CN100562489C - Metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method - Google Patents
Metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method Download PDFInfo
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- CN100562489C CN100562489C CNB2007101563352A CN200710156335A CN100562489C CN 100562489 C CN100562489 C CN 100562489C CN B2007101563352 A CNB2007101563352 A CN B2007101563352A CN 200710156335 A CN200710156335 A CN 200710156335A CN 100562489 C CN100562489 C CN 100562489C
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- thf
- zncl
- metal organic
- zinc peroxide
- legal system
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- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229940105296 zinc peroxide Drugs 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 title claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 46
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 3
- 239000011592 zinc chloride Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 230000000740 bleeding effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- NFBPCQSTZITERU-UHFFFAOYSA-N C1CCCCC1[Zn]C1CCCCC1 Chemical compound C1CCCCC1[Zn]C1CCCCC1 NFBPCQSTZITERU-UHFFFAOYSA-N 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- -1 azo carbon Chemical compound 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses the method that a kind of metal organic intermediate legal system is equipped with the nanometer zinc peroxide.Adopt zinc chloride and Grignard reagent to prepare dicyclohexyl zinc precursor body, tetrahydrofuran (THF) is as organic solvent, and octylame has prepared nanometer zinc peroxide particle as tensio-active agent at normal temperatures with metal organic intermediate method.Because adopt chemical process, entire reaction is carried out at normal temperatures, be easy to control; The reaction product size distribution is even; The product purity height.
Description
Technical field
The present invention relates to technical field of material, particularly a kind of metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method.
Background technology
Nano science and nanotechnology are current one of the most great-hearted research fields, because the performance of nano material and potential are used the dependency for size and pattern, have reported the nano-oxide that has synthesized such as nanotube, nano wire, nanometer rod, nanometer plate, nanometer square or the like various patterns.In recent years, Chinese scholars to the new oxide photocatalyst (as ZnO, Cu
2O, NiO, Co
3O
4, Fe
3O
4) carried out big quantity research, obtained encouraging progress, wherein zinc oxide has advantages of high catalytic activity as semiconductor light-catalyst, have good uv-absorbing function and good piezoelectric property, the energy gap of its body phase material is 312eV, is the UV-light of 387nm corresponding to wavelength, and ZnO
2Band-gap energy more taller than ZnO, be the several oxide semiconductor materials that can realize quantum size effect of only a few in the photocatalyst.In industrial application, zinc peroxide can be used to make the foam thermal molding product of dystectic synthetic resins such as polymeric amide, polyolefine, polyester, polycarbonate, ABS resin, polysulfone resin etc. with azo carbon combination as the winding-up agent.Zinc peroxide is used to produce anti-oil and anti-aging sealing agent, pipeline etc. as vulcanizing agent in the sulfuration of polysulfide rubber, and the sulfuration that is used for the carbonyl paracril is with the production rubber that resistance to wears.Strengthen the anti-carbon-burning capacity and the storage stability of unhardened rubber as stiffening agent at carboxylic acid nitrile butadiene rubber nitrile rubber zinc peroxide.Zinc peroxide can be used as the oxygenant and the oxygenate of explosive substance (as explosive, pyrotechnics).In the production process of ceramics insulator, help to quicken the combustion of organic binder bond or the residual carbon content in the removal minimizing Low fire ceramic material thereby add zinc peroxide.In the oil and natural gas excavation industry, zinc peroxide is used to prepare the mud that drilling fluid decomposes caking under the well bore, makes exploitation more smooth.In addition, zinc peroxide can be used for making the dermopathic anticorrosive additive of treatment.Zinc peroxide also can be used for other field as oxygenant and SYNTHETIC OPTICAL WHITNER and also is widely used.
Nano-ZnO
2Material has broad application prospects because of its unique character, there is apparatus expensive in physical preparation method, the preparation process complexity, the cost height, shortcomings such as productive rate is low, and chemical method is because the method that low, the equipment of product cost of preparation is simple, the product purity advantages of higher is considered to the potentialization of following some practicability nano material of preparation.
Summary of the invention
The object of the present invention is to provide a kind of metal organic intermediate legal system to be equipped with nanometer zinc peroxide particulate method.
