CN102515250A - Method for preparing low-agglomeration amphiphilic nanometer zinc oxide - Google Patents
Method for preparing low-agglomeration amphiphilic nanometer zinc oxide Download PDFInfo
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Abstract
A method for preparing low-agglomeration amphiphilic nanometer zinc oxide belongs to the technical field of nanometer zinc oxide preparation. The method provided by the invention comprises the following steps of: using cellulose, an activator, zinc nitrate and urea as raw materials, activating cellulose, preparing a nanometer zinc oxide precursor, followed by simple processes such as coupling, grafting, washing, extraction, drying and the like, so as to prepare the product. The product produced by the method has good amphipathy, the grafting ratio of cellulose on the surface of zinc oxide is high, and dispersibility is good. The method is simple and has advantages of few processing steps, simple equipment, mild reaction condition and little energy consumption. As material resources are fully utilized during the production process, there is no discharge of ''three wastes (waste gas, waste water and industrial residue)''. Therefore, the method is beneficial to environmental protection. The low-agglomeration amphiphilic nanometer zinc oxide product prepared by the method is characterized in that the minimum particle size of the product reaches 20nm and the grafting ratio reaches as high as 76%. The product provided by the invention can be widely applied in industries such as glass, ceramic, paint, cosmetic and the like, and is an ideal high-function fine inorganic functional material.
Description
Technical field
The invention belongs to the nano zine oxide preparing technical field, be specifically related to nano-ZnO preparation.
Background technology
Nano zine oxide is white powder, and density is about 5.47g/cm3, and specific surface area is greater than 12m
2/ g is needle-like or spheroidal, is a kind of novel fine inorganic product.Because its size is between cluster and macroscopical particulate; Have the special propertys that many macroscopic material did not have such as small-size effect, surface effects, macro quanta tunnel effect; Demonstrate many properties (like piezoelectricity, fluorescence, nontoxic and non-migrating property, absorption and scatters ultraviolet ability etc.) and purposes, it has specifically functional that common zinc oxide product troops under one's command possess at aspects such as magnetic, light, electricity, sensitivity, antibiotic and sterilizing, ultraviolet screeners, is a kind of new function material that has a extensive future; Can be widely used in pottery; Glass, coating, fields such as daily cosmetics.
Existing nano-ZnO preparation; It like application number " method for preparing the compound split of nano zine oxide with natural polysaccharide " patent of 200910067985.9; Disclosed method is: after earlier being dissolved in starch or CMC 99.5 in the hot water, join in the zinc nitrate solution, then dropping sodium solution again; After spinning, dry and product.The main drawback of this method is: it is lower that the starch of usefulness or CMC 99.5 are made the properties-correcting agent reactive behavior; Mainly the mode with physical adsorption covers the nano granular of zinc oxide surface; A little less than the surface action of properties-correcting agent and nano particle; When modified nanoparticles being added organic medium such as paint resin, starch that is adsorbed or CMC 99.5 properties-correcting agent easily from the nano grain surface desorption get off and cause nano particle gather group again, thereby reduced the performance of material.And for example application number is " a kind of preparation method who utilizes CDI catalysis amidate action coupling engrafted nanometer zinc oxide " patent of 201010224226.4; Disclosed method is: nano zine oxide is carried out surface-active-treatment with amino silicane coupling agent KH-550 earlier; Again with the graft reaction that is coupled with the Triple Pressed Stearic Acid after the CDI activation; Then through filtering, Suo Shi extract and dry and product.The main drawback of this method is: need carry out fully diffusingly to nano zine oxide, the modifying process flow process is long, and energy consumption is too much, is unfavorable for cleaner production, and through the nano zine oxide of modification good dispersiveness in organic solvent only, use range is narrower.
Summary of the invention
The objective of the invention is the weak point to existing nano zine oxide preparation method, a kind of low reunion, amphiphatic nano zine oxide preparation method are provided, it is simple to have equipment; Invest little; Characteristics such as technical process is short, and energy consumption is low and pollution-free, and the product application scope is wide.
