blue of 250mL, 4mg/L, dark place leaves standstill 2h, and recording saturated adsorption capacity is 1.6mg/g, under room temperature visible light-inducing, carry out photocatalytic degradation experiment, after reaction 3h, records degradation rate and reaches 94%.After the grafting embedding reaction of above-mentioned condition, the composite photocatalyst material diameter obtained is about 500 μm.
Embodiment 3:
With high density polyethylene (HDPE) particle (HDPE, average diameter about 200 μm) be polymer base material, 10g above-mentioned material is put into the PE bag containing nitrogen, within the scope of-40 DEG C to-30 DEG C, use high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction; Illuminate condition is irradiation voltage 1MeV, exposure dose is 80kGy, close rate 20kGy/pass, postradiation above-mentioned particle drops in the emulsion reaction system be made up of 35% PAA, 2% Tween 80,8% ferriporphyrin and 55% water at once, and the emulsion reaction system of sodium acrylate monomers and ferriporphyrin is blown into the nitrogen of 30min, before use continuously to discharge the oxygen in water.Glycerol polymerization embedding reaction carries out 3h at 50 DEG C.Obtain the polymer of grafting embedding reaction under these conditions: the percent grafting of high density polyethylene (HDPE) particulate substrate is 106%, and embedding rate is 94%.Above-mentioned sodium acrylate monomers grafting embedding product, can obtain the final product of the present invention after clean dry.Get basis weight products to drop in the aqueous solution of methylene blue of 250mL, 4mg/L, dark place leaves standstill 2h, and recording saturated adsorption capacity is 1.8mg/g, under room temperature visible light-inducing, carry out photocatalytic degradation experiment, after reaction 3h, records degradation rate and reaches 97%.After the grafting embedding reaction of above-mentioned condition, the composite photocatalyst material diameter obtained is about 380 μm.
Embodiment 4:
With PVC sheets (PVC, average diameter about 5 μm) be polymer base material, 10g above-mentioned material is put into the PE bag containing nitrogen, within the scope of-30 DEG C to-20 DEG C, use high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction; Illuminate condition is irradiation voltage 1MeV, and exposure dose is 10kGy, close rate 10kGy/pass, and postradiation above-mentioned particle drops into by 10% chlorostyrene acid sodium, 1% Tween 80,8%InVO at once
4with in the emulsion reaction system of 81% water composition, chlorostyrene acid sodium monomer and InVO
4emulsion reaction system be blown into continuously before use 30min nitrogen, to discharge the oxygen in water.Glycerol polymerization embedding reaction carries out 2h at 40 DEG C.Obtain the polymer of grafting embedding reaction under these conditions: the percent grafting of PVC sheets base material is 86%, and embedding rate is 81%.The above-mentioned monomer-grafted embedding product of chlorostyrene acid sodium, can obtain the final product of the present invention after clean dry.Get basis weight products to drop in the aqueous solution of methylene blue of 250mL, 4mg/L, dark place leaves standstill 2h, and recording saturated adsorption capacity is 0.8mg/g, under room temperature visible light-inducing, carry out photocatalytic degradation experiment, after reaction 3h, records degradation rate and reaches 78%.After the grafting embedding reaction of above-mentioned condition, the composite photocatalyst material diameter obtained is about 106 μm.
Embodiment 5:
With PP GRANULES (PP, average diameter about 300 μm) be polymer base material, 10g above-mentioned material is put into the PE bag containing nitrogen, within the scope of-65 DEG C to-45 DEG C, use high-energy electron accelerator to carry out radiation, make it produce to can be used for the living radical of graft reaction; Illuminate condition is irradiation voltage 1MeV, exposure dose is 250kGy, close rate 50kGy/pass, postradiation above-mentioned particle drops in the emulsion reaction system be made up of 80% styrene acid, 10% Tween 80,8%CdS and 2% water at once, and the emulsion reaction system of styrene acid monomers and CdS is blown into the nitrogen of 30min, before use continuously to discharge the oxygen in water.Glycerol polymerization embedding reaction carries out 4h at 80 DEG C.Obtain the polymer of grafting embedding reaction under these conditions: the percent grafting of PP GRANULES base material is 151%, and embedding rate is 84%.Above-mentioned styrene acid monomers grafting embedding product, can obtain the final product of the present invention after clean dry.Get basis weight products to drop in the aqueous solution of methylene blue of 250mL, 4mg/L, dark place leaves standstill 2h, and recording saturated adsorption capacity is 1.1mg/g, under room temperature visible light-inducing, carry out photocatalytic degradation experiment, after reaction 3h, records degradation rate and reaches 79%.After the grafting embedding reaction of above-mentioned condition, the composite photocatalyst material diameter obtained is about 460 μm.
