CN101691352A - Efficient polymerization inhibitor 2,2,6,6-tetramethyl-4-hydroxy piperidine nitroxides and production method thereof - Google Patents
Efficient polymerization inhibitor 2,2,6,6-tetramethyl-4-hydroxy piperidine nitroxides and production method thereof Download PDFInfo
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- CN101691352A CN101691352A CN200910036231A CN200910036231A CN101691352A CN 101691352 A CN101691352 A CN 101691352A CN 200910036231 A CN200910036231 A CN 200910036231A CN 200910036231 A CN200910036231 A CN 200910036231A CN 101691352 A CN101691352 A CN 101691352A
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- hydroxy piperidine
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Abstract
The invention discloses efficient polymerization inhibitor 2,2,6,6-tetramethyl-4-hydroxy piperidine nitroxides and a production method thereof. The efficient polymerization inhibitor 2,2,6,6-tetramethyl-4-hydroxy piperidine nitroxides are prepared by taking 2,2,6,6-tetramethyl-4-hydroxy piperidine and 35% hydrogen peroxide as raw materials and reacting with existence of catalyst; the catalyst is a mixture of sodiumtungstate, oxidation accelerator and ethylene diamine tetraacetic acid (EDTA) with the mass ratio being 1:0.1-1.0:0.01-0.1. The invention adopts 35% hydrogen peroxide as oxidant to synthesize 2,2,6,6-tetramethyl-4-hydroxy piperidine nitroxides and uses a novel compound catalyst, thus simplifying separation and purification processes, having short reaction time and high yield which is over 96%, higher purity, less energy consumption, little environment pollution and low cost, and is a relatively ideal technique for realizing industrialized production.
Description
Technical field:
The present invention relates to a kind of high-efficiency polymerization inhibitor 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical and production method thereof.
Background technology:
2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is the free radical of recent a kind of novel stabilising of finding, widespread use on its resonable spin labeling of touching upon is noticeable, 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is very stable to photo-thermal, can stop oxidative chain, so can serve as the antiaging agent of macromolecular material, the thermal destruction inhibitor of efficient ultraviolet absorbers and poly-formyl, polyvinylamine.Because 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 the hindered amines 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.Its chemical name is: 2,2,6, and 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical
Molecular formula: C
9H
18O
2N; Molecular weight: 172.25
Molecular structural formula:
Physico-chemical property: outward appearance is the orange xln, fusing point mp:68-70 ℃.
At present, preparation 2,2,6, the method for 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is to be catalyzer with the magnesium hydroxide, 2,2,6,6-tetramethyl--4-hydroxy piperidine and hydrogen peroxide oxidation react and get.Because the magnesium hydroxide catalyzer is slightly soluble in water, makes to be reflected under the heterogeneous state and carries out, and is unfavorable for 2,2,6, the oxidizing reaction of 6-tetramethyl--4-hydroxy piperidine, product yield is lower.
Summary of the invention:
The object of the present invention is to provide the high high-efficiency polymerization inhibitor of a kind of product yield 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical and production method thereof.
Technical solution of the present invention is:
A kind of high-efficiency polymerization inhibitor 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical and production method thereof, it is characterized in that: be with 2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide are raw material, reaction makes 2 under the condition that catalyzer exists, 2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical; Described catalyzer is the mixture of sodium wolframate, oxidation promotor, disodium ethylene diamine tetraacetate, and three's mass ratio is: sodium wolframate: oxidation promotor: disodium ethylene diamine tetraacetate=1: 0.1～1.0: 0.01～0.1.
2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide, catalyst consumption ratio are by mass: 2,2,6, and 6-tetramethyl--4-hydroxy piperidine: 30～35% hydrogen peroxide: catalyzer=1: 0.9～1.9: 0.01～0.5.
