CN107674017A - The synthetic method of the piperidine alcohols of 1,2,2,6,6 pentamethyl of light stabilizer intermediate 4 - Google Patents
The synthetic method of the piperidine alcohols of 1,2,2,6,6 pentamethyl of light stabilizer intermediate 4 Download PDFInfo
- Publication number
- CN107674017A CN107674017A CN201711015303.0A CN201711015303A CN107674017A CN 107674017 A CN107674017 A CN 107674017A CN 201711015303 A CN201711015303 A CN 201711015303A CN 107674017 A CN107674017 A CN 107674017A
- Authority
- CN
- China
- Prior art keywords
- piperidine alcohols
- reaction
- pentamethyl
- light stabilizer
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
Abstract
The present invention provides a kind of light stabilizer intermediate 1,2,2, the synthetic method of the piperidine alcohols of 6,6 pentamethyl 4, and in particular to light stabilizer preparing technical field, including two-step reaction, the first step, by 2,2,6, the piperidine alcohols of 6 tetramethyl 4 are mixed to join in solvent by a certain percentage with paraformaldehyde, under normal pressure, under certain reaction temperature, stir certain time, make 2,2,6, the reaction of the piperidine alcohols of 6 tetramethyl 4 is complete, room temperature is cooled to, excessive paraformaldehyde is filtered to remove, obtains methylolation product；Second step, reduced form solid catalyst is fitted into fixed bed reactors, above-mentioned reaction solution is added into solvent, fixed bed reactors are continually fed into certain charging rate, and it is passed through hydrogen, heating, reaction solution continue to flow out from fixed bed reactors lower end, and the reaction solution of outflow obtains through cooling, gas-liquid separation, liquid filtering, filtrate steaming removal solvent and after purification target product.The present invention prepares easy, economic and environment-friendly, product quality height, high income, suitable industrialized production.
Description
Technical field
The invention belongs to light stabilizer preparing technical field, and in particular to a kind of light stabilizer intermediate 1,2,2,6,6- five
The synthetic method of methyl -4- piperidine alcohols.
Background technology
Hindered amine light stabilizer (HALS) is the high-molecular organic material auxiliary agent of a kind of light, good heat stability, this kind of
The compatibilities of polymeric additive and most polymer is good, light stability is excellent, thus always domestic and international light is steady
Determine one of focus of agent research and development, 1,2,2,6,6- pentamethyl -4- piperidine alcohols are the main of biosynthesis block amine light stabilizer
Intermediate, with the continuous development of hindered amine light stabilizer application field, the demand of pentamethvl alcohol is gradually increased.
At present, the method for the pentamethyl -4- piperidine alcohols of synthesis 1,2,2,6,6- of report is disclosed in the world typically by each
Kind mode methylates to 2,2,6,6- tetramethyl -4- piperidine alcohols.US3364220(A)、EP0837057(A1)、
WO2004072035 (A1) etc. discloses the method reacted using Eschweiler-Clarke and carry out N-methyl, tetramethyl piperazine
Pyridine alcohol reacts with formaldehyde in the presence of formic acid, and wherein formic acid serves as reducing agent and is converted into CO2, this method is more common at present
Industrial process, can reach higher yield and higher product quality, but can be used in reaction and last handling process
Substantial amounts of bronsted lowry acids and bases bronsted lowry so that a large amount of waste water can be produced in production process, seriously pollute environment, then CN105820108 (A) is open
Face the method that hydrogen method prepares by tetramethylpiperidinol pentamethvl alcohol with formaldehyde, although this method avoids making for formic acid
With, but noble metal catalyst has been used, increase production cost, and conversion ratio fails to reach 100%, due to tetramethylpiperidinol
Approached with the boiling point of pentamethvl alcohol, certain difficulty is brought to final products purification, and easily influence the quality of product, this
Outside, CN101198604 (A) discloses the method to be methylated using iodomethane, but the price of iodomethane is higher, increases greatly
Production cost is added, and the alkali for being also required to add monovalent in reacting reacts to be quenched so that there is a certain amount of waste water to generate, cause
Environmental pollution.
Therefore, it is badly in need of one kind and prepares simplicity, economic and environment-friendly, product quality is high, high income, is adapted to the light of industrialized production steady
Determine the synthetic method of agent intermediate 1,2,2,6,6- pentamethyl -4- piperidine alcohols.
The content of the invention
The purpose of the present invention is to be directed to production cost height in existing 1,2,2,6,6- pentamethyl -4- piperidine alcohols preparation process,
Product quality is low, pollute environment the problems such as, there is provided a kind of conjunction of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6-
Into method, have and prepare easy, economic and environment-friendly, product quality is high, high income, the advantages of being adapted to industrialized production.
