CN101948421A - Method for preparing polymerization inhibitor (4-benzoyl-2,2,6,6-tetramethylpiperidine-1-nitroxide free radical) - Google Patents
Method for preparing polymerization inhibitor (4-benzoyl-2,2,6,6-tetramethylpiperidine-1-nitroxide free radical) Download PDFInfo
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- CN101948421A CN101948421A CN 201010519438 CN201010519438A CN101948421A CN 101948421 A CN101948421 A CN 101948421A CN 201010519438 CN201010519438 CN 201010519438 CN 201010519438 A CN201010519438 A CN 201010519438A CN 101948421 A CN101948421 A CN 101948421A
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Abstract
The invention discloses a method for preparing a polymerization inhibitor (4-benzoyl-2,2,6,6-tetramethylpiperidine-1-nitroxide free radical). 4-benzoyl-2,2,6,6-tetramethylpiperidine and hydrogen peroxide are used as raw materials and reacted in the presence of a composite catalyst to obtain the 4-benzoyl-2,2,6,6-tetramethylpiperidine-1-nitroxide free radical. The method for synthesizing the 4-benzoyl-2,2,6,6-tetramethylpiperidine-1-nitroxide free radical by adopting the composite catalyst simplifies the separation and purification processes, has the advantages of short reaction time, high product yield which reaches over 91 percent of product yield, high product purity, low energy consumption, low environmental pollution and low cost, and is an ideal process for realizing industrialized production.
Description
Technical field
The present invention relates to the preparation method of a kind of stopper (4-benzoyl-2,2,6,6-tetramethyl piperidine-1-nitroxyl free radical).
Background technology
4-benzoyl-2; 2; 6; 6-tetramethyl piperidine-1-nitroxyl free radical is the free radical of recent a kind of novel stabilising of finding; because the nitrogen nitroxyl free radical is good to the polymerization inhibition performance of unsaturated compound; application development in unsaturated monomer compound production process is rapid in recent years to make it, so replace traditional phenolic inhibitor with hindered amines nitrogen compound oxygen radical of nitrogen very big practical significance is arranged.Can be applicable to the prevention polymerization fouling of low-carbon alkene, also can be applicable to compounds such as esters of acrylic acid, methyl acrylic ester and vinylformic acid, its polymerization inhibition performance is better than compound polymerization inhibition effects such as quinhydrones, hydroquinone monomethyl ether, phenothiazine and copper dibutyldithiocarbamate.Chemical name is a 4-benzoyl-2,2,6, the molecular formula of 6-tetramethyl piperidine-1-nitroxyl free radical: C
16H
23NO
3, molecular weight: 292.24, molecular structural formula:, physico-chemical property: outward appearance is the orange xln, fusing point: 104-105 ℃.4-benzoyl-2; 2; 6; 6-tetramethyl piperidine-existing synthetic method of 1-nitroxyl free radical is with methyl benzoate and 4-hydroxyl-2; 2,6,6-tetramethyl piperidine-1-nitroxyl free radical is a raw material; carry out transesterification reaction and get in the presence of sodium methylate or titanate ester compound, product yield is 74%.Because magnesium methylate and tetrabutyl titanate catalyzer have the water of chance facile hydrolysis, make the Ph value raising of system, transesterification reaction is had a negative impact shortcoming such as product yield is low.
Summary of the invention
The objective of the invention is in order to overcome above deficiency, the preparation method of a kind of product yield height, less energy consumption, environmental pollution is little, cost is low stopper (4-benzoyl-2,2,6,6-tetramethyl piperidine-1-nitroxyl free radical) is provided.
The present invention is achieved through the following technical solutions: a kind of stopper (4-benzoyl-2; 2; 6,6-tetramethyl piperidine-1-nitroxyl free radical) preparation method is with 4-benzoyl-2; 2; 6, the 6-tetramethyl piperidine; hydrogen peroxide is a raw material, carries out oxidizing reaction under the condition that composite catalyst exists; after reaction finishes; the sherwood oil that adds 60-90 ℃ of boiling range stirs; static, the aqueous solution of lower floor is put only; carry out reflux water-dividing then; cooling; crystallization; filter, promptly get the 4-benzoyl-2,2 of orange; 6,6-tetramethyl piperidine-1-nitroxyl free radical product.
Further improvement of the present invention is: composite catalyst is made up of sodium wolframate, quaternary ammonium salt and oxidation promotor, and its consumption mass ratio is a sodium wolframate: quaternary ammonium salt: oxidation promotor=1:0.25-1.75:0.01-0.15.