With 2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide are raw material, under the condition that catalyzer exists, react, and be 55-60 ℃ with the temperature of reaction, the reaction times is 7h, insulation 2h after reaction finishes, adds sherwood oil, tells organic layer; Dewater in the solution after telling organic layer, the organic layer that obtains lower the temperature cooling, crystallization, filter 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical.Described the present invention is the oxygenant Synthetic 2 with 30～35% hydrogen peroxide, 2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical adopts a kind of novel composite catalyst, has simplified the separation purification process, reaction times is short, the product yield height reaches more than 96% the yield of product, and it is higher to obtain product purity, less energy consumption, environmental pollution is little, and cost is low, is the comparatively ideal technology that realizes suitability for industrialized production.
The invention will be further described below in conjunction with embodiment:
Embodiment:
Embodiment 1:
In that being housed, temperature takes into account in the four-hole boiling flask of reflux condensing tube, add 2,2,6,6-tetramethyl--4-hydroxy piperidine 15.7g (0.1mol) and a certain amount of water solvent, composite catalyst 0.3g, begin heating and start induction stirring in electric mantle, wherein composite catalyst is the mixture of sodium wolframate, oxidation promotor, disodium ethylene diamine tetraacetate, and three's mass ratio is: sodium wolframate: oxidation promotor: disodium ethylene diamine tetraacetate=1: 0.1～1.0: 0.01～0.1.Electric mantle is transferred to specified Heating temperature pick up counting, the hydrogen peroxide 19.4g (0.2mol) of Dropwise 35 % in 7h is incubated 2h down at 55-60 ℃, stopped reaction also is cooled to 35 ℃, and adding 12g boiling range is 90-120 ℃ a sherwood oil, stirs 20min, static 20min is put the aqueous solution of lower floor only, carries out reflux water-dividing then, divide water to finish back cooling, crystallization, filtration, promptly get 2,2,6 of orange, 6-tetramethyl piperidine nitrogen oxygen free radical product, product yield are 96.36%.
Embodiment 2:
In that being housed, temperature takes into account in the four-hole boiling flask of reflux condensing tube, add 2,2,6,6-tetramethyl--4-hydroxy piperidine 15.7g (0.1mol) and a certain amount of water solvent, composite catalyst 0.35g, the composition of this catalyzer and the proportion of each composition are with embodiment 1, in electric mantle, begin heating and start induction stirring, electric mantle is transferred to specified Heating temperature pick up counting, the hydrogen peroxide 19.4g (0.2mol) of Dropwise 35 % in 7h is incubated 2h down at 55-60 ℃, stopped reaction also is cooled to 35 ℃, adding 12g boiling range is 90-120 ℃ a sherwood oil, stirs 20min, static 20min, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, divide water to finish the back cooling, crystallization, filter, promptly get 2 of orange, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical product, product yield are 97.12%.
Embodiment 3:
In that being housed, temperature takes into account in the four-hole boiling flask of reflux condensing tube, add 2,2,6,6-tetramethyl--4-hydroxy piperidine 15.7g (0.1mol) and a certain amount of water solvent, composite catalyst 0.3g, the composition of this catalyzer and the proportion of each composition are with embodiment 1, in electric mantle, begin heating and start induction stirring, electric mantle is transferred to specified Heating temperature pick up counting, the hydrogen peroxide 24.28g (0.25mol) of Dropwise 35 % in 7h is incubated 2h down at 55-60 ℃, stopped reaction also is cooled to 35 ℃, adding 12g boiling range is 90-120 ℃ a sherwood oil, stirs 20min, static 20min, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, divide water to finish the back cooling, crystallization, filter, promptly get 2 of orange, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical product, product yield are 96.94%.
Embodiment 4:
In that being housed, temperature takes into account in the four-hole boiling flask of reflux condensing tube, add 2,2,6,6-tetramethyl--4-hydroxy piperidine 15.7g (0.1mol) and a certain amount of water solvent, composite catalyst 0.3g, the composition of this catalyzer and the proportion of each composition are with embodiment 1, in electric mantle, begin heating and start induction stirring, electric mantle is transferred to specified Heating temperature pick up counting, the hydrogen peroxide 17.48g (0.18mol) of Dropwise 35 % in 7h is incubated 2h down at 55-60 ℃, stopped reaction also is cooled to 35 ℃, adding 12g boiling range is 90-120 ℃ a sherwood oil, stirs 20min, static 20min, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, divide water to finish the back cooling, crystallization, filter, promptly get 2 of orange, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical product, product yield are 96.56%.