The invention provides following technical scheme：
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
2,2,6,6- tetramethyl -4- piperidine alcohols and paraformaldehyde are mixed to join in solvent by a certain percentage, under normal pressure,
Under certain reaction temperature, certain time is stirred, makes the reaction of 2,2,6,6- tetramethyl -4- piperidine alcohols complete, is cooled to room
Temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols；
The structural formula of 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols is：
Second step：Catalytic hydrogenolytic cleavage
Reduced form solid catalyst is fitted into fixed bed reactors, the reaction solution after above-mentioned hydroxymethylation is added
Solvent, after the concentration of methylolation product is reached 20%~40%, fixed bed reactors are continually fed into certain charging rate,
And be passed through hydrogen, heat, reaction solution continues to flow out from fixed bed reactors lower end, the reaction solution of outflow through cooling, gas-liquid separation,
Liquid filtering, filtrate steaming removal solvent and target product 1,2,2,6,6- pentamethyl -4- piperidine alcohols are obtained after purification.
The structural formula of 1,2,2,6,6- pentamethyl -4- piperidine alcohols is：
Preferably, the mol ratio of 2,2,6,6- tetramethyl -4- piperidine alcohols and formaldehyde is 1 in the first step reaction:1.2~
1:3。
Preferably, the solvent in the first step reaction and second step reaction is methanol, ethanol, isopropanol
At least one of with toluene.
Preferably, the reaction temperature in the first step reaction is 50~110 DEG C, and the reaction time is 4~16 hours.
Preferably, the reaction temperature in the first step reaction is 70~110 DEG C, and the reaction time is 6~12 hours.
Preferably, the reduced form solid catalyst in the second step reaction is with γ-Al2O3For carrier, Cu, Ni
With Cr at least one loaded catalyst for active component, load capacity is 10~40%, the reduced form solid catalyst
Preparation method be to dissolve the nitrate of metal, by impregnating, drying, being calcined and obtain oxidized form solid catalyst, then in hydrogen
Atmosphere encloses lower reduction.
The method for expressing of catalyst is made up of carried metal and carrier, and metal is got a foothold and is designated as it in obtained catalyst
Weight/mass percentage composition.With Cu30Cr5/γ-Al2O3Exemplified by, its specific preparation method is as follows：By 22.73g Cu (NO3)2·3H2O、
7.69g Cr(NO3)3·9H2O is dissolved in 200mL deionized waters, is made into nitrate solution.By 13.08g Na2CO3It is dissolved in 200mL
Precipitating reagent is made into deionized water.Then in the case where 70 DEG C of water-bath Quick mechanicals stir, nitrate solution is dripped simultaneously with precipitating reagent
Add in the beaker equipped with 200mL deionized waters, maintain pH value between 7~8, aging 1h after precipitating completely, filtering, by filter cake
It is washed with deionized to without nitrate ion, filter cake is dried into 6h at 110 DEG C.Intend thin water aluminium with 15.58g after filter cake is crushed
Stone and the mixing of the dust technologies of 30mL 2%, are sufficiently stirred, grind, then shaped, be placed in 110 in baking oven with homemade extrusion device extrusion
DEG C fully drying after, be to slowly warm up in Muffle furnace 500 DEG C roasting 4h.Before use, catalyst is cut into 3~5mm length
Afterwards in 150 DEG C of catalyst needed for being obtained after hydrogen reducing 4h.
Preferably, the load capacity of active component is 15~30% in the second step reaction.
Preferably, the charging rate in second step reaction be 0.2~1.0mL/min, Hydrogen Vapor Pressure for 2.0~
6.0MPa, reaction temperature are 80~200 DEG C.
Preferably, the charging rate in second step reaction be 0.4~0.6mL/min, Hydrogen Vapor Pressure for 2.0~
4.0MPa, reaction temperature are 80~120 DEG C.
Preferably, the purification process in the second step reaction is vacuum distillation, the recycled solvent steamed.
The beneficial effects of the invention are as follows：
1st, the present invention is to make up the deficiencies in the prior art, it is proposed that a kind of two-step method prepares 1,2,2,6,6- pentamethyl -4-
The method of piperidine alcohols, 2,2,6,6- tetramethyl -4- piperidine alcohols are first made to react generation 4- hydroxyls -2,2,6,6- tetramethyl -1- completely
Piperidine alcohols, then catalytic hydrogenolysis obtain the pentamethyl -4- piperidine alcohols of product 1,2,2,6,6- of high quality.