The technical solution used in the present invention is that the step of this method is as follows:
One, material mixture ratio:
Analytical pure zinc chloride ZnCl
2,
Analytical pure Grignard reagent 1.3mol/L Mg (C
6H
11) Cl/THF,
Analytical pure tetrahydrofuran (THF) C
4H
8O,
Concentration is 99% octylame C
8H
19N,
Analytical pure dehydrated alcohol C
2H
6O,
The hydrogen peroxide H of analytical pure 30%
2O
2
Two, preparation process:
1) with ZnCl
2Be dissolved in the tetrahydrofuran (THF) that to form concentration be the clear solution of 0.04mol/L;
2) use nitrogen protection, under 78HW-3 type constant temperature magnetic agitation instrument, add Grignard reagent Mg (C
6H
11) Cl/THF, react after 2～3 hours, add octylame C
8H
19The N reaction got faint yellow turbid solution, wherein ZnCl in 15～20 hours
2, grignard reagent, the mol ratio of octylame=1: 2: 1～2
3) heating is until evaporate to dryness down at 50～60 ° above prepared solution to be placed thermostatic bath, and the solid residue behind the taking-up evaporate to dryness adds hydrogen peroxide H under room temperature
2O
2Dissolving, placed 10～20 hours, reacted mixing solutions obtains solid product and successively uses distilled water and absolute ethanol washing through 10000r/min SORVALL LEGEND-T whizzer centrifugation 15～30min, the difference recentrifuge, the solid that obtains at room temperature is dried to pressed powder.
In order to prevent ZnCl
2Suction also can be in advance to ZnCl
2Carry out purification process, purification process: at ZnCl
2In add thionyl chloride and refluxed 1 hour in 80～90 °, the thionyl chloride evaporate to dryness, the removal residual impurity of bleeding in the vacuum.
In order to remove moisture possible in the tetrahydrofuran (THF) and impurity,, reflux and collect after 30 minutes in advance to the tetrahydrofuran (THF) purification process.
Because the beneficial effect that has adopted chemical method, the present invention to have is:
1) entire reaction is carried out at normal temperatures, is easy to control.
2) the reaction product size distribution is even.
3) product purity height.
Description of drawings
Fig. 1 is the ZnO according to embodiment 1 preparation
2The XRD diffractogram of nano particle;
Fig. 2 is the ZnO according to embodiment 1 preparation
2The TEM photo of nano particle.
Embodiment
Embodiment 1:
Carry out according to preparation process, with 0.136g ZnCl
2Be dissolved among the 25ml THF, form the clear solution of 0.04mol/L, under 78HW-3 type constant temperature magnetic agitation instrument, add 1.54ml Grignard reagent Mg (C
6H
11) Cl.Reaction 2h adds 0.165ml octylame C
8H
19N reacted 15 hours.More than operation is all at N
2Carry out under the protection.Place thermostatic bath to heat until evaporate to dryness down above prepared solution at 50 °.Solid residue behind the taking-up evaporate to dryness adds 20ml hydrogen peroxide H under room temperature
2O
2, reaction 10h.Reacted mixing solutions obtains solid product and disperses washing respectively with distilled water and dehydrated alcohol through 10000r/min SORVALL LEGEND-T whizzer centrifugation 15min, the difference recentrifuge, and the solid that obtains at room temperature is dried to pressed powder.The purity of zinc peroxide is 91% (mass ratio) in the product.Fig. 1 carries out X-ray diffraction analysis (XRD) to sample powder.The test of transmission electron microscope observation TEM is that dried powder supersound process is dispersed in the ethanol, then with drips of solution on the copper mesh that is coated with carbon film, drying at room temperature, TEM model are JEOL200CX.Fig. 2 presses the ZnO of embodiment preparation
2The TEM photo of nano particle.
Embodiment 2:
Carry out according to preparation process, with 0.136g ZnCl
2Be dissolved among the 25ml THF, form the clear solution of 0.04mol/L, under 78HW-3 type constant temperature magnetic agitation instrument, add 1.54ml Grignard reagent Mg (C
6H
11) Cl.Reaction 3h adds 0.33ml octylame C
8H
19N reacted 20 hours.More than operation is all at N
2Carry out under the protection.Place thermostatic bath to heat until evaporate to dryness down above prepared solution at 60 °.Solid residue behind the taking-up evaporate to dryness adds 30ml hydrogen peroxide H under room temperature
2O
2, reaction 20h.Reacted mixing solutions obtains solid product and disperses washing respectively with distilled water and dehydrated alcohol through 10000r/min SORVALL LEGEND-T whizzer centrifugation 30min, the difference recentrifuge, and the solid that obtains at room temperature is dried to pressed powder.The purity of zinc peroxide is 76% (mass ratio) in the product.
