CN102765745A - Zinc sulfide nano particle with sulfydryl surface finish and preparation method thereof - Google Patents
Zinc sulfide nano particle with sulfydryl surface finish and preparation method thereof Download PDFInfo
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- CN102765745A CN102765745A CN201210293596XA CN201210293596A CN102765745A CN 102765745 A CN102765745 A CN 102765745A CN 201210293596X A CN201210293596X A CN 201210293596XA CN 201210293596 A CN201210293596 A CN 201210293596A CN 102765745 A CN102765745 A CN 102765745A
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Abstract
Provided are a zinc sulfide nano particle with sulfydryl surface finish and a preparation method thereof. A solvent heat synthesis method is adopted, thiourea is selected to serve as a sulfur source, zinc acetate is a zinc source, and N,N-dimethylformamide serves as a reaction medium. 2,3-dimercaprol ethyl sulfo-propanethiol (BES) serves as dressing agent ligand which is mixed with zinc and the sulfur source according to certain proportion, reaction is carried out for 6-12 hours at the temperature of 120-160 DEG C through condensation backflow, the zinc sulfide nano particle with the sulfydryl surface finish is synthetized in situ, particles are even in dispersion, and average size is within 100nm. The zinc sulfide nano particle provided with the sulfydryl surface finish and obtained by using the preparation method is high in interface refractive index, good in dispersibility and moderate in reaction, contribute to in situ polymerization compound with macromolecules, can serve as an electroluminescence material, is particularly suitable to compound with optic plastic to improve refractive index, and serves as optical elements such as a lens.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of Zinc sulfide nano-particle and preparation method thereof, particularly have Zinc sulfide nano-particle of sulfydryl finishing and preparation method thereof.
Technical background
Zinc sulfide nano-particle control is synthetic to be a research direction of present field of nanoparticles.Body phase zinc sulfide crystal material has higher refractive index (n
620nm=2.36) be a kind of semiconductor material of broad-band gap, and (400～14000nm) all have lower optical absorption characteristics, have the good optical characteristic in very wide wavelength band.Therefore, often be introduced in the performances such as specific refractory power that improve polymer materials in the polymer materials.
At present chemical process prepare the Zinc sulfide nano-particle main path be adopt water miscible tensio-active agent (like mercaptoethanol (CN 102061079), Thiovanic acid (Zhao, Q. R.; Xie, Y.; Zhang, Z. G.; Bai, X., Size-selective synthesis of zinc sulfide hierarchical structures and their photocatalytic activity.
Crystal Growth & Design 2007, 7(1), 153-158.) be the coating materials part) etc., in the polar reaction medium, under the certain reaction condition, obtain Zinc sulfide nano-particle.The nano-particles size that this method obtains is less, can overcome effectively that inorganic particulate is reunited in polymkeric substance and the shortcoming of scattering of light.The defective that this method exists is: the content through coating in the nanoparticle of coating materials modification is very high, though the specific refractory power of Zinc sulfide nano-particle itself reaches 2.368, and lower (the mercaptoethanol n of the specific refractory power of coating materials
d=1.4996, Thiovanic acid n
d=1.5030), it is lofty that the interface changes, and it is a lot of that the specific refractory power of the Zinc sulfide nano-particle after modifying also can corresponding reduction, and residual hydroxyl and carboxyl activity height, and it is wayward to make that Zinc sulfide nano-particle and polymerization single polymerization monomer in-situ polymerization prepare composite material.
Summary of the invention
The technical problem that the present invention will solve provides a kind of Zinc sulfide nano-particle and chemical prepn process thereof of sulfydryl finishing; With the specific refractory power that improves Zinc sulfide nano-particle, improve the dispersiveness of nanoparticle in polymkeric substance, promote interfacial refraction rate and reactivity (associativity); Thereby the raising composite property, and resulting Zinc sulfide nano-particle prepare composite material be easy to control.
In order to realize above-mentioned technical problem, technical scheme of the present invention is following.