Further improvement of the present invention is: quaternary ammonium salt is 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide or cetyl trimethylammonium bromide or Dodecyl trimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.Quaternary ammonium salt is preferably cetyl trimethylammonium bromide or dodecyl benzyl dimethyl ammonium chloride or 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide.
Further improvement of the present invention is: oxidation promotor is water glass or Magnesium Silicate q-agent or tripoly phosphate sodium STPP and MgSO
4Compound or sal epsom and monoethanolamine phosphoric acid and picolinic acid three's mixture or Magnesium Stearate or phytic acid or diethylamine pentaacetic acid or glucose and hydroxyethanoic acid and stearic composite compound or polyacrylamide fatty acid magnesium salt.The compound of optimization polypropylene acid amides fatty acid magnesium salt or tripoly phosphate sodium STPP and MgSO4 or sal epsom and monoethanolamine phosphoric acid and picolinic acid three's mixture.
Further improvement of the present invention is: 4-benzoyl-2,2,6, the usage ratio of 6-tetramethyl piperidine, hydrogen peroxide, composite catalyst is by mass: 1:0.20-0.65:0.01-0.1.
Further improvement of the present invention is: the temperature of oxidizing reaction is 50-65 ℃, and the time of oxidizing reaction is 8-16h.
The present invention compared with prior art has the following advantages: in order to overcome above-mentioned shortcoming, we have found a kind of 4-benzoyl-2,2,6, the new synthetic method of 6-tetramethyl piperidine-1-compound oxygen radical of nitrogen.Adopt complex catalyst system, in ethanolic soln, use hydrogen peroxide oxidation 4-benzoyl-2,2; 6, the 6-tetramethyl piperidine synthesizes 4-benzoyl-2,2; 6,6-tetramethyl piperidine-1-nitroxyl free radical, the catalyst system of this method has high reactivity and highly selective; speed of response is fast; the few product yield height of consumption, chemical stability is good, and aftertreatment is simple; etching apparatus not, low cost and other advantages.The present invention adopts composite catalyst to synthesize 4-benzoyl-2,2,6; 6-tetramethyl piperidine-1-nitroxyl free radical; simplified the separation purification process, the reaction times is moderate, the product yield height; the yield of product is reached more than 91%; it is higher to obtain product purity, less energy consumption, and environmental pollution is little; cost is low, is the comparatively ideal technology that realizes suitability for industrialized production.
Embodiment:
In order to deepen the understanding of the present invention, the invention will be further described below in conjunction with embodiment, and following examples only are used to explain the present invention, do not constitute the qualification to protection domain of the present invention.
Stopper (4-benzoyl-2,2,6,6-tetramethyl piperidine-1-nitroxyl free radical) preparation method, be with 4-benzoyl-2,2,6, the 6-tetramethyl piperidine, hydrogen peroxide is a raw material, under the condition that composite catalyst exists, carry out oxidizing reaction, 4-benzoyl-2,2,6, the 6-tetramethyl piperidine, hydrogen peroxide, the usage ratio of composite catalyst is by mass: 1:0.20-0.65:0.01-0.1, composite catalyst are by sodium wolframate, quaternary ammonium salt and oxidation promotor are formed, its consumption mass ratio is a sodium wolframate: quaternary ammonium salt: oxidation promotor=1:0.25-1.75:0.01-0.15, wherein, quaternary ammonium salt is 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide or cetyl trimethylammonium bromide or Dodecyl trimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride, preferred cetyl trimethylammonium bromide, dodecyl benzyl dimethyl ammonium chloride, 4-propyl bromide, the tetra isopropyl brometo de amonio, Tetrabutyl amonium bromide; Oxidation promotor is the compound of water glass or Magnesium Silicate q-agent or tripoly phosphate sodium STPP and MgSO4 or sal epsom and monoethanolamine phosphoric acid and picolinic acid three's mixture or Magnesium Stearate or phytic acid or diethylamine pentaacetic acid or glucose and hydroxyethanoic acid and stearic composite compound or polyacrylamide fatty acid magnesium salt, the compound of optimization polypropylene acid amides fatty acid magnesium salt or tripoly phosphate sodium STPP and MgSO4 or sal epsom and monoethanolamine phosphoric acid and picolinic acid three's mixture.The temperature of oxidizing reaction is 50-65 ℃; the 8-16h afterreaction finishes; the sherwood oil that adds 60-90 ℃ of boiling range stirs staticly, and the aqueous solution of lower floor is put only; carry out reflux water-dividing then; cooling, crystallization, filtration promptly get the 4-benzoyl-2,2 of orange; 6,6-tetramethyl piperidine-1-nitroxyl free radical product.