Mechanism of the present invention: the present invention, adds silane coupling agent and carries out pre-treatment among the preparation nano zine oxide preparation technology of sodium hydroxide as alkali source through adopting with zinc nitrate as the zinc source, again with through overactivation fibrin reaction.Effect below producing like this: on the one hand, tensio-active agent makes between the oxygen Zinc oxide powder and can't reduce the particle agglomeration probability near contact being grafted to the sterically hindered effect of zinc hydroxide surface generation; Also reduce simultaneously the reunion of the ZnO that zinc hydroxide produces and grow up in decomposition course.On the other hand, because the nano zine oxide of modification is grafted with the Mierocrystalline cellulose of long carbochain on it, in organic solvent, has good solubility; And the fiber rope in the grafting also has a large amount of hydroxyls, so this nano zine oxide also can dissolve in water solvent simultaneously, possesses amphiphilic.
The technical scheme that realizes the object of the invention is: a kind of low reunion, amphiphatic nano zine oxide preparation method; With Mierocrystalline cellulose, acvator, zinc nitrate, urea etc. is raw material; Earlier Mierocrystalline cellulose is carried out activation, back preparation nanometer zinc oxide precursor also carries out coupling, grafting and washing, extraction, exsiccant simple process and makes product it.Its concrete steps are following:
(1) Cellulose activation
With Mierocrystalline cellulose and acvator is raw material, according to cellulosic quality (g): the quality of acvator (g): the quality of toluene (g): N in the toluene solution, N in the N dimethyl formamide solution; The ratio of the quality of N N (g) be 1: 0～1.5: 20～60: 10～50 ratio in three mouthfuls of tankages, earlier toluene solution is joined N, in the N solvent dimethylformamide; Stir, in mixed solution, add Mierocrystalline cellulose again, and after under protection of nitrogen gas, adding acvator; Be warming up to 25～80 ℃, stirring reaction 2～8h stops heating; Naturally cool to room temperature then, carry out suction filtration, collect filtrating and filter cake respectively.The filtrating of collecting is distilled recovery, recycling.Then according to filter cake: the volume ratio of distilled water wash agent is 1: 3～5 ratio, with the distilled water wash agent filter cake is washed 3～5 times, the filter cake after collecting washings respectively and washing.Washings to collecting distills the back and recycles at last; Filter cake after the washing is put in the baking oven, and under 80～150 ℃, dry 2～6h makes the activatory Mierocrystalline cellulose.Wherein: Mierocrystalline cellulose is CMC 99.5 or Natvosol or Vltra tears or methylcellulose gum or TKK 021; Acvator is N, N '-carbonyl dimidazoles or tolylene diisocyanate or isocyanic acid chlorsulfonic acid ester or methyl isocyanate.
(2) preparation of zinc hydroxide presoma
After the completion of (1) step; Zinc nitrate solution is added in three mouthfuls of tankages, and drip urea soln while stirring, wherein the mole number of zinc nitrate in the zinc nitrate solution: the mole number of urea is 1: 1～3 ratio in the urea soln; Stirring reaction 2～6h makes the zinc hydroxide precursor solution then.
(3) zinc hydroxide presoma coupled reaction
After the completion of (2) step; Quality (g) in (2) the zinc hydroxide presoma that makes of step: the ratio of the quality of silane coupling agent (g) is 1: 0.01～0.1 ratio; Go on foot in the zinc hydroxide presoma zinc solution that makes (2); Add silane coupling agent earlier, restir carries out coupled reaction 2～6h, just prepares the zinc hydroxide precursor solution of coupling.Wherein: silane coupling agent is KH550 (γ-An Bingjisanyiyangjiguiwan) or KH560 (γ-glycidyl ether oxygen propyl trimethoxy silicane) or KH570 (γ-methacryloxypropyl trimethoxy silane) or KH792 (N-(β one aminoethyl)-γ-aminopropyl front three (second) TMOS) silane coupling agent.
