CN101148422A - Preparation for p-benzoquionone dioxime - Google Patents
Preparation for p-benzoquionone dioxime Download PDFInfo
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- CN101148422A CN101148422A CNA2007100475405A CN200710047540A CN101148422A CN 101148422 A CN101148422 A CN 101148422A CN A2007100475405 A CNA2007100475405 A CN A2007100475405A CN 200710047540 A CN200710047540 A CN 200710047540A CN 101148422 A CN101148422 A CN 101148422A
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Abstract
The present invention relates to catalytic synthesis process of p-benzoquinone dioxime, belongs to the field of organic synthesis technology, and is especially catalytic synthesis process of p-benzoquinone dioxime with p-benzoquinone and hydroxylamine chloride as material and calcium carbonate as catalyst and in certain temperature. P-benzoquinone dioxime, p-benzoquinone and hydroxylamine chloride are first reacted in alcohol inside a reactor; and through the subsequent vacuum evaporation to eliminate solvent, adding HCl and water through stirring and suction filtering, product is obtained. The process has high yield, high product purity, mild reaction condition, low energy consumption, environment friendship, and cheap and reuseable catalyst.
Description
Technical field
This method that relates to the synthetic p-benzoqui(o)none dioxime of a kind of catalysis, definite says, is with para benzoquinone, hydroxylamine chloride is a raw material, is catalyzer with lime carbonate, one goes on foot the method that p-benzoqui(o)none dioxime is synthesized in catalysis at a certain temperature, belongs to the technical field of organic synthesis.
Background technology
P-benzoqui(o)none dioxime is a kind of linking agent, have in sizing material and easily disperse, vulcanization rate is fast, and sizing material tensile modulus height is heat-resisting, anti-ozone, characteristics such as electrical insulating property is good can be used as acrylic acid stopper, the tackiness agent of metallic glass hot melt, the conditioning agent that olefin copolymer is crosslinked, organic monomer stablizer and self-vulcanizing type tackiness agent.To oxygenant (Pb
3O
4, PbO
2) activation arranged, the resistance to heat that improves the trevira tire cord is [referring to Gogotov A.W., Parilova M.V., Amosov V.V., Khaliullin A.K. (OAO " angarskayaNeftekhicheskaya Kompaniya " .Russia) .Proizvodstvo iIspol ' zovanie Elastomerov2001, (3), 7-10 (Russ); Russak Aleksandr Vladimirovich, Borejko Natalya Pavlovna, Tabaev Rakhim Garifovich, Melnikov Gennadij Nikolaevich, Salyakhov DanisRavilovich (Nizhnekamskoe proizvodstvennoe Ob ' edinenie " Nizhnekamskneftekhim ", Estonia) Russ, RU 2,039,757 (Cl.C08F2/42), 20 Jul 1995, SU Appl.5,042,180,15 May 1992 (Russ) .].Be specially adapted to the tensile modulus height, the isoprene-isobutylene rubber that vulcanization rate is fast, natural rubber; butadiene-styrene rubber; thiorubber, ethylene-propylene rubber(EPR) and prevent rubber item of nuclear radiation etc. [referring to EtoAkiko, Hirata Yasusshi (Bridgestone Corp.) Jpn.Kakai Tokkyo KohoJP 03 37; 240,[91 37; 240] (Cl.C08L7/00), 18 Feb1991, Appl.89/171; 232,04 Jul 1989; 6pp.].The method of industrial in recent years production p-benzoqui(o)none dioxime mainly is: at 0 ℃, finite concentration sulfuric acid exists down, the Sodium Nitrite nitrosification is dissolved in the phenol of 30%NaOH solution and produces the para benzoquinone monoxime, then the para benzoquinone monoxime that makes is added the azanol oximate and produces final product p-benzoqui(o)none dioxime [referring to Shanxi-Prov Inst of Chemical Industry's " plastic, rubber auxiliary agent " (05 month nineteen eighty-three first version Page351)]; Yang Xianlin " fine chemical product prescription and use technology " (03 month nineteen ninety-five first version Page456)].This method steps is loaded down with trivial details, needs cooling and heats two covering devices, productive rate lower (about 60%), product purity is subjected to the restriction (≤95%) of this synthetic method, contains more impurity, and owing to used Sodium Nitrite, the disagreeableness reagent of environment such as sulfuric acid causes the building-up process blowdown serious.
Summary of the invention
The objective of the invention is defective, a kind of reaction conditions gentleness is provided, environmental friendliness, productive rate height, the method for the synthetic p-benzoqui(o)none dioxime that green degree is high at above-mentioned synthetic method.
The technical scheme that realizes the object of the invention is with para benzoquinone, and lime carbonate, hydroxylamine chloride are raw material.Concrete steps:
The first step is 4: 3～4: 5.4 para benzoquinone of mass ratio, lime carbonate and and quality be that the hydroxylamine chloride of 2.50～2.75 times of para benzoquinone is put into reactor.Add ethanol 60～80ml, water 20ml, 60～70 ℃ of constant temperature, constant temperature time 4h.
Second step was revolved steaming with the first step reaction product in 50 ℃ of vacuum, after solvent evaporation finishes, added dense HCL of 11.2g and 60ml water in reactor, and suction filtration behind the stirring 5min will be filtered to such an extent that the product water cleans after drying, promptly get product.