The present invention provides a kind of Zinc sulfide nano-particle of sulfydryl finishing, and selecting sulphur source and zinc source is raw material, with N; Dinethylformamide is a reaction medium; With 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan (BES) is the modifier part, the synthetic Zinc sulfide nano-particle with sulfydryl finishing of original position.
The zinc source can be in zinc acetate, zinc nitrate, zinc sulfate, the zinc chloride any.
The sulphur source can receive for thiocarbamide, sulfuration, in the thioacetamide any.
Zinc sulfide nano-particle is uniformly dispersed, and mean sizes is in 100nm.
The present invention proposes a kind of preparation method with Zinc sulfide nano-particle of sulfydryl finishing, adopts solvent-thermal method to comprise the steps:
(1) preparation zinc source/dimethyl formamide solution I;
(2) preparation modifier part 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan/dimethyl formamide solution II;
(3) preparation sulphur source/dimethyl formamide solution III;
(4) solution I described in the step (1) is added in the reactor drum, and logical nitrogen protection is stirred down;
(5) solution II described in the step (2) is joined in the described reactor drum of step (4), mix with solution I, and heat temperature raising to temperature of reaction (120-150 ℃);
(6) solution III described in the step (3) is joined in the described reactor drum of step (4), keep nitrogen protection and be stirred under the temperature of reaction (120-150 ℃) condensing reflux 6-12 hour;
(7) treat that step (6) reaction finishes after, with vacuum pump underpressure distillation enriched product solution, liquid concentrator is used ethanol sedimentation; The centrifugal zinc sulphide particles that obtains; And wash 3 times with absolute ethyl alcohol, wash 2 times with anhydrous methanol again, drying obtains the title product Zinc sulfide nano-particle in vacuum drying oven.
Among the above preparation method, the mol ratio in zinc source and sulphur source is 1:1～1:4, and 2, the middle sulfydryl of 3-dimercapto ethylenebis dithiocarbamate propylmercaptan (BES) and the mol ratio in zinc source are 1:1～4:1; The zinc source is any in zinc acetate, zinc nitrate, zinc sulfate, the zinc chloride; The sulphur source be thiocarbamide, sulfuration receive, in the thioacetamide any.
The present invention has beneficial effect.The present invention is through with 2 of high refractive index (specific refractory power is 1.6430); 3-dimercapto ethylenebis dithiocarbamate propylmercaptan synthesizes zinc sulphide particles for the modifier part through solvent-thermal method; Through control reaction temperature, reaction conditions and raw material part; Realize effective control of microcosmic particle diameter, thereby obtain Zinc sulfide nano-particle.BES is modified at the zinc sulphide particles surface; Make the zinc sulphide particles surface have functional mercapto groups; The dispersibility that strengthens Zinc sulfide nano-particle also can be reacted with organic monomer; Other raw materials such as the direct reaction such as isocyanic ester, the different propane of epoxy that use in the time of can preparing with optical resin and optical thin film are fixed to nanoparticle in the organic phase, help its dispersion in polymkeric substance, improved the interface associativity, improved compound after the specific refractory power of macromolecule matrix.Therefore the Zinc sulfide nano-particle of the sulfydryl finishing that obtains of the present invention can be used as electroluminescent material; Can constitute the performance that matrix material improves macromolecular material with polymer; Be particularly useful for and the compound raising specific refractory power of optical plastics, as optics such as eyeglasses.
Description of drawings
Do further detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is the X-ray diffractogram of prepared Zinc sulfide nano-particle.
Fig. 2 is the infrared spectrogram of prepared Zinc sulfide nano-particle.
Fig. 3 is the sem photograph of prepared Zinc sulfide nano-particle.
Fig. 4 is the size distribution figure of prepared Zinc sulfide nano-particle.
Embodiment
Following instance is to further specify of the present invention, rather than limits scope of the present invention.