(4) zinc hydroxide presoma grafted cellulose
After the completion of (3) step; In the zinc hydroxide precursor solution of (3) the step coupling of preparing, add the activatory Mierocrystalline cellulose that (1) step made, wherein the quality (g) of the zinc hydroxide precursor solution of (3) the step coupling of preparing: the cellulosic quality of activatory (g) that (1) step made is 1: 0.01～0.1.Graft reaction 1～6h is carried out in stirring, just prepares the mixed solution behind the zinc hydroxide coupling graft reaction.
(5) preparation of nanometer Zinc oxide powder
After (4) step accomplished, the mixed solution behind the zinc hydroxide coupling graft reaction that (4) step was prepared, naturally cool to room temperature after, carry out suction filtration, collect filtrating and filter cake respectively.The filtrating of collecting is transferred in the container, as the initial feed of producing fertilizer; To the filter cake of collecting, according to the volume of filter cake: the volume ratio of distilled water wash agent is 1: 1～5 ratio, with the distilled water wash agent filter cake is washed 3～5 times, the filter cake after collecting washings respectively and washing.Washings to collecting distills recovery, recycling.Filter cake after the washing of collecting is put into baking oven earlier, under 80～180 ℃, dry 2～6h.Again dried filter cake (being pressed powder) is put into apparatus,Soxhlet's,, carry out Suo Shi and extract 10～24h, in order to remove excess fiber element, acvator and other organic by-products in the reaction process with toluene solution and under the boiling temperature of toluene; Take out the pressed powder after Suo Shi extracts then, put into loft drier, under 100～280 ℃ of temperature, dry 4～12h.Just prepare low reunion, amphiphatic nanometer Zinc oxide powder finished product.
After the present invention adopts technique scheme, mainly contain following effect:
1 adopts the cellulose modified nano zine oxide of activatory, both can be dispersed in organic medium, can be distributed in the water again, has good amphiphilic performance, can enlarge the range of application of nano zine oxide.
2 pass through acvator to the cellulose graft priming reaction, have improved cellulosic reactive behavior, have increased substantially the percentage of grafting of Mierocrystalline cellulose at zinc oxide surface.
The cellulosic material of 3 employings is cheap and easy to get, no matter the nano zine oxide after the modification is all fine at the organic medium or the dispersiveness of inorganic medium.
4 the inventive method are simple, and process step is few, and equipment is simple, and reaction conditions is gentle, and energy consumption is little, easy and simple to handle and be easy to control in the production process, and is easy to utilize.
5 in process of production, makes full use of material resource, do not have " three wastes " discharging, pollution-free, helps environment protection.
Adopt the low reunion that forwarding method of the present invention prepares, the particle diameter minimum of amphiphilic nano zinc oxide product to reach 20nm, percentage of grafting up to 76%.Can be widely used in the industries such as glass, pottery, coating, makeup, be the high function fine inorganic of ideal functional materials.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
A kind of low reunion, amphiphilic nano zinc oxide preparing method's concrete steps are following:
(1) Cellulose activation
With Mierocrystalline cellulose and acvator is raw material, according to cellulosic quality (g): the quality of acvator (g): the quality of toluene (g): N in the toluene solution, N in the N dimethyl formamide solution; The ratio of the quality of N N (g) is 1: 0.8: 30: 20 ratio joins N with toluene solution earlier, in the N solvent dimethylformamide in three mouthfuls of tankages; Stir, in mixed solution, add Mierocrystalline cellulose again, and after under protection of nitrogen gas, adding acvator; Be warming up to 60 ℃, stirring reaction 3h stops heating; Naturally cool to room temperature, carry out suction filtration, collect filtrating and filter cake respectively.The filtrating of collecting is distilled recovery, recycling.Then according to filter cake: the volume ratio of distilled water wash agent is 1: 3 a ratio, with the distilled water wash agent filter cake is washed 5 times, the filter cake after collecting washings respectively and washing.Washings to collecting distills the back and recycles at last; Filter cake after the washing is put in the baking oven, under 100 ℃, dry 2.5h, and make the activatory Mierocrystalline cellulose.Wherein: Mierocrystalline cellulose is a CMC 99.5; Acvator is N, N '-carbonyl dimidazoles.