Embodiment 3:
Carry out according to preparation process, with 0.136g ZnCl
2Be dissolved among the 25ml THF, form the clear solution of 0.04mol/L, under 78HW-3 type constant temperature magnetic agitation instrument, add 1.54ml Grignard reagent Mg (C
6H
11) Cl.Reaction 2.5h adds 0.248ml octylame C
8H
19N reacted 17 hours.More than operation is all at N
2Carry out under the protection.Place thermostatic bath to heat until evaporate to dryness down above prepared solution at 55 °.Solid residue behind the taking-up evaporate to dryness adds 30ml hydrogen peroxide H under room temperature
2O
2, reaction 15h.Reacted mixing solutions obtains solid product and disperses washing respectively with distilled water and dehydrated alcohol through 10000r/min SORVALL LEGEND-T whizzer centrifugation 15min, the difference recentrifuge, and the solid that obtains at room temperature is dried to pressed powder.The purity of zinc peroxide is 82% (mass ratio) in the product.
Claims (3)
1, a kind of metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method, it is characterized in that the step of this method is as follows:
One, material mixture ratio:
Analytical pure zinc chloride ZnCl
2,
Analytical pure Grignard reagent 1.3mol/L Mg (C
6H
11) Cl/THF,
Analytical pure tetrahydrofuran (THF) C
4H
8O,
Concentration is 99% octylame C
8H
19N,
Analytical pure dehydrated alcohol C
2H
6O,
The hydrogen peroxide H of analytical pure 30%
2O
2
Two, preparation process
1) with ZnCl
2Be dissolved in the tetrahydrofuran (THF) that to form concentration be the clear solution of 0.04mol/L;
2) use nitrogen protection, under 78HW-3 type constant temperature magnetic agitation instrument, add Grignard reagent Mg (C
6H
11) Cl/THF, react after 2～3 hours, add octylame C
8H
19The N reaction got faint yellow turbid solution, wherein ZnCl in 15～20 hours
2, Grignard reagent, the mol ratio of octylame=1: 2: 1～2;
3) heating is until evaporate to dryness down at 50～60 ° above prepared solution to be placed thermostatic bath, and the solid residue behind the taking-up evaporate to dryness adds hydrogen peroxide H under room temperature
2O
2Dissolving, placed 10～20 hours, reacted mixing solutions obtains solid product and successively uses distilled water and absolute ethanol washing through 10000r/min SORVALL LEGEND-T whizzer centrifugation 15～30min, the difference recentrifuge, the solid that obtains at room temperature is dried to pressed powder.
2, a kind of metal organic intermediate legal system according to claim 1 is equipped with nanometer zinc peroxide particulate method, it is characterized in that: in advance to ZnCl
2Carry out purification process, purification process: at ZnCl
2In add thionyl chloride and refluxed 1 hour in 80～90 °, the thionyl chloride evaporate to dryness, the removal residual impurity of bleeding in the vacuum.
3, a kind of metal organic intermediate legal system according to claim 1 is equipped with nanometer zinc peroxide particulate method, it is characterized in that: in advance to tetrahydrofuran (THF) C
4H
8The O purification process refluxes and collects after 30 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101563352A CN100562489C (en) | 2007-10-19 | 2007-10-19 | Metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101563352A CN100562489C (en) | 2007-10-19 | 2007-10-19 | Metal organic intermediate legal system is equipped with nanometer zinc peroxide particulate method |
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| Publication Number | Publication Date |
|---|---|
| CN101177247A CN101177247A (en) | 2008-05-14 |
| CN100562489C true CN100562489C (en) | 2009-11-25 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022015180A1 (en) * | 2020-07-17 | 2022-01-20 | NANOXO sp. z o.o. | Method of preparation of zinc-oxygen-based nanoparticles, zinc peroxide nanoparticles obtained by this method and their use |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2467952C1 (en) * | 2011-03-21 | 2012-11-27 | Открытое акционерное общество "Корпорация "Росхимзащита" (ОАО "Корпорация "Росхимзащита") | Method of producing zinc peroxide |
-
2007
- 2007-10-19 CN CNB2007101563352A patent/CN100562489C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 纳米过氧化锌的光催化性能研究. 王培义等.精细化工，第24卷第5期. 2007 |
| 纳米过氧化锌的光催化性能研究. 王培义等.精细化工，第24卷第5期. 2007 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022015180A1 (en) * | 2020-07-17 | 2022-01-20 | NANOXO sp. z o.o. | Method of preparation of zinc-oxygen-based nanoparticles, zinc peroxide nanoparticles obtained by this method and their use |
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| Publication number | Publication date |
|---|---|
| CN101177247A (en) | 2008-05-14 |
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