The 0.81g Zinc diacetate dihydrate joined mix the back in the 50ml N to going in the there-necked flask and feed nitrogen to stir; Then at the premixture that in there-necked flask, adds 1.145gBES and 25ml N, be warming up to 120 ℃ after stirring 20min, the premixture of adding 0.28g thiocarbamide and 25ml N was 120 ℃ of refluxed 10 hours.Use vacuum pump underpressure distillation concentration response thing then, liquid concentrator is used ethanol sedimentation, the centrifugal zinc sulphide particles that obtains, and wash 3 times with ethanol, to wash 2 times with methyl alcohol again, vacuum-drying obtains the white powder Zinc sulfide nano-particle at last.During this implements just, zinc source/sulphur source/modifier sulfydryl=1/1/3 (mol ratio).
Prepare the product of gained by this embodiment, its X-ray diffraction analysis is as shown in Figure 1, X-coordinate angle among the figure (
O), be 2 θ angles, be the angle of diffraction spectrometer scanning, ordinate zou is the detected counting of receptor, is relative signal intensity, diffractogram has the crystal structure characteristic of zinc sulphide, shows that prepared product is a Zinc sulfide nano-particle.In addition, its IR spectroscopy spectrogram is as shown in Figure 2, and X-coordinate is a wave number, the cm of unit
-1, ordinate zou is the per-cent transmitance, 2531cm among Fig. 2
-1The place explains that for the sulfydryl absorption peak Zinc sulfide nano-particle surface arrangement has sulfydryl.It is as shown in Figure 3 that this embodiment prepares the ESEM morphology analysis of Zinc sulfide nano-particle of gained.Through size distribution figure such as Fig. 4 that laser light scattering instrument is measured, wherein X-coordinate is a particle dia, and unit is nanometer (nm), and ordinate zou is the relative percentage of weight of the particle of respective diameters, and Fig. 4 shows that average particle size is less than 100nm.
Embodiment 2
The 0.81g Zinc diacetate dihydrate joined mix the back in the 50ml N to going in the there-necked flask and feed nitrogen to stir; Then at the premixture that in there-necked flask, adds 1.145g BES and 25ml N, be warming up to 150 ℃ after stirring 20min, the premixture of adding 0.28g thiocarbamide and 25ml N was 120 ℃ of refluxed 10 hours.Use vacuum pump underpressure distillation concentration response thing then, liquid concentrator is used ethanol sedimentation, the centrifugal zinc sulphide particles that obtains, and wash 3 times with ethanol, to wash 2 times with methyl alcohol again, vacuum-drying obtains the white powder Zinc sulfide nano-particle at last.Among this embodiment, zinc source/sulphur source/modifier sulfydryl=1/1/3 (mol ratio).The Zinc sulfide nano-particle for preparing gained through this embodiment is identical with embodiment 1 preparation thus obtained microsphere structure, has same premium properties.
Embodiment 3
The 0.81g Zinc diacetate dihydrate joined mix the back in the 50ml N to going in the there-necked flask and feed nitrogen to stir; Then at the premixture that in there-necked flask, adds 1.145g BES and 25ml N, be warming up to 150 ℃ after stirring 20min, the premixture of adding 0.558g thiocarbamide and 25ml N was 120 ℃ of refluxed 8 hours.Use vacuum pump underpressure distillation concentration response thing then, liquid concentrator is used ethanol sedimentation, the centrifugal zinc sulphide particles that obtains, and wash 3 times with ethanol, to wash 2 times with methyl alcohol again, vacuum-drying obtains the white powder Zinc sulfide nano-particle at last.Among this embodiment, zinc source/sulphur source/modifier sulfydryl=1/2/3 (mol ratio).The Zinc sulfide nano-particle for preparing gained through this embodiment is identical with embodiment 1 preparation thus obtained microsphere structure, has same premium properties.