Advantage of the present invention is:
1. reaction yield height, the productive rate of p-benzoqui(o)none dioxime can reach more than 95%, the product purity height, product is through washing drying, and purity can reach more than 98%.Reaction conditions is 60 ℃, and comparatively gentle, energy consumption is less.
2. environmental friendliness, the reagent that this reaction is used all belongs to for nontoxic, because solvent can be recycled, so discharging of waste liquid is less, and environmental sound.
3. catalyzer is cheap and easy to get, and reacts the renewable after treatment use of rear catalyst waste liquid that finishes.
Embodiment
Embodiment 1:
The first step, with the 4.0g para benzoquinone, 5.4g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 80ml ethanol and 20ml water, evenly stirs.React 3h down at 70 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.05g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 79.2%.
Embodiment 2:
The first step, with the 4.0g para benzoquinone, 4.1g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 80ml ethanol and 20ml water, evenly stirs.React 3h down at 70 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.49g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 87.9%.
Embodiment 3:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 80ml ethanol and 20ml water, evenly stirs.React 3h down at 70 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.77g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 93.3%.
Embodiment 4:
The first step, with the 4.0g para benzoquinone, 2.7g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 80ml ethanol and 20ml water, evenly stirs.React 3h down at 70 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.63g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 90.6%.
Embodiment 5:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 60ml ethanol and 20ml water, evenly stirs.React 3h down at 70 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.87g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 95.3%.
Embodiment 6:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, the 10.0g hydroxylamine chloride is put into reactor, adds 60ml ethanol and 20ml water, evenly stirs.React 4h down at 60 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.82g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 94.3%.
Embodiment 7:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, the 8.0g hydroxylamine chloride is put into reactor, adds 60ml ethanol and 20ml water, evenly stirs.React 4h down at 60 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.70g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 92.0%.
Embodiment 8:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, the 8.0g hydroxylamine chloride is put into reactor, adds 80ml ethanol and 20ml water, evenly stirs.React 4h down at 60 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.73g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 92.6%.
Embodiment 9:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, 9.0 hydroxylamine chlorides are put into reactor, add 80ml ethanol and 20ml water, evenly stir.React 4h down at 60 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.66g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 91.2%.
Embodiment 10:
The first step, with the 4.0g para benzoquinone, 3.4g lime carbonate, 9.0 hydroxylamine chlorides are put into reactor, add 60ml ethanol and 20ml water, evenly stir.React 4h down at 60 ℃, after reaction is finished the product vacuum is revolved steaming and remove solvent.
Second step added 60ml water and 11.3g massfraction in the container of removing behind the solvent and is 36.5% hydrochloric acid, evenly stirred 5min, then with the product suction filtration, and washing, drying gets product 4.71g.Through efficient liquid phase chromatographic analysis, with the standard model comparison, product purity reaches more than 99%.The target product productive rate is 92.2%.
Claims (1)
1. the preparation method of a p-benzoqui(o)none dioxime is characterized in that comprising the steps:
The first step is 4: 3～4: 5.4 para benzoquinone of mass ratio and lime carbonate, and quality is that the hydroxylamine chloride of 2.50～2.75 times of para benzoquinone is put into reactor, adds ethanol 60ml～80ml, water 20ml, 60 ℃～70 ℃ of constant temperature, constant temperature time 4 hours;
Second step was revolved steaming with the first step reaction product in 50 ℃ of vacuum, after solvent evaporation finishes, added the 11.3g massfraction in the reactor and be 36.5% HCL and 60ml water, stirred suction filtration behind the 5min, will filter product water cleaning after drying, promptly get p-benzoqui(o)none dioxime.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100475405A CN101148422A (en) | 2007-10-29 | 2007-10-29 | Preparation for p-benzoquionone dioxime |
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| CNA2007100475405A CN101148422A (en) | 2007-10-29 | 2007-10-29 | Preparation for p-benzoquionone dioxime |
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| CNA2007100475405A Pending CN101148422A (en) | 2007-10-29 | 2007-10-29 | Preparation for p-benzoquionone dioxime |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712634B (en) * | 2008-10-08 | 2014-06-25 | 扬州庆凯高新材料厂 | Method for preparing parabenzoquinone dioxime |
| CN114787122A (en) * | 2019-08-13 | 2022-07-22 | 威娜德国有限责任公司 | Novel polycondensation synthesis of 2-methoxymethyl-p-phenylenediamine |
| CN116082187A (en) * | 2023-01-04 | 2023-05-09 | 江苏华星新材料科技股份有限公司 | Dibenzoyl 1, 4-naphthoquinone dioxime compound and preparation method and application thereof |
-
2007
- 2007-10-29 CN CNA2007100475405A patent/CN101148422A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712634B (en) * | 2008-10-08 | 2014-06-25 | 扬州庆凯高新材料厂 | Method for preparing parabenzoquinone dioxime |
| CN114787122A (en) * | 2019-08-13 | 2022-07-22 | 威娜德国有限责任公司 | Novel polycondensation synthesis of 2-methoxymethyl-p-phenylenediamine |
| CN116082187A (en) * | 2023-01-04 | 2023-05-09 | 江苏华星新材料科技股份有限公司 | Dibenzoyl 1, 4-naphthoquinone dioxime compound and preparation method and application thereof |
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Open date: 20080326 |