CN1320602A - Retinyl Schiff's base-iron complex as microwave absorbent and its preparing process - Google Patents
Retinyl Schiff's base-iron complex as microwave absorbent and its preparing process Download PDFInfo
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- CN1320602A CN1320602A CN 01100573 CN01100573A CN1320602A CN 1320602 A CN1320602 A CN 1320602A CN 01100573 CN01100573 CN 01100573 CN 01100573 A CN01100573 A CN 01100573A CN 1320602 A CN1320602 A CN 1320602A
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Abstract
A retinyl Schiff's base-iron complex as microwave absorbent and its preparing process are disclosed. The vitamine A acetate is used as raw material. Said process includes hydrolysis of vitamine A acetate in the mixture of alcohol and water in the presence of alkali as catalyst, oxidizing with MnO2 as oxidant, and acting with binary amine (ethylenediamine) and metal salt (FeCl3). Its advantages are broad absorption band including radar/infrared waves, and light mass.
Description
The present invention relates to a kind of retinyl Schiff's base-iron complex as microwave absorbent and preparation method.The manufacturing technology that belongs to a kind of microwave absorbing material.
The microwave absorbing material of development research both at home and abroad has at present: the conducting polymer composite of particulate absorption agent, nano material, chirality absorption agent, polycrystalline fibre absorption agent, characteristic of semiconductor.Above-mentioned microwave absorbing agent material is generally than great, and the absorbing material of manufacturing uses and owes flexibly, accessibility.
The object of the present invention is to provide a kind of retinyl Schiff's base-iron complex as microwave absorbent and preparation method.This absorption agent not only can the compatible ripple that absorbs radar, and inhales the ripple bandwidth, and light weight, preparation method are simple.
For achieving the above object, the present invention is realized by the following technology that makes things convenient for.With is raw material.Generate vitamin A through hydrolysis reaction
1This intermediate (I) is through peroxidation, generate retinene, this intermediate (II) is through generating the small molecules retinyl Schiff's base with the diamine reaction, this intermediate (III) again with diamine and metal-salt effect, generate suc as formula 1 or formula 2 shown in the small molecules retinyl Schiff's base-iron complex as microwave absorbent.
Above-mentioned preparation process is characterized in that, hydrolysis reaction is to carry out in alcohol-water mixture, and adds alkaline catalysts in reaction solution, and catalyst consumption is the 90-110% (mol) of material quantity; Oxidizing reaction adopts MnO
2Or NaBiO
3Be oxygenant, its consumption and vitamin A
1Ratio be (2-5): 1, temperature of reaction is 10-40 ℃; The diamine that the preparation of small molecules retinyl Schiff's base is adopted is a quadrol, or butanediamine, perhaps Ursol D, and reaction is to carry out in the blending agent of ethanol and benzene, catalyzer employing sulfuric acid or nitric acid; The diamine that the preparation of retinyl Schiff's base-iron complex is adopted is a quadrol, or butanediamine, or Ursol D, and metal-salt is an iron trichloride, and temperature of reaction is 60-90 ℃.
Above-mentioned alcohol-water mixture is good with the ethanol/water mixed solution; Above-mentioned alkaline catalysts is good with NaOH.
Below the present invention is described in detail.
Vitamin A of the present invention
1The preparation of intermediate is shown below:
In this process, gordian technique is to have selected pure water medium, and be catalyzer with NaOH and determined catalyst consumption, suitably heating the assurance reaction system in the reaction process carries out under fast speed, and adopt lucifuge and logical nitrogen measure, to prevent the decomposition reaction under aerial oxidizing reaction of raw material and the illumination.
The preparation of retinene intermediate of the present invention is shown below:
Gordian technique in this process is the selection of oxygenant and determining of consumption thereof.Adopt MnO
2Better for the oxygenant effect, the temperature of reaction of controlling well can prevent effectively that part-OH over oxidation from generating carboxyl, improves the yield of intermediate product.
The preparation of small molecules retinyl Schiff's base intermediate of the present invention is shown below:
The gordian technique of this preparation process is the selection of diamine and the selection of reaction medium, select ethanol benzene medium, help forming ethanol benzene/water ternary azeotrope with water, this can fully guarantee shifting out of by product, favourable reaction is carried out to the resultant direction, makes to react completely.
The gordian technique of final product small molecules retinyl Schiff's base-iron complex preparation process of the present invention is the control of selective reaction thing diamine and metal-salt and temperature of reaction, in the preparation heat treated of jeweler's rouge is removed crystal water and can guarantee that reaction carries out fully and quality product.Final product of the present invention is powder or liquid, and proportion is at 1.0g-1.2g/cm
3, be soluble in dimethyl alum, Glacial acetic acid, be insoluble to ethanol, in acetone, chloroform, sherwood oil etc.