Embodiment 1:
In the four-hole reaction flask of electric mixer, reflux exchanger and thermometer is housed; the 4-benzoyl-2 that adds 27.7g successively; 2; 6, the hydrogen peroxide of 6-tetramethyl piperidine, 28.3g, the composite catalyst of 1g are loaded onto reflux condensing tube, thermometer; start agitator; when being warming up to 50-65 ℃, pick up counting reaction times 10h (using the gas-chromatography monitoring reaction).After reaction finishes, add the sherwood oil of 60-90 ℃ of boiling range, stir, static, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, cooling, crystallization, filtration promptly get the 4-benzoyl-2,2,6 of orange, 6-tetramethyl piperidine-1-nitroxyl free radical product.Yield reaches 91.63%, and fusing point is 104-105 ℃.
Embodiment 2:
In the four-hole reaction flask of electric mixer, reflux exchanger and thermometer is housed; the 4-benzoyl-2 that adds 27.7g successively; 2; 6, the hydrogen peroxide of 6-tetramethyl piperidine, 39.7g, the composite catalyst of 1g are loaded onto reflux condensing tube, thermometer; start agitator; when being warming up to 50-65 ℃, pick up counting reaction times 10h (using the gas-chromatography monitoring reaction).After reaction finishes, add the sherwood oil of 60-90 ℃ of boiling range, stir, static, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, cooling, crystallization, filtration promptly get the 4-benzoyl-2,2,6 of orange, 6-tetramethyl piperidine-1-nitroxyl free radical product.Yield reaches 91.95%, and fusing point is 104-105 ℃.
Embodiment 3:
In the four-hole reaction flask of electric mixer, reflux exchanger and thermometer is housed; the 4-benzoyl-2 that adds 27.7g successively; 2; 6, the hydrogen peroxide of 6-tetramethyl piperidine, 28.3g, the composite catalyst of 1.5g are loaded onto reflux condensing tube, thermometer; start agitator; when being warming up to 50-65 ℃, pick up counting reaction times 10h (using the gas-chromatography monitoring reaction).After reaction finishes, add the sherwood oil of 60-90 ℃ of boiling range, stir, static, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, cooling, crystallization, filtration promptly get the 4-benzoyl-2,2,6 of orange, 6-tetramethyl piperidine-1-nitroxyl free radical product.Yield reaches 92.01%, and fusing point is 104-105 ℃.
Embodiment 4:
In the four-hole reaction flask of electric mixer, reflux exchanger and thermometer is housed; the 4-benzoyl-2 that adds 27.7g successively; 2; 6, the hydrogen peroxide of 6-tetramethyl piperidine, 28.3g, the composite catalyst of 1g are loaded onto reflux condensing tube, thermometer; start agitator; when being warming up to 50-65 ℃, pick up counting reaction times 11h (using the gas-chromatography monitoring reaction).After reaction finishes, add the sherwood oil of 60-90 ℃ of boiling range, stir, static, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, cooling, crystallization, filtration promptly get the 4-benzoyl-2,2,6 of orange, 6-tetramethyl piperidine-1-nitroxyl free radical product.Yield reaches 92.12%, and fusing point is 104-105 ℃.
Embodiment 5:
In the four-hole reaction flask of electric mixer, reflux exchanger and thermometer is housed; the 4-benzoyl-2 that adds 27.7g successively; 2; 6, the hydrogen peroxide of 6-tetramethyl piperidine, 28.3g, the composite catalyst of 1g are loaded onto reflux condensing tube, thermometer; start agitator; when being warming up to 50-65 ℃, pick up counting reaction times 12h (using the gas-chromatography monitoring reaction).After reaction finishes, add the sherwood oil of 60-90 ℃ of boiling range, stir, static, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, cooling, crystallization, filtration promptly get the 4-benzoyl-2,2,6 of orange, 6-tetramethyl piperidine-1-nitroxyl free radical product.Yield reaches 92.94%, and fusing point is 104-105 ℃.