2nd, the present invention avoids the problem of tetramethylpiperidinol can not convert completely in conventional method, institute by stepwise reaction
It is high to obtain product quality, high income.
3rd, relatively inexpensive reduced form solid catalyst is used in course of reaction of the present invention, prepares easy, economic ring
Protect, and selectivity and activity are very high, are adapted to industrialized production.
Embodiment
Embodiment 1
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
157.25g 2,2,6,6- tetramethyl -4- piperidine alcohols, 45.04g paraformaldehydes, 400mL ethanol are added to 1L tetra-
In mouth bottle, stirring reaction 10 hours at 80 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Ni30/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
After obtained reaction solution adds 400mL ethanol to dilute, fixed bed reactors are continually fed into 0.6mL/min charging rate, and lead to
Enter hydrogen, heat, it is 4.0MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 100 DEG C, and reaction solution continues anti-from fixed bed
Device lower end is answered to flow out, the reaction solution of outflow filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, and yield is
98.34%, 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained after vacuum distillation.
Embodiment 2
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
157.25g 2,2,6,6- tetramethyl -4- piperidine alcohols, 90.09g paraformaldehydes, 400mL methanol are added to 1L tetra-
In mouth bottle, stirring reaction 16 hours at 50 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Ni30/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
Obtained reaction solution is continually fed into fixed bed reactors with 0.4mL/min charging rate, and is passed through hydrogen, heating, makes fixation
Hydrogen Vapor Pressure is 2.0MPa in bed reactor, and temperature is 80 DEG C, and reaction solution continues to flow out from fixed bed reactors lower end, outflow
Reaction solution filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, yield 97.76%, after vacuum distillation
Obtain 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings.
Embodiment 3
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
125.80g 2,2,6,6- tetramethyl -4- piperidine alcohols, 28.83g paraformaldehydes, 200mL toluene are added to 1L tetra-
In mouth bottle, stirring reaction 8 hours at 110 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Cu30Cr5/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm will be upper
After the reaction solution that step obtains adds 20mL dilution with toluene, fixed bed reactors are continually fed into 0.2mL/min charging rate, and lead to
Enter hydrogen, heat, it is 3.0MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 150 DEG C, and reaction solution continues anti-from fixed bed
Device lower end is answered to flow out, the reaction solution of outflow filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, and yield is
96.97%, 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained after vacuum distillation.
Embodiment 4
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
By 125.80g 2,2,6,6- tetramethyl -4- piperidine alcohols, 48.05g paraformaldehydes, 200mL ethanol, 200mL isopropyls
Alcohol is added in 1L four-hole bottles, stirring reaction 6 hours at 80 DEG C, and it is anti-that gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols
Should be complete, room temperature is cooled to, is filtered to remove excessive paraformaldehyde, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Cu40/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
After obtained reaction solution adds 200mL ethanol to dilute, fixed bed reactors are continually fed into 1.0mL/min charging rate, and lead to
Enter hydrogen, heat, it is 6.0MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 120 DEG C, and reaction solution continues anti-from fixed bed
Device lower end is answered to flow out, the reaction solution of outflow filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, and yield is
97.41%, 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained after vacuum distillation.
Embodiment 5
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
157.25g 2,2,6,6- tetramethyl -4- piperidine alcohols, 39.04g paraformaldehydes, 400mL isopropanols are added to 1L
In four-hole bottle, stirring reaction 12 hours at 70 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cold
But to room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Ni15/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
After obtained reaction solution adds 200mL isopropanols, fixed bed reactors are continually fed into 0.5mL/min charging rate, and
Hydrogen is passed through, is heated, it is 4.0MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 90 DEG C, and reaction solution continues from fixed bed
Reactor lower end is flowed out, and the reaction solution of outflow filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, and yield is
97.24%, 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained after vacuum distillation.
Embodiment 6
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
157.25g 2,2,6,6- tetramethyl -4- piperidine alcohols, 60.06g paraformaldehydes, 400mL toluene are added to 1L tetra-
In mouth bottle, stirring reaction 4 hours at 100 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Ni10/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
Obtained reaction solution is continually fed into fixed bed reactors with 0.3mL/min charging rate, and is passed through hydrogen, heating, makes fixation
Hydrogen Vapor Pressure is 3.0MPa in bed reactor, and temperature is 200 DEG C, and reaction solution continues to flow out from fixed bed reactors lower end, outflow
Reaction solution through cooling, gas-liquid separation, liquid filter, filtrate gas chromatographic analysis, yield 96.69%, through vacuum distillation
1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained afterwards.