Embodiment 6: two kinds of photocatalyst for degrading dynamics compare
The microcrystalline cellulose base material composite photo-catalyst 0.25g prepared in embodiment 1 is added in organic dyestuff methylene blue (MB) solution and is made into 250mL suspension sample, after slow-witted fully dissolving, loaded in Pyrex heat resistant glass reactor, opening thermostat makes water circulate in Pyrex heat resistant glass reactor, when temperature reaches required temperature and remains unchanged, open the source of turning on light, observe Photocatalytic Degradation Process, after 3h, stop reaction; Conveniently compare, simultaneously by existing business photochemical catalyst P25, evaluate its kinetics of photocatalytic degradation characteristic according to same experiment condition.
Kinetics of photocatalytic degradation evaluation experimental has been carried out according to above-mentioned condition, by to the fixed time interval, to carrying out centrifugal to the MB extract of each catalyst, measure its absorbance under wavelength is 665nm, calculate degradation rate and speed constant, the catalytic activity of catalyst is weighed by degradation rate and speed constant, as shown in Figure 1, what represent with rhombus in Fig. 1 is the exploitation product prepared by the inventive method---the kinetics of photocatalytic degradation behavior curve of NEW TYPE OF COMPOSITE photochemical catalyst, what represent by circle in Fig. 1 is the kinetics of photocatalytic degradation behavior curve of existing business photochemical catalyst P25.
By the result of comparison diagram 1; we find that business P25 photochemical catalyst is after photocatalytic degradation 2h; its degradation rate is only 58%; and its degradation rate of composite photo-catalyst prepared by the inventive method is faster than existing business P25 photochemical catalyst; and degradation rate is up to 98%; its core index evaluating catalytic performance is obviously better than business P25 photochemical catalyst, is expected in field of environment protection, obtain certain application.
The performance of several composite photocatalyst materials that radiation grafting embedding preparation method of the present invention is obtained and the performance comparison of business photochemical catalyst P25.Degradation solution is the aqueous solution of methylene blue of 4mg/L, and the various photocatalyst concentrations preparing gained is 1g/L, and in table, the degradation rate of catalyst is the core index weighing catalyst performance.The performance of several composite photocatalyst material and the performance comparison of business P25 as shown in table 1.
With reference to embodiment 6, respectively kinetics of photocatalytic degradation evaluation experimental is carried out to different composite photochemical catalyst prepared by embodiment 2, embodiment 3, embodiment 4, these 4 experimental systems of embodiment 5, by to the fixed time interval, to carrying out centrifugal to the MB extract of each catalyst, measure its absorbance under wavelength is 665nm, calculate degradation rate and speed constant, weigh the catalytic activity of catalyst by degradation rate and speed constant.As shown in table 1, different experiments system is described, adopt different parameters, the different composite photochemical catalyst of gained has different rates of vaccination, embedding rate and catalytic performance.
Show further, 5 kinds of its degradation rates of composite photo-catalyst prepared by the inventive method are minimum reaches 78%, most high degradation rate is up to 98%, and all higher than existing business P25 photocatalyst for degrading rate (being only 58%), this absolutely proves that developing by the radiation grafting embedding preparation method of a kind of composite Nano of the present invention catalysis material its photocatalysis performance of Novel series composite photo-catalyst obtained is better than existing business photochemical catalyst, existing commercial product can be replaced in actual applications completely, there are huge application prospect and market prospects.