Embodiment 5:
In that being housed, temperature takes into account in the four-hole boiling flask of reflux condensing tube, add 2,2,6,6-tetramethyl--4-hydroxy piperidine 15.7g (0.1mol) and a certain amount of water solvent, composite catalyst 0.3g, the composition of this catalyzer and the proportion of each composition are with embodiment 1, in electric mantle, begin heating and start induction stirring, electric mantle is transferred to specified Heating temperature pick up counting, the hydrogen peroxide 29.14g (0.3mol) of Dropwise 35 % in 7h is incubated 2h down at 55-60 ℃, stopped reaction also is cooled to 35 ℃, adding 12g boiling range is 90-120 ℃ a sherwood oil, stirs 20min, static 20min, the aqueous solution of lower floor is put only, carry out reflux water-dividing then, divide water to finish the back cooling, crystallization, filter, promptly get 2 of orange, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical product, product yield are 97.37%.
Claims (7)
1. high-efficiency polymerization inhibitor 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical, it is characterized in that: be with 2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide are raw material, and reaction makes 2,2 under the condition that catalyzer exists, 6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical, described catalyzer is the mixture of sodium wolframate, oxidation promotor, disodium ethylene diamine tetraacetate, and three's mass ratio is: sodium wolframate: oxidation promotor: disodium ethylene diamine tetraacetate=1: 0.1～1.0: 0.01～0.1.
2. high-efficiency polymerization inhibitor 2 according to claim 1,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: 2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide, catalyst consumption ratio are by mass: 2,2,6,6-tetramethyl--4-hydroxy piperidine: 30～35% hydrogen peroxide: catalyzer=1: 0.9～1.9: 0.01～0.5.
3. high-efficiency polymerization inhibitor 2,2,6, the production method of 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: with 2,2,6,6-tetramethyl--4-hydroxy piperidine, 30～35% hydrogen peroxide are raw material, react under the condition that catalyzer exists, described catalyzer is the mixture of sodium wolframate, oxidation promotor, disodium ethylene diamine tetraacetate, after reaction finishes, add sherwood oil, tell organic layer, dewater in the solution after telling organic layer, the organic layer that obtains lower the temperature cooling, crystallization, filter 2,2,6,6-tetramethyl--4-hydroxy piperidine nitroxyl free radical.
4. high-efficiency polymerization inhibitor 2,2,6 according to claim 3, the production method of 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: described 2,2,6,6-tetramethyl--4-hydroxy piperidine: 30～35% hydrogen peroxide: catalyzer=1: 0.9～1.9: 0.01～0.5.
5. according to claim 3 or 4 described high-efficiency polymerization inhibitors 2,2,6, the production method of 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: described sodium wolframate: oxidation promotor: disodium ethylene diamine tetraacetate=1: 0.1～1.0: 0.01～0.1.
6. according to each described high-efficiency polymerization inhibitor 2,2,6 of claim 3-5, the production method of 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: the temperature of described reaction is 55-60 ℃, and the reaction times is 7h, insulation 2h.
7. high-efficiency polymerization inhibitor 2,2,6 according to claim 3, the production method of 6-tetramethyl--4-hydroxy piperidine nitroxyl free radical is characterized in that: after reaction finished, adding 12g boiling range was 90-120 ℃ a sherwood oil, stirs 20min, static 20min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN108569996A (en) * | 2017-12-29 | 2018-09-25 | 江苏富比亚化学品有限公司 | A kind of synthetic method of high-efficiency polymerization inhibitor 701 |
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2009
- 2009-10-10 CN CN200910036231A patent/CN101691352A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102049248B (en) * | 2010-11-23 | 2012-12-19 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN108569996A (en) * | 2017-12-29 | 2018-09-25 | 江苏富比亚化学品有限公司 | A kind of synthetic method of high-efficiency polymerization inhibitor 701 |
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