With embodiment the present invention is further specified again below.
Embodiment one:
In reaction vessel, add the 100ml NaOH aqueous solution (about 0.1mol), 200ml ethanol and 30g.In 80 ℃ of reaction 4hr end down.To neutral, use petroleum ether extraction with 0.2mol salt acid for adjusting pH value, concentrate after drying, obtain vitamin A
1(intermediate compound I), productive rate is about 95%.
The above-mentioned intermediate compound I and the 15g Manganse Dioxide that in Erlenmeyer flask, add 100ml sherwood oil, 4g respectively, behind the jam-pack lid 25 ℃ of following oscillatory reactions 5 days, reaction product is filtered, washed to clear solution, concentrate with rotary film evaporator, obtain retinene (intermediate II), productive rate is about 55%.
In the four-hole bottle that reflux condensate device is housed, add 14mmol retinene, 70ml benzene, 180ml dehydrated alcohol, 10mmol anhydrous sodium carbonate successively, treat to drip when temperature rises to 80 ℃ the benzole soln that contains quadrol, under agitation be back to anhydrous deviate from till, get the two Schiff's base (intermediate III) of retinyl-quadrol after separation, washing and drying, productive rate is 69%.
In reactor, add two Schiff's base (intermediate III-1) of 4.3g retinyl-quadrol and 45ml ethanol successively, and heating under agitation, drip iron trichloride ethanolic soln (the 5g iron trichloride is dissolved in the 25ml dehydrated alcohol) with dropping funnel during to 80 ℃, reacted again after dripping off 4 hours, leach precipitation after the cooling, and wash 3-4 time with dehydrated alcohol, after the drying yellow powder (product TSBS-1), productive rate is 59%.Infrared spectra, nucleus magnetic resonance and ESR analysis are determined its structure as shown in Equation 1, and this title complex is the paramagnetic substance of octahedra configuration.
Embodiment two:
The preparation of intermediate compound I and intermediate II is with identical with embodiment one.
In the four-hole bottle that reflux condensate device is housed, add 7mmol retinene, 70ml benzene, 180ml dehydrated alcohol, 15mmol anhydrous sodium carbonate successively, treat to drip when temperature rises to 80 ℃ the ethanol solution (14mmol retinene/12ml dehydrated alcohol) that contains retinene (intermediate II), under agitation be back to anhydrous deviate from till, get the two Schiff's base (intermediate III-2) of retinyl-Ursol D after separation, washing and drying, productive rate is 55%.
Add two Schiff's base (intermediate III-2) of 5.5mmol retinyl-Ursol D and 45ml ethanol successively at reactor, and heating under agitation, drip iron trichloride ethanolic soln (the 5g iron trichloride is dissolved in the 25ml dehydrated alcohol) with dropping funnel during to 80 ℃, reacted again after dripping off 4 hours, leach precipitation after the cooling, and wash 3-4 time with dehydrated alcohol, after the drying black powder (product TSBS-2), productive rate is 56%.Infrared spectra, nucleus magnetic resonance, ultimate analysis and ESR analysis obtain structure (as shown in Equation 2), and this title complex is the paramagnetic substance of octahedra configuration.
Embodiment three:
The preparation of intermediate compound I, intermediate II and intermediate III-2 is identical with embodiment two.
In reactor, add two Schiff's base (intermediate III-2) of 5mmol retinyl-Ursol D and 50ml ethanol successively, and heating under agitation, drip iron trichloride ethanolic soln (the 6g iron trichloride is dissolved in the 40ml dehydrated alcohol) at a slow speed with dropping funnel during to 80 ℃, reacted again after dripping off 6 hours, leach precipitation after the cooling, and wash 3-4 time with dehydrated alcohol, after the drying black powder (product TSBS-2), productive rate is 62%.
Retinyl Schiff's base-iron complex as microwave absorbent of the present invention, suction ripple bandwidth can the compatible ripples that absorbs radar, and its quality is 1/10 of a ferric oxide, and goods utilize the waveguide method at 8.2-12.4GH
2To the material complex permittivity, complex permeability is carried out sweep test in the frequency range, and by calculating reflectivity with the variation of frequency as shown in Figure 1.Figure center line 1 is represented retinyl-quadrol Schiff's base iron complex, and line 2 is represented retinyl-Ursol D Schiff's base iron complex.
As seen at the 8.4GHz-10.7GHz frequency band range, reflectivity is lower than-9dB, demonstrates wide band absorbing property.