The performance comparison table of composite photo-catalyst prepared by the different system of table 1
Shown in composition graphs 1, Fig. 1 is the kinetics of photocatalytic degradation evaluating characteristics figure of organic dyestuff methylene blue (MB) when use two kinds of different catalysis materials.What represent with rhombus in Fig. 1 is the exploitation product prepared by the inventive method---the kinetics of photocatalytic degradation behavior curve of NEW TYPE OF COMPOSITE catalysis material, what represent by circle in Fig. 1 is the kinetics of photocatalytic degradation behavior curve of existing business photochemical catalyst P25.As shown in Figure 1, the composite Nano catalysis material that the present invention obtains has better catalytic degradation effect.
Further, above embodiment only in order to the present invention is described and and unrestricted technical scheme described in the invention; Therefore, although this description with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. the radiation grafting embedding preparation method of a composite Nano catalysis material, it is characterized in that: comprise make polymer base material produce living radical ionising radiation process, on described living radical grafted monomers graft polymerization and inorganic nano photochemical catalyst is introduced the embedding process of graft product
Wherein, ionising radiation process is: enclosed by polymer base material in the PE bag containing nitrogen, in the scope of-79 DEG C to-20 DEG C, carries out radiation, make it produce to can be used for the living radical of graft reaction to polymer base material use high-energy electron accelerator,
Glycerol polymerization embedding process is: the described polymer base material creating living radical is put into modulate in advance be blown in the water system emulsified solution of nitrogen, glycerol polymerization embedding reaction is carried out in heating, cleaning after reaction is also dry, obtains end product composite Nano catalysis material
By mass fraction, its water system emulsified solution comprise 10 ~ 80% acrylates or benzene alkene salt intermediate monomer and 4 ~ 10% inorganic nano catalyst.
2. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, it is characterized in that: described polymer base material shape to be average diameter the be spheroidal particle of 20-800 μm, or diameter be 5-300 μm, length is the microfibrous or laminated structure of 50-10000 μm.
3. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, is characterized in that: described ionising radiation is by gamma ray, and electron ray, the ionizing ray that X-ray produces, dose of radiation is 10-250kGy.
4. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, it is characterized in that: it is make them be formed in water system in stable emulsification system at interfacial agent to carry out that described polymer base material and acrylates or benzene alkene salt intermediate monomer carry out graft polymerization reaction, and emulsion grafting polymerization reaction temperature is 40-80 DEG C, emulsion grafting polymerization reaction time 2-4h.
5. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, it is characterized in that: the percent grafting of described intermediate monomer is more than 85%, the density of grafted monomers is more than 0.8mmol/g.
6. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, is characterized in that: described polymer base material is one or more in microcrystalline cellulose, PP, LDPE, HDPE, PVC, PVDF, PET.
7. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, is characterized in that: described inorganic nano photochemical catalyst is TiO
2, ZnO, Cu
2o, InVO
4, Fe
2o
3, CdSe, CdS, POM, SrTiO
3, WO
3, the complex of bipyridyl-iron, ferriporphyrin, iron-phthalocyanine, one or more in rare-earth oxide.
8. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, is characterized in that: described monomer is one or more in GMA, acrylic acid, PAA, chloroethene olefin(e) acid, chloroethene olefin(e) acid sodium, styrene acid sodium, chlorostyrene acid sodium.
9. the radiation grafting embedding preparation method of composite Nano catalysis material according to claim 1, is characterized in that: the embedding rate of the inorganic nano photochemical catalyst of described embedding is more than 80%.
10. the composite Nano catalysis material that the radiation grafting embedding preparation method any one of claim 1 to claim 9 described in claim obtains.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108837851A (en) * | 2018-07-12 | 2018-11-20 | 湖北科技学院 | A kind of pre-irradiation grafting synthetic method of the nano TiO 2 based photocatalyst of efficient absorption-reduction high toxicity hexavalent chromium |
| CN108855011A (en) * | 2016-07-08 | 2018-11-23 | 苏州大学 | With absorption-visible light photocatalytic degradation synergistic effect composite material and application thereof |
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| CN102784625A (en) * | 2012-07-26 | 2012-11-21 | 湖北科技学院 | Radiation synthetic method for high-speed selective adsorption material |
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| CN101537349A (en) * | 2009-04-22 | 2009-09-23 | 东华大学 | Preparation of core/shell structural polystyrene/titanium dioxide composite photo catalyst |
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