CN102643224B - Preparation method of light stabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine - Google Patents
Preparation method of light stabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine Download PDFInfo
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- CN102643224B CN102643224B CN201210147065.XA CN201210147065A CN102643224B CN 102643224 B CN102643224 B CN 102643224B CN 201210147065 A CN201210147065 A CN 201210147065A CN 102643224 B CN102643224 B CN 102643224B
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Abstract
The invention discloses a preparation method of a light stabilizer and an intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine. 4-allyloxy-1,2,2,6,6-pentamethylpiperidine and an oxidant, which are used as raw materials, react in the presence of a catalyst and a solvent to obtain the light stabilizer and the intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine. Since the 4-allyloxy-1,2,2,6,6-pentamethylpiperidine and the oxidant are used as the raw materials to synthesize the light stabilizer and the intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine, the invention has the advantages of simple separation and purification process, short reaction time, high product yield and low cost, and is an ideal technique for implementing industrialized production; and the product yield is up to more than 95%.
Description
Technical field
The present invention relates to a kind of photostabilizer and intermediate 4-acetonyl-1, the preparation method of 2,2,6,6-pentamethyl-piperidines.
Background technology
Photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines is novel hindered amine light stabilizer, can extend the duration of service that various plastic cement and coating irradiate out of doors.In use, the course of processing, can not produce smell with polymer, can not affect the original color of material yet.Also can be used as the intermediate of photostabilizer, the compound containing the structure of hindered amine that can synthetic macromolecule amount.4-acetonyl-1,2,2,6,6-pentamethyl-piperidines and most industry solvent phase dissolubility are good, have superior polymer intermiscibility, in order to prevent the destruction of UV-light, with photostabilizer, solve the degradation problem under sun exposure.Concerning the polymkeric substance of most of easy photodegradations, hindered amine light stabilizer is a kind of efficient stablizer.Due to the regeneration feature of photostabilizer and the low-molecular-weight stablizer feature of typicalness, make hindered amines stablizer can there is the light and heat stability of long duration, can be used for the plastics such as polyethylene, polypropylene, polyoxymethylene, its light stabilising effect is good.Its molecular formula is C
13h
25nO
2, molecular weight: 227.38, molecular structural formula:
Due to raw material 4-allyloxy-1 adopting, 2,2,6,6-pentamethyl-piperidines is slightly soluble in water, contains two keys oxidizing reaction easily occurs in molecule.Photostabilizer and intermediate 4-acetonyl-1, the synthetic method of 2,2,6,6-pentamethyl-piperidines is 4-allyloxy-1 under the existence of catalysts and solvents, 2,2,6,6-pentamethyl-piperidines and oxygenant carry out two key oxidizing reactions, synthetic 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.
Summary of the invention
The object of the present invention is to provide photostabilizer and intermediate 4-acetonyl-1 that a kind of product yield is high, the preparation method of 2,2,6,6-pentamethyl-piperidines.
Technical solution of the present invention is:
A kind of photostabilizer and intermediate 4-acetonyl-1,2,2, the preparation method of 6,6-pentamethyl-piperidines, present method adopts 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines, oxygenant are raw material, 4-allyloxy-1 under the existence of catalysts and solvents, 2,2,6,6-pentamethyl-piperidines and oxygenant carry out oxidizing reaction, after reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filter, crude product carries out recrystallization with dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Described oxygenant is oxygen or ozone, preferably oxygen; Described catalyzer is palladium or Cobaltous diacetate or manganese acetate, preferably palladium; Described solvent is acetic acid or propionic acid, preferably acetic acid; Described oxidizing reaction temperature is 85-110 ℃, and oxidation time is 8-15h.。
4-allyloxy-1,2,2,6, the usage ratio of 6-pentamethyl-piperidines, oxygenant, catalyzer, solvent, dehydrated alcohol is by mass: 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines: oxygenant: catalyzer: solvent: dehydrated alcohol=1:0.38-1.25:0.05-0.25:1.90-3.32:2.03-4.05.
The present invention compared with prior art has the following advantages: the present invention uses 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines, oxygenant are the synthetic photostabilizer of raw material and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines, separating-purifying process is simple, and the reaction times is short, and product yield is high, reach more than 95%, less energy consumption, cost is low, is the comparatively ideal technique that realizes suitability for industrialized production.
embodiment:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and the following example only, for explaining the present invention, does not form limiting the scope of the present invention.
A kind of photostabilizer and intermediate 4-acetonyl-1,2,2, the preparation method of 6,6-pentamethyl-piperidines, present method adopts 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines, oxygenant are raw material, 4-allyloxy-1 under the existence of catalysts and solvents, 2,2,6,6-pentamethyl-piperidines and oxygenant carry out oxidizing reaction, after reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filter, the crude product after filtration carries out recrystallization with dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Described oxygenant is oxygen or ozone, preferably oxygen; Described catalyzer is palladium or Cobaltous diacetate or manganese acetate, preferably palladium; Described solvent is acetic acid or propionic acid, preferably acetic acid; Described oxidizing reaction temperature is 85-110 ℃, oxidation time is 8-15h, wherein, and 4-allyloxy-1,2, the usage ratio of 2,6,6-pentamethyl-piperidines, oxygenant, catalyzer, solvent, dehydrated alcohol is by mass: 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines: oxygenant: catalyzer: solvent: dehydrated alcohol=1:0.38-1.25:0.05-0.25:1.90-3.32:2.03-4.05.