(2) preparation of zinc hydroxide presoma
After the completion of (1) step; Zinc nitrate solution is added in three mouthfuls of tankages, and drip urea soln more while stirring, wherein the mole number of zinc nitrate in the zinc nitrate solution: the mole number of urea is 1: 1.25 a ratio in the urea soln; Stirring reaction 2.5h makes the zinc hydroxide precursor solution then.
(3) zinc hydroxide presoma coupled reaction
After the completion of (2) step; Quality (g) in (2) the zinc hydroxide presoma that makes of step: the ratio of the quality of silane coupling agent (g) is 1: 0.014 a ratio; Go on foot in the zinc hydroxide presoma zinc solution that makes (2); Add silane coupling agent earlier, restir carries out coupled reaction 2h, just prepares the zinc hydroxide precursor solution of coupling.Wherein silane coupling agent is KH550.
(4) zinc hydroxide presoma grafted cellulose
After the completion of (3) step; In the zinc hydroxide precursor solution of (3) the step coupling of preparing, add the activatory Mierocrystalline cellulose that (1) step made, wherein the quality (g) of the zinc hydroxide precursor solution of (3) the step coupling of preparing: the cellulosic quality of activatory (g) that (1) step made is 1: 0.02.Graft reaction 2h is carried out in stirring, just prepares the mixed solution behind the zinc hydroxide coupling graft reaction.
(5) preparation of nanometer Zinc oxide powder
After (4) step accomplished, the mixed solution behind the zinc hydroxide coupling graft reaction that (4) step was prepared, naturally cool to room temperature after, carry out suction filtration, collect filtrating and filter cake respectively.The filtrating of collecting is transferred in the container, as the initial feed of producing fertilizer; To the filter cake of collecting, according to the volume of filter cake: the volume ratio of distilled water wash agent is 1: 3 a ratio, with the distilled water wash agent filter cake is washed 5 times, the filter cake after collecting washings respectively and washing.Washings to collecting distills recovery, recycling.Filter cake after the washing of collecting is put into baking oven earlier, under 110 ℃, dry 2h.Again dried filter cake (being pressed powder) is put into apparatus,Soxhlet's,, carry out Suo Shi and extract 10h, in order to remove excess fiber element, acvator and other organic by-products in the reaction process with toluene solution and under the boiling temperature of toluene; Take out the pressed powder after Suo Shi extracts then, put into loft drier, under 130 ℃ of temperature, dry 6h.Just prepare low reunion, amphiphatic nanometer Zinc oxide powder finished product.
Embodiment 2
A kind of low reunion, amphiphilic nano zinc oxide preparation method, with embodiment 1, wherein:
In (1) step, cellulosic quality (g): the quality of acvator (g): the quality of toluene (g): N in the toluene solution, N in the N dimethyl formamide solution, the ratio of the quality of N N (g) is 1: 0.6: 20: 10; Mierocrystalline cellulose is a Natvosol; Acvator is a tolylene diisocyanate.
In (3) step, silane coupling agent is KH560.
Embodiment 3
A kind of low reunion, amphiphilic nano zinc oxide preparation method, with embodiment 1, wherein:
In (1) step, cellulosic quality (g): the quality of acvator (g): the quality of toluene (g): N in the toluene solution, N in the N dimethyl formamide solution, the ratio of the quality of N N (g) is 1: 1.5: 60: 50; Mierocrystalline cellulose is a Vltra tears; Acvator is an isocyanic acid chlorsulfonic acid ester.
In (3) step, silane coupling agent is KH570.
Embodiment 4
A kind of low reunion, amphiphilic nano zinc oxide preparation method, with embodiment 1, wherein:
In (1) step, be warming up to 80 ℃; The stirring reaction time is 3h; Reaction solution: the ratio of distilled water wash agent is 1: 5; Washing times is 3 times; The filtration cakes torrefaction temperature is 80 ℃; The filtration cakes torrefaction time is 2h; The Mierocrystalline cellulose methylcellulose gum; Acvator is a methyl isocyanate.
In (2) step, the mole number of zinc nitrate in the middle zinc nitrate solution: the mole number of urea is 1: 1 a ratio in the urea soln; Reaction times is 2h.