Embodiment 4
The 0.81g Zinc diacetate dihydrate joined mix the back in the 50ml N to going in the there-necked flask and feed nitrogen to stir; Then at the premixture that in there-necked flask, adds 1.145g BES and 25ml N, be warming up to 150 ℃ after stirring 20min, the premixture of adding 0.84g thiocarbamide and 25ml N was 120 ℃ of refluxed 5 hours.Use vacuum pump underpressure distillation concentration response thing then, liquid concentrator is used ethanol sedimentation, the centrifugal zinc sulphide particles that obtains, and wash 3 times with ethanol, to wash 2 times with methyl alcohol again, vacuum-drying obtains the white powder Zinc sulfide nano-particle at last.Among this embodiment, zinc source/sulphur source/modifier sulfydryl=1/3/3 (mol ratio).The Zinc sulfide nano-particle for preparing gained through this embodiment is identical with embodiment 1 preparation thus obtained microsphere structure, has same premium properties.
Embodiment 5
The 0.81g Zinc diacetate dihydrate joined mix the back in the 50ml N to going in the there-necked flask and feed nitrogen to stir; Then at the premixture that in there-necked flask, adds 0.573g BES and 25ml N, be warming up to 150 ℃ after stirring 20min, the premixture of adding 0.558g thiocarbamide and 25ml N was 150 ℃ of refluxed 10 hours.Use vacuum pump underpressure distillation concentration response thing then, liquid concentrator is used ethanol sedimentation, the centrifugal zinc sulphide particles that obtains, and wash 3 times with ethanol, to wash 2 times with methyl alcohol again, vacuum-drying obtains the white powder Zinc sulfide nano-particle at last.Among this embodiment, zinc source/sulphur source/modifier sulfydryl=1/2/2 (mol ratio).The Zinc sulfide nano-particle for preparing gained through this embodiment is identical with embodiment 1 preparation thus obtained microsphere structure, has same premium properties.
Claims (6)
1. Zinc sulfide nano-particle with sulfydryl finishing; Selecting sulphur source and zinc source is raw material; With N, dinethylformamide is a reaction medium, it is characterized in that: with 2; 3-dimercapto ethylenebis dithiocarbamate propylmercaptan (BES) is the modifier part, the synthetic Zinc sulfide nano-particle with sulfydryl finishing of original position.
2. Zinc sulfide nano-particle as claimed in claim 1 is characterized in that: described zinc source is any in zinc acetate, zinc nitrate, zinc sulfate, the zinc chloride.
3. Zinc sulfide nano-particle as claimed in claim 1 is characterized in that: described sulphur source is any in thiocarbamide, sodium sulphite, the thioacetamide.
4. Zinc sulfide nano-particle as claimed in claim 1 is characterized in that: described particle is uniformly dispersed, and mean sizes is in 100nm.
5. one kind prepares the method with Zinc sulfide nano-particle of sulfydryl finishing as claimed in claim 1, adopts the solvent thermal synthesis method, it is characterized in that comprising the steps:
Preparation zinc source/dimethyl formamide solution I;
Preparation modifier part 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan/dimethyl formamide solution II;
Preparation sulphur source/dimethyl formamide solution III;
Solution I described in the step (1) is added in the reactor drum, and logical nitrogen protection is stirred down;
Solution II described in the step (2) is joined in the described reactor drum of step (4), mix with solution I, and heat temperature raising to temperature of reaction (120-150 ℃);
Solution III described in the step (3) is joined in the described reactor drum of step (4), keep nitrogen protection and be stirred under the temperature of reaction (120-150 ℃) condensing reflux 6-12 hour;
After treating that step (6) reaction finishes,, liquid concentrator is used ethanol sedimentation with vacuum pump underpressure distillation enriched product solution; The centrifugal zinc sulphide particles that obtains; And wash 3 times with absolute ethyl alcohol, wash 2 times with anhydrous methanol again, drying obtains the title product Zinc sulfide nano-particle in vacuum drying oven.