Claims (7)
1. stopper (4-benzoyl-2; 2; 6,6-tetramethyl piperidine-1-nitroxyl free radical) preparation method is characterized in that: be with 4-benzoyl-2; 2; 6,6-tetramethyl piperidine, hydrogen peroxide are raw material, carry out oxidizing reaction under the condition that composite catalyst exists; after reaction finishes; the sherwood oil that adds 60-90 ℃ of boiling range, stirring, static is put the aqueous solution of lower floor only; carry out reflux water-dividing then; cooling, crystallization, filtration promptly get the 4-benzoyl-2,2 of orange; 6,6-tetramethyl piperidine-1-nitroxyl free radical product.
2. according to the described stopper of claim 1 (4-benzoyl-2; 2; 6; 6-tetramethyl piperidine-1-nitroxyl free radical) preparation method; it is characterized in that: selected composite catalyst is made up of sodium wolframate, quaternary ammonium salt and oxidation promotor, and its consumption mass ratio is a sodium wolframate: quaternary ammonium salt: oxidation promotor=1:0.25-1.75:0.01-0.15.
3. according to the described stopper of claim 2 (4-benzoyl-2; 2; 6; 6-tetramethyl piperidine-1-nitroxyl free radical) preparation method is characterized in that: described quaternary ammonium salt is 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide or cetyl trimethylammonium bromide or Dodecyl trimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.
4. according to claim 1 or 2 described stopper (4-benzoyls-2; 2; 6; 6-tetramethyl piperidine-1-nitroxyl free radical) preparation method is characterized in that: described oxidation promotor is the compound of water glass or Magnesium Silicate q-agent or tripoly phosphate sodium STPP and MgSO4 or sal epsom and monoethanolamine phosphoric acid and picolinic acid three's mixture or Magnesium Stearate or phytic acid or diethylamine pentaacetic acid or glucose and hydroxyethanoic acid and stearic composite compound or polyacrylamide fatty acid magnesium salt.
5. according to the described stopper of claim 4 (4-benzoyl-2; 2; 6; 6-tetramethyl piperidine-1-nitroxyl free radical) preparation method; it is characterized in that: described 4-benzoyl-2; 2,6, the usage ratio of 6-tetramethyl piperidine, hydrogen peroxide, composite catalyst is by mass: 1:0.20-0.65:0.01-0.1.
6. according to the preparation method of the described stopper of claim 5 (4-benzoyl-2,2,6,6-tetramethyl piperidine-1-nitroxyl free radical), it is characterized in that: the temperature of described oxidizing reaction is 50-65 ℃.
7. according to the preparation method of the described stopper of claim 5 (4-benzoyl-2,2,6,6-tetramethyl piperidine-1-nitroxyl free radical), it is characterized in that: the time of described oxidizing reaction is 8-16h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN103524402A (en) * | 2012-07-06 | 2014-01-22 | 上海友豪化工有限公司 | Preparation method of efficient stable inhibitor |
| CN108914549A (en) * | 2018-06-23 | 2018-11-30 | 浙江滨康印染有限公司 | A kind of Alkali Weight Reduction Treatment of Polyester processing method |
| WO2022127410A1 (en) * | 2020-12-17 | 2022-06-23 | 上海华谊新材料有限公司 | Catalyst, preparation method therefor, and use thereof in preparation of 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544598A (en) * | 2009-05-06 | 2009-09-30 | 南通大学 | Diester sebacate (2,2,6,6-tetramethyl-4-hydroxypiperidine) nitroxide radical of high-efficiency polymerization inhibitor and production method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544598A (en) * | 2009-05-06 | 2009-09-30 | 南通大学 | Diester sebacate (2,2,6,6-tetramethyl-4-hydroxypiperidine) nitroxide radical of high-efficiency polymerization inhibitor and production method thereof |
Non-Patent Citations (2)
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| 《印染》 19991231 黄茂福 略论双氧水漂白稳定剂(一) 45-49 4-7 , 第1期 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN103524402A (en) * | 2012-07-06 | 2014-01-22 | 上海友豪化工有限公司 | Preparation method of efficient stable inhibitor |
| CN108914549A (en) * | 2018-06-23 | 2018-11-30 | 浙江滨康印染有限公司 | A kind of Alkali Weight Reduction Treatment of Polyester processing method |
| WO2022127410A1 (en) * | 2020-12-17 | 2022-06-23 | 上海华谊新材料有限公司 | Catalyst, preparation method therefor, and use thereof in preparation of 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy |
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