Claims (3)
1. a retinyl Schiff's base-iron complex as microwave absorbent is a raw material with, generates vitamin A through hydrolysis reaction
1This intermediate (I) is through peroxidation, generate retinene, this intermediate (II) is through generating the small molecules retinyl Schiff's base with the diamine reaction, this intermediate (III) again with diamine and metal-salt effect, generate suc as formula 1 or formula 2 shown in the small molecules retinyl Schiff's base-iron complex as microwave absorbent.
2. preparation method according to the said retinyl Schiff's base-iron complex as microwave absorbent of claim 1, it is characterized in that: hydrolysis reaction is to carry out in alcohol-water mixture, and in reaction solution, adding alkaline catalysts, catalyst consumption is the 90-110% (mol) of material quantity; Oxidizing reaction adopts MnO
2Or NaBiO
3Be oxygenant, its consumption and vitamin A
1Ratio be (2-5): 1, temperature of reaction is 10-40 ℃; The diamine that the preparation of small molecules retinyl Schiff's base is adopted is a quadrol, or butanediamine, perhaps Ursol D, and reaction is to carry out in the blending agent of ethanol and benzene, catalyzer employing sulfuric acid or nitric acid; The diamine that the preparation of retinyl Schiff's base-iron complex is adopted is a quadrol, or butanediamine, or Ursol D, and metal-salt is an iron trichloride, and temperature of reaction is 60-90 ℃.
3. according to the preparation method of the said retinyl Schiff's base-iron complex as microwave absorbent of claim 2, it is characterized in that: said alcohol-water mixture is good with the ethanol/water mixed solution; Alkaline catalysts is good with NaOH.
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| CN 01100573 CN1320602A (en) | 2001-01-16 | 2001-01-16 | Retinyl Schiff's base-iron complex as microwave absorbent and its preparing process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351322C (en) * | 2004-05-11 | 2007-11-28 | 南京工业大学 | Iron powder absorbent and preparation method thereof |
| CN100371396C (en) * | 2004-05-11 | 2008-02-27 | 南京工业大学 | Iron powder absorbent and preparation method and application thereof |
| CN102660221A (en) * | 2012-05-16 | 2012-09-12 | 南昌航空大学 | Graphite-doped poly-Schiff base/carbonyl iron powder composite stealth material |
| CN102675876A (en) * | 2012-05-16 | 2012-09-19 | 南昌航空大学 | Carbon nano tube-doped poly-schiff base/ carbonyl iron powder composite stealth material |
| CN105062091A (en) * | 2015-08-03 | 2015-11-18 | 南昌航空大学 | Ferrocene-based chiral poly Schiff base salt/graphene composite wave-absorbing material |
| CN108623507A (en) * | 2017-03-15 | 2018-10-09 | 四川海思科制药有限公司 | The preparation method of Retinol Palmitate |
| CN114957075A (en) * | 2022-06-13 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of beta-carotene |
| CN115895258A (en) * | 2022-10-26 | 2023-04-04 | 中国航发北京航空材料研究院 | Polythioether sealant and synthetic method thereof |
-
2001
- 2001-01-16 CN CN 01100573 patent/CN1320602A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351322C (en) * | 2004-05-11 | 2007-11-28 | 南京工业大学 | Iron powder absorbent and preparation method thereof |
| CN100371396C (en) * | 2004-05-11 | 2008-02-27 | 南京工业大学 | Iron powder absorbent and preparation method and application thereof |
| CN102660221A (en) * | 2012-05-16 | 2012-09-12 | 南昌航空大学 | Graphite-doped poly-Schiff base/carbonyl iron powder composite stealth material |
| CN102675876A (en) * | 2012-05-16 | 2012-09-19 | 南昌航空大学 | Carbon nano tube-doped poly-schiff base/ carbonyl iron powder composite stealth material |
| CN102675876B (en) * | 2012-05-16 | 2014-06-18 | 南昌航空大学 | Carbon nano tube-doped poly-schiff base/ carbonyl iron powder composite stealth material |
| CN105062091A (en) * | 2015-08-03 | 2015-11-18 | 南昌航空大学 | Ferrocene-based chiral poly Schiff base salt/graphene composite wave-absorbing material |
| CN108623507A (en) * | 2017-03-15 | 2018-10-09 | 四川海思科制药有限公司 | The preparation method of Retinol Palmitate |
| CN114957075A (en) * | 2022-06-13 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of beta-carotene |
| CN114957075B (en) * | 2022-06-13 | 2023-09-19 | 万华化学集团股份有限公司 | Preparation method of beta-carotene |
| CN115895258A (en) * | 2022-10-26 | 2023-04-04 | 中国航发北京航空材料研究院 | Polythioether sealant and synthetic method thereof |
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