In (3) step, the quality of zinc hydroxide presoma (g): the ratio of the quality of silane coupling agent (g) is 1: 0.01 a ratio; Silane coupling agent is KH792; Reaction times is 3h.
In (4) step, the quality of zinc hydroxide precursor solution (g): the cellulosic quality of activatory (g) that (1) step made is 1: 0.01; Reaction times is 1h.
In (5) step, the volume of filter cake: the volume ratio of distilled water wash agent is 1: 5 a ratio; Washing times is 3 times; The filtration cakes torrefaction temperature is 80 ℃; The filtration cakes torrefaction time is 6h; Suo Shi extraction time is 24h; The product drying temperature is 100 ℃; The product drying time is 4h.
Embodiment 5
A kind of low reunion, amphiphilic nano zinc oxide preparation method, with embodiment 1, wherein:
In (1) step, be warming up to 25 ℃; The stirring reaction time is 8h; Reaction solution: the ratio of distilled water wash agent is 1: 4; Washing times is 4 times; The filtration cakes torrefaction temperature is 150 ℃; The filtration cakes torrefaction time is 6h; The Mierocrystalline cellulose TKK 021.
In (2) step, the mole number of zinc nitrate in the middle zinc nitrate solution: the mole number of urea is 1: 3 a ratio in the urea soln; Reaction times is 6h.
In (3) step, the quality of zinc hydroxide presoma (g): the ratio of the quality of silane coupling agent (g) is 1: 0.1 a ratio; Reaction times is 6h.
In (4) step, the quality of zinc hydroxide precursor solution (g): the cellulosic quality of activatory (g) that (1) step made is 1: 0.1; Reaction times is 6h.
In (5) step, the volume of filter cake: the volume ratio of distilled water wash agent is 1: 4 a ratio; Washing times is 4 times; The filtration cakes torrefaction temperature is 180 ℃; The filtration cakes torrefaction time is 3h; Suo Shi extraction time is 12h; The product drying temperature is 280 ℃; The product drying time is 12h.
Embodiment 6
A kind of low reunion, amphiphilic nano zinc oxide preparation method, with embodiment 1, wherein:
In (1) step, cellulosic quality (g): the quality of acvator (g): the quality of toluene (g): N in the toluene solution, N in the N dimethyl formamide solution, the ratio of the quality of N N (g) is 1: 0: 30: 20.
Experimental result
To the prepared nano oxidized zinc product that goes out of embodiment 1～6, carry out the XRD experiment, calculate median size; Through the thermal weight loss experiment, it is calculated percentage of grafting, its result is following:
Table 1
| Embodiment | Nano zine oxide median size (nm) | Percentage of grafting (%) |
| 1 | 20 | 76 |
| 2 | 32 | 72 |
| 3 | 28 | 70 |
| 4 | 43 | 65 |
| 5 | 37 | 68 |
| 6 | 45 | 7.9 |
Can know that from above-mentioned experimental result the I of nano zine oxide product cut size of the present invention reaches 20nm, percentage of grafting up to 76%.
Claims (1)
1. one kind is hanged down reunion, amphiphatic nano zine oxide preparation method, it is characterized in that the concrete steps of said method are following:
(1) Cellulose activation
With Mierocrystalline cellulose and acvator is raw material, according to cellulosic quality: the quality of acvator: the quality of toluene: N in the toluene solution, N in the N dimethyl formamide solution; The ratio of the quality of N N is 1: 0～1.5: 20～60: 10～50 ratio, in three mouthfuls of tankages, earlier toluene solution is joined N; In the N solvent dimethylformamide, stir, in mixed solution, add Mierocrystalline cellulose again; And after under protection of nitrogen gas, adding acvator, be warming up to 25～80 ℃, stirring reaction 2～8h; Stop heating, naturally cool to room temperature then, carry out suction filtration; Collect filtrating and filter cake respectively, the filtrating of collecting is distilled recovery, then according to filter cake: the volume ratio of distilled water wash agent is 1: 3～5 ratio; With the distilled water wash agent filter cake is washed 3～5 times, the filter cake after collecting washings respectively and washing reclaims the washings of collecting at last; Filter cake after the washing is put in the baking oven, under 80～150 ℃, dry 2～6h, wherein: Mierocrystalline cellulose is CMC 99.5 or Natvosol or Vltra tears or methylcellulose gum or TKK 021; Acvator is N, N '-carbonyl dimidazoles or tolylene diisocyanate or isocyanic acid chlorsulfonic acid ester or methyl isocyanate;
(2) preparation of zinc hydroxide presoma
(1) step added zinc nitrate solution in three mouthfuls of tankages after accomplishing, and drip urea soln while stirring, wherein the mole number of zinc nitrate in the zinc nitrate solution: the mole number of urea is 1: 1～3 ratio in the urea soln, then stirring reaction 2～6h;
(3) zinc hydroxide presoma coupled reaction
After the completion of (2) step; Quality in (2) the zinc hydroxide presoma that makes of step: the ratio of the quality of silane coupling agent is 1: 0.01～0.1 ratio; Go on foot in the zinc hydroxide presoma zinc solution that makes (2); Add silane coupling agent earlier, restir carries out coupled reaction 2～6h, and wherein: silane coupling agent is KH550 or KH560 or KH570 or KH792 silane coupling agent;
(4) zinc hydroxide presoma grafted cellulose
After the completion of (3) step; Go on foot in the zinc hydroxide precursor solution of the coupling of preparing (3); Add the activatory Mierocrystalline cellulose that (1) step made; The quality of the zinc hydroxide precursor solution of (3) the step coupling of preparing wherein: the cellulosic quality of activatory that (1) step made is 1: 0.01～0.1, stirs and carries out graft reaction 1～6h;
(5) preparation of nanometer Zinc oxide powder
After (4) step accomplished, the mixed solution behind the zinc hydroxide coupling graft reaction that (4) step was prepared, naturally cool to room temperature after, carry out suction filtration; Collect filtrating and filter cake respectively, to the filter cake of collecting, according to the volume of filter cake: the volume ratio of distilled water wash agent is 1: 1～5 ratio, with the distilled water wash agent filter cake is washed 3～5 times; Filter cake after collecting washings respectively and washing distills recovery to the washings of collecting, and the filter cake after the washing of collecting is put into baking oven earlier; Under 80～180 ℃, dry 2～6h puts into apparatus,Soxhlet's with dried pressed powder again; With toluene solution and under the boiling temperature of toluene, carry out Suo Shi and extract 10～24h, take out the pressed powder after Suo Shi extracts then; Put into loft drier, under 100～280 ℃ of temperature, dry 4～12h.
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| CN108570850A (en) * | 2018-02-15 | 2018-09-25 | 湖北大学 | A kind of preparation method of the excellent super wetting woven fabric of stabilization patience for water-oil separating |
| CN113136182A (en) * | 2021-04-21 | 2021-07-20 | 西南石油大学 | High-temperature-resistant Pickering emulsion type drilling fluid and preparation method thereof |
| CN114652823A (en) * | 2022-02-28 | 2022-06-24 | 扬州大学 | Atractylodes macrocephala polysaccharide-nano zinc oxide compound and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107383937A (en) * | 2017-06-06 | 2017-11-24 | 安徽腾龙泵阀制造有限公司 | A kind of preparation method of pump housing coating modified nano zinc oxide |
| CN108570850A (en) * | 2018-02-15 | 2018-09-25 | 湖北大学 | A kind of preparation method of the excellent super wetting woven fabric of stabilization patience for water-oil separating |
| CN108570850B (en) * | 2018-02-15 | 2021-03-02 | 湖北大学 | Preparation method of super-wetting woven fabric with excellent stability and tolerance for oil-water separation |
| CN113136182A (en) * | 2021-04-21 | 2021-07-20 | 西南石油大学 | High-temperature-resistant Pickering emulsion type drilling fluid and preparation method thereof |
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| CN114652823B (en) * | 2022-02-28 | 2023-10-27 | 扬州大学 | Atractylodes macrocephala polysaccharide-nano zinc oxide compound and preparation method and application thereof |
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| CN102515250B (en) | 2014-03-26 |
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