6. preparation method as claimed in claim 5 is characterized in that: the mol ratio in said zinc source and sulphur source is 1:1～1:4, and 2, the middle sulfydryl of 3-dimercapto ethylenebis dithiocarbamate propylmercaptan (BES) and the mol ratio in zinc source are 1:1～4:1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613117A (en) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | Method for regulating and controlling zinc sulfide nanoparticle morphology by regulating proportion of mixed solvent |
| CN107325240A (en) * | 2017-07-10 | 2017-11-07 | 齐鲁工业大学 | A kind of polymerizable ZnS nanoparticles, preparation method and its method for preparing the high ophthalmically acceptable correction of refractive errors material of refraction |
| CN109627386A (en) * | 2018-12-12 | 2019-04-16 | 潍坊科技学院 | A kind of resin monomer composition |
| CN112410932A (en) * | 2019-08-20 | 2021-02-26 | Tcl集团股份有限公司 | Nano material and preparation method thereof |
| WO2022198438A1 (en) * | 2021-03-23 | 2022-09-29 | Wuhan Vast Conduct Science Foundation Co., Ltd. | Ligand-bound zinc sulfide nanoparticles, methods for making the same, and their use for treatment |
| CN116099744A (en) * | 2023-01-04 | 2023-05-12 | 中国科学院合肥物质科学研究院 | ZnS nanosphere antireflection film with medium and low refractive indexes and preparation method thereof |
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| CN102061079A (en) * | 2010-11-12 | 2011-05-18 | 吉林大学 | Method for preparing transparent high-refractive-index nano composite bulk phase optical material |
| CN102079541A (en) * | 2011-03-10 | 2011-06-01 | 北京科技大学 | Method for preparing doping type hexagonal system nano ZnS at low temperature |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102061079A (en) * | 2010-11-12 | 2011-05-18 | 吉林大学 | Method for preparing transparent high-refractive-index nano composite bulk phase optical material |
| CN102079541A (en) * | 2011-03-10 | 2011-06-01 | 北京科技大学 | Method for preparing doping type hexagonal system nano ZnS at low temperature |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613117A (en) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | Method for regulating and controlling zinc sulfide nanoparticle morphology by regulating proportion of mixed solvent |
| CN103613117B (en) * | 2013-12-02 | 2016-01-06 | 镇江市高等专科学校 | A kind of method adjusting the ratio regulation and control zinc sulfide nano pattern of mixed solvent |
| CN107325240A (en) * | 2017-07-10 | 2017-11-07 | 齐鲁工业大学 | A kind of polymerizable ZnS nanoparticles, preparation method and its method for preparing the high ophthalmically acceptable correction of refractive errors material of refraction |
| CN107325240B (en) * | 2017-07-10 | 2019-08-13 | 齐鲁工业大学 | A kind of polymerizable ZnS nanoparticle, preparation method and its it is used to prepare the high method for reflecting ophthalmically acceptable correction of refractive errors material |
| CN109627386A (en) * | 2018-12-12 | 2019-04-16 | 潍坊科技学院 | A kind of resin monomer composition |
| CN109627386B (en) * | 2018-12-12 | 2022-01-28 | 潍坊科技学院 | Resin monomer composition |
| CN112410932A (en) * | 2019-08-20 | 2021-02-26 | Tcl集团股份有限公司 | Nano material and preparation method thereof |
| WO2022198438A1 (en) * | 2021-03-23 | 2022-09-29 | Wuhan Vast Conduct Science Foundation Co., Ltd. | Ligand-bound zinc sulfide nanoparticles, methods for making the same, and their use for treatment |
| CN116099744A (en) * | 2023-01-04 | 2023-05-12 | 中国科学院合肥物质科学研究院 | ZnS nanosphere antireflection film with medium and low refractive indexes and preparation method thereof |
| CN116099744B (en) * | 2023-01-04 | 2023-12-26 | 中国科学院合肥物质科学研究院 | ZnS nanosphere antireflection film with medium and low refractive indexes and preparation method thereof |
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Application publication date: 20121107 |