Embodiment 1:
Homemade Glass tubing (
mm) in reactor, add 50g solvent, water 15g, 4-allyloxy-1, 2, 2, 6, 6-pentamethyl-piperidines 42.2g, catalyzer 2g, by reactor bottom, pass into oxygen, make the mixture in Glass tubing carry out oxidizing reaction, control oxygen flow is 895mL/h, control oxidizing reaction temperature is 85-110 ℃, oxidation time is 8-15h, after oxidizing reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filter, crude product after filtration carries out recrystallization with 50g dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1, 2, 2, 6, 6-pentamethyl-piperidines, product yield is 95.68%.
Embodiment 2:
Homemade Glass tubing (
mm) in reactor, add 60g solvent, water 15g, 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines 42.2g, catalyzer 3g, by reactor bottom, pass into oxygen, make the mixture in Glass tubing carry out oxidizing reaction, control oxygen flow is 1.12L/h, control temperature of reaction is 85-110 ℃, and the reaction times is 8-15h.After oxidizing reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filters, and the crude product after filtration carries out recrystallization with 60g dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Product yield is 95.81%.
Embodiment 3:
Homemade Glass tubing (
mm) in reactor, add 50g solvent, water 15g, 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines 42.2g, catalyzer 4g, by reactor bottom, pass into oxygen, make the mixture in Glass tubing carry out oxidizing reaction, control oxygen flow is 560mL/h, control temperature of reaction is 85-110 ℃, and the reaction times is 8-15h.After oxidizing reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filters, and the crude product after filtration carries out recrystallization with 70g dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Product yield is 95.12%.
Embodiment 4:
Homemade Glass tubing (
mm) in reactor, add 40g solvent, water 15g, 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines 42.2g, catalyzer 1.5g, by reactor bottom, pass into oxygen, make the mixture in Glass tubing carry out oxidizing reaction, control oxygen flow is 750mL/h, control temperature of reaction is 85-110 ℃, and the reaction times is 8-15h.After oxidizing reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filters, and the crude product after filtration carries out recrystallization with 55g dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Product yield is 95.33%.
Embodiment 5:
Homemade Glass tubing (
mm) in reactor, add 40g solvent, water 15g, 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines 42.2g, catalyzer 5g, by reactor bottom, pass into oxygen, make the mixture in Glass tubing carry out oxidizing reaction, control oxygen flow is 1.12L/h, control temperature of reaction is 85-110 ℃, and the reaction times is 8-15h.After oxidizing reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filters, and the crude product after filtration carries out recrystallization with 40g dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines.Product yield is 96.17%.
The present invention uses 4-allyloxy-1,2,2,6,6-pentamethyl-piperidines, oxygenant are the synthetic photostabilizer of raw material and intermediate 4-acetonyl-1,2,2,6,6-pentamethyl-piperidines, separating-purifying process is simple, and the reaction times is short, and product yield is high, reach more than 95%, less energy consumption, cost is low, is the comparatively ideal technique that realizes suitability for industrialized production.
Claims (1)
1. a photostabilizer and intermediate 4-acetonyl-1, 2, 2, 6, the preparation method of 6-pentamethyl-piperidines, it is characterized in that: adopt 4-allyloxy-1, 2, 2, 6, 6-pentamethyl-piperidines, oxygenant is raw material, 4-allyloxy-1, 2, 2, 6, 6-pentamethyl-piperidines, oxygenant, catalyzer, solvent, the usage ratio of dehydrated alcohol is by mass: 4-allyloxy-1, 2, 2, 6, 6-pentamethyl-piperidines: oxygenant: catalyzer: solvent: dehydrated alcohol=1:0.38-1.25:0.05-0.25:1.90-3.32:2.03-4.05, described oxygenant is oxygen or ozone, described catalyzer is palladium or Cobaltous diacetate or manganese acetate, described solvent is acetic acid or propionic acid, under the existence of catalysts and solvents, carry out oxidizing reaction and prepare 4-acetonyl-1, 2, 2, 6, 6-pentamethyl-piperidines, the temperature of described oxidizing reaction is 85-110 ℃, oxidation time is 8-15h, after reaction finishes, filter, be cooled to 8-10 ℃, crystallization, filter, crude product after filtration carries out recrystallization with dehydrated alcohol, can obtain photostabilizer and intermediate 4-acetonyl-1, 2, 2, 6, 6-pentamethyl-piperidines.
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| CN115557935A (en) * | 2022-10-17 | 2023-01-03 | 南通大学 | Preparation method of hindered amine light stabilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101343248A (en) * | 2008-08-24 | 2009-01-14 | 浙江华海药业股份有限公司 | Fine purification method for key intermediate of Donepezil Hydrochloride |
| CN102001991A (en) * | 2010-11-12 | 2011-04-06 | 南通惠康国际企业有限公司 | Method for preparing light stabilizer (4-n-butoxy-2,2,6,6-tetramethylpiperidine) |
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| JP2002255873A (en) * | 2001-03-02 | 2002-09-11 | Showa Denko Kk | Method for producing carbonyl compound, method for producing alcohol compound using the carbonyl compound and method for producing diol compound using the alcohol compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101343248A (en) * | 2008-08-24 | 2009-01-14 | 浙江华海药业股份有限公司 | Fine purification method for key intermediate of Donepezil Hydrochloride |
| CN102001991A (en) * | 2010-11-12 | 2011-04-06 | 南通惠康国际企业有限公司 | Method for preparing light stabilizer (4-n-butoxy-2,2,6,6-tetramethylpiperidine) |
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