Embodiment 7
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
125.80g 2,2,6,6- tetramethyl -4- piperidine alcohols, 36.03g paraformaldehydes, 300mL ethanol are added to 1L tetra-
In mouth bottle, stirring reaction 12 hours at 75 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Ni30Cr5/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm will be upper
After the reaction solution that step obtains adds 100mL isopropanols, fixed bed reactors are continually fed into 0.6mL/min charging rate,
And hydrogen is passed through, heat, it is 3.0MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 110 DEG C, and reaction solution continues from fixation
The outflow of bed reactor lower end, the reaction solution of outflow filter through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, yield
For 97.81%, after vacuum distillation 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings.
Embodiment 8
A kind of synthetic method of 1,2,2,6,6- pentamethyl -4- piperidine alcohols, including following two-step reaction：
The first step：Hydroxymethylation
125.80g 2,2,6,6- tetramethyl -4- piperidine alcohols, 43.24g paraformaldehydes, 300mL isopropanols are added to 1L
In four-hole bottle, stirring reaction 7 hours at 85 DEG C, gas phase monitors 2,2,6,6- tetramethyl -4- piperidine alcohols and has reacted complete, cools down
To room temperature, excessive paraformaldehyde is filtered to remove, obtains 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols.
Second step：Catalytic hydrogenolytic cleavage
By Cu20/γ-Al2O3It is fitted into fixed bed reactors, reactor inside diameter 14mm, pipe range 650mm, by upper step
After obtained reaction solution adds 100mL ethanol to dilute, fixed bed reactors are continually fed into 0.5mL/min charging rate, and lead to
Enter hydrogen, heat, it is 3.5MPa to make Hydrogen Vapor Pressure in fixed bed reactors, and temperature is 130 DEG C, and reaction solution continues anti-from fixed bed
Device lower end is answered to flow out, the reaction solution of outflow filters through cooling, gas-liquid separation, liquid, filtrate gas chromatographic analysis, and yield is
96.82%, 1,2,2,6,6- pentamethyl -4- piperidine alcohols sterlings are obtained after vacuum distillation.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, although with reference to foregoing reality
Apply example the present invention is described in detail, for those skilled in the art, it still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic.All essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (10)
1. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6-, it is characterised in that including following two
Step reaction：
The first step：Hydroxymethylation
2,2,6,6- tetramethyl -4- piperidine alcohols and paraformaldehyde are mixed to join in solvent by a certain percentage, under normal pressure, one
Under fixed reaction temperature, certain time is stirred, makes the reaction of 2,2,6,6- tetramethyl -4- piperidine alcohols complete, is cooled to room temperature, mistake
Excessive paraformaldehyde is filtered out, obtains methylolation product 4- hydroxyls -2,2,6,6- tetramethyl -1- piperidine alcohols；
Second step：Catalytic hydrogenolytic cleavage
Reduced form solid catalyst is fitted into fixed bed reactors, the reaction solution after above-mentioned hydroxymethylation added molten
Agent, after the concentration of methylolation product is reached 20%~40%, fixed bed reactors are continually fed into certain charging rate, and
Hydrogen is passed through, is heated, reaction solution continues to flow out from fixed bed reactors lower end, and the reaction solution of outflow is through cooling, gas-liquid separation, liquid
Body filtering, filtrate steaming removal solvent and target product 1,2,2,6,6- pentamethyl -4- piperidine alcohols are obtained after purification.
2. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1, its
It is characterised by, the mol ratio of 2,2,6,6- tetramethyl -4- piperidine alcohols and paraformaldehyde is 1 in the first step reaction:1.2~1:
3。
3. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1, its
It is characterised by, the solvent in the first step reaction and second step reaction is methanol, ethanol, isopropanol and toluene
At least one of.
4. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1, its
It is characterised by, the reaction temperature in the first step reaction is 50~110 DEG C, and the reaction time is 4~16 hours.
5. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 4, its
It is characterised by, the reaction temperature in the first step reaction is 70~110 DEG C, and the reaction time is 6~12 hours.
6. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1, its
It is characterised by, the reduced form solid catalyst in the second step reaction is with γ-Al2O3For carrier, Cu, Ni and Cr's
At least one loaded catalyst for active component, load capacity are 10~40%, the preparation of the reduced form solid catalyst
Method is to dissolve the nitrate of metal, by impregnating, drying, being calcined and obtain oxidized form solid catalyst, then in atmosphere of hydrogen
Lower reduction.
7. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 6, its
It is characterised by, the load capacity of active component is 15~30% in the second step reaction.
8. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1, its
It is characterised by, the charging rate in the second step reaction is 0.2~1.0mL/min, and Hydrogen Vapor Pressure is 2.0~6.0MPa, instead
It is 80~200 DEG C to answer temperature.
9. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 8, its
It is characterised by, the charging rate in the second step reaction is 0.4~0.6mL/min, and Hydrogen Vapor Pressure is 2.0~4.0MPa, instead
It is 80~120 DEG C to answer temperature.
10. the synthetic method of the pentamethyl -4- piperidine alcohols of light stabilizer intermediate 1,2,2,6,6- according to claim 1,
Characterized in that, the purification process in the second step reaction is vacuum distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711015303.0A CN107674017B (en) | 2017-10-25 | 2017-10-25 | Synthesis method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711015303.0A CN107674017B (en) | 2017-10-25 | 2017-10-25 | Synthesis method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107674017A true CN107674017A (en) | 2018-02-09 |
| CN107674017B CN107674017B (en) | 2020-05-15 |
Family
ID=61142343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711015303.0A Active CN107674017B (en) | 2017-10-25 | 2017-10-25 | Synthesis method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107674017B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180562A (en) * | 2018-10-25 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of N- methyl piperidine |
| CN110655487A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Synthetic method of 1,2,2,6, 6-pentamethylpiperidinol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974127A (en) * | 1973-09-17 | 1976-08-10 | E. I. Du Pont De Nemours And Company | Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols |
| US20070015802A1 (en) * | 2002-07-08 | 2007-01-18 | Nicholas Piramal India Limited | Inhibitors of cyclin dependent kinases and their use |
| CN104130161A (en) * | 2014-07-14 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Synthetic method of carbonic diamide di(methylamino valerate) |
-
2017
- 2017-10-25 CN CN201711015303.0A patent/CN107674017B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974127A (en) * | 1973-09-17 | 1976-08-10 | E. I. Du Pont De Nemours And Company | Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols |
| US20070015802A1 (en) * | 2002-07-08 | 2007-01-18 | Nicholas Piramal India Limited | Inhibitors of cyclin dependent kinases and their use |
| CN104130161A (en) * | 2014-07-14 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Synthetic method of carbonic diamide di(methylamino valerate) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655487A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Synthetic method of 1,2,2,6, 6-pentamethylpiperidinol |
| CN109180562A (en) * | 2018-10-25 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of N- methyl piperidine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107674017B (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101255109B (en) | Technique for producing propenoic acid by dehydrating biomass lactic acid | |
| CN109485568B (en) | Preparation method of high-optical indoxacarb intermediate | |
| CN103113187A (en) | Method for producing ethanol and coproducing ethyl acetate with acetic acid | |
| CN107674017A (en) | The synthetic method of the piperidine alcohols of 1,2,2,6,6 pentamethyl of light stabilizer intermediate 4 | |
| WO2021093292A1 (en) | Co-production method for 2-(2-amino-propoxy)ethanol and polyether polyol | |
| CN109867596B (en) | Method for continuously producing 3-methyl-3-pentene-2-ketone by reactive distillation | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN101544601B (en) | Method for synthesizing 5,6,7,8-tetrahydroquinoline | |
| CN108126748B (en) | Alkaline monolithic catalyst with regular pore channels and preparation method and application thereof | |
| CN112206808B (en) | Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof | |
| CN110170327B (en) | Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof | |
| CN107987011A (en) | A kind of piperidines is continuously synthesizing to method | |
| CN111689893B (en) | Preparation method of 2,2,6, 6-tetramethyl-4-aminopiperidine | |
| CN108786846B (en) | Zirconium silicate modified sulfonic acid grafted mesoporous silica catalyst, and preparation method and application thereof | |
| CN110467534A (en) | A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene | |
| CN107445786B (en) | Method for preparing biphenyl by hydrogenation of dibenzofuran | |
| CN101195600A (en) | Method for producing 4-hydroxyindole | |
| CN101205192B (en) | Method for preparing 1,3-di(4-amino-benzene oxygen) benzene | |
| CN104529730A (en) | Method for preparing 3-pentanone by using 2-pentene | |
| CN109337714B (en) | Preparation method of low-naphthalene high-boiling-point aromatic solvent for rubber resin plasticizer | |
| CN108424373A (en) | A kind of method that primary amine oxidative coupling prepares imine compound | |
| CN104496939B (en) | A kind of catalytic hydrogenation prepares the method for piperazine or alkyl piperazine | |
| CN112521346A (en) | Method for synthesizing pyrrolidine by continuously catalyzing amine with tetrahydrofuran | |
| CN113354806A (en) | Epoxy-terminated allyl alcohol polyether and preparation method thereof | |
| CN104447255A (en) | Method for preparing 2-pentanone from 2-amylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |