CN109825847A - The preparation method of the alkoxylated intermediate of hindered amine - Google Patents
The preparation method of the alkoxylated intermediate of hindered amine Download PDFInfo
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Abstract
The invention belongs to light stabilizer preparation technical fields, in particular to the preparation method of a kind of alkoxylated intermediate of hindered amine, the alkoxylated intermediate of hindered amine is made in catalytic and oxidative electrolysis technology under the conditions of tetramethyl piperidine nitrogen oxygen free radical, tetramethylpiperidone NO free radical or tetramethylpiperidinol NO free radical are existing for water, alcohol, alkali, the RCOOH；The present invention uses catalytic and oxidative electrolysis technology method to synthesize NOR type hindered amine light stabilizer intermediate for the first time；Have the characteristics that reaction temperature is low and rapid, high income；It is extensive to prepare raw material sources, inexpensively.
Description
Technical field
The invention belongs to light stabilizer preparation technical field, in particular to the system of a kind of alkoxylated intermediate of hindered amine
Preparation Method.
Background technique
In the weather-proof use process of plastics, addition hindered amine light stabilizer is a kind of mature and stable means, is effectively mentioned
The weatherability of high plastic products.The secondary amine structure alkalinity all with higher of conventional hindered amine light stabilizer, limits in acid
Application under the conditions of property.In general, the alkoxylated hindered amine alkalinity of N- is substantially reduced, Representative Cultivars such as light stabilizer 371,
Light stabilizer 123 etc..It is found in weather resistant experiment, the alkoxylated hindered amine of N- is not only acidproof, and light stablizing effect compares secondary amine
The hindered amine light stabilizer effect of structure is more excellent, but the conventional alkoxylated hindered amine synthesis technology of N- is complex,
Yield is relatively low.
Summary of the invention
The present invention solves the above-mentioned technical problems in the prior art, provides a kind of alkoxylated intermediate of hindered amine
Preparation method.
To solve the above problems, technical scheme is as follows:
A kind of preparation method of the alkoxylated intermediate of hindered amine, comprising the following steps:
Hindered amine alkoxylate is made in catalytic and oxidative electrolysis technology under the conditions of NO free radical is existing for water, alcohol, alkali, the RCOOH
Intermediate；The alkoxylated intermediate of hindered amine is as shown in formula I, II, III:
R is CnH2n+1, n=0~18；
The NO free radical is tetramethyl piperidine nitrogen oxygen free radical, tetramethylpiperidone NO free radical, tetramethyl piperazine
Any one in pyridine alcohol NO free radical.
Reaction equation is as follows:
Tetramethyl piperidine nitrogen oxygen free radical
Tetramethylpiperidone NO free radical
Tetramethylpiperidinol NO free radical
Preferably, the alcohol is methanol, ethyl alcohol, propyl alcohol, any one in isopropanol；Methanol is optimal.
Preferably, the alkali is LiOH, Li2CO3、NaOH、Na2CO3、KOH、K2CO3In any one；KOH and K2CO3Most
It is excellent.
Preferably, the NO free radical: water: alcohol: alkali: the mass ratio of the material of RCOOH be 1~20:1~30:50~
200:1~3:10~40；The mass ratio of the material is that 10~15:10~20:100~150:2~3:30~40 are optimal.
Preferably, the electrolysis temperature of the catalytic and oxidative electrolysis technology is 20~100 DEG C；50~60 DEG C are optimal.
Preferably, the anode material of the catalytic and oxidative electrolysis technology is graphite, DSA anode, any one in vitreous carbon, preferably
Graphite.
Preferably, the cathode material of the catalytic and oxidative electrolysis technology is graphite, any one in stainless steel, preferably stainless steel.
Preferably, the current density of the catalytic and oxidative electrolysis technology is maintained at 200~3000A/m3；It is preferred that current density is
800~1500A/m3。
More specifically, recommending method of the present invention is to follow the steps below: the NO free radical of 55g
The electrolysis of (tetramethyl piperidine nitrogen oxygen free radical, tetramethylpiperidone NO free radical or tetramethylpiperidinol NO free radical) investment
In reaction flask, then water, 90g methanol, 6g potassium carbonate, the 40g acetic acid of 10g is put into respectively, in 1000A/m3It is electrolysed under current density
Catalysis oxidation, anode material are graphite, and cathode material is stainless steel, filter electrolyte after being electrolysed 12h, can obtain corresponding NOR
Type hindered amine light stabilizer intermediate.
Compared with the existing technology, advantages of the present invention is as follows,
1, the present invention synthesizes NOR type hindered amine light stabilizer intermediate using catalytic and oxidative electrolysis technology method for the first time；
2, the features such as this reaction is low compared with popular response temperature and rapid, high income；
3, raw material sources are extensive, inexpensively.
Detailed description of the invention
Fig. 1 is that when R is H, the infrared spectrogram of product is made in the RCOOH of embodiment 7.
Specific embodiment
Embodiment 1:
The raw material A of 50g is put into cell reaction bottle, then puts into water, 60g methanol, the 3g potassium carbonate, 40g second of 4g respectively
Acid, electrolysis temperature is at 60 DEG C, in 800A/m3Catalytic and oxidative electrolysis technology under current density, anode material are graphite, and cathode material is not
Become rusty steel, filters electrolyte after being electrolysed 12h, can obtain the methoxy based products 44g of tetramethyl piperidine, content (GC) 98.5%, yield
About 80%.
Raw material A
Embodiment 2:
In the raw material B of 50g investment cell reaction bottle, then put into respectively the water of 15g, 100g methanol, 5g potassium hydroxide,
60g propionic acid, electrolysis temperature is at 60 DEG C, in 1000A/m3Catalytic and oxidative electrolysis technology under current density, anode material are graphite, cathode material
Material is stainless steel, filters electrolyte after being electrolysed 12h, can obtain the ethoxy based products 49g of tetramethylpiperidone, content (GC)
98.2%, yield about 78%.
Raw material B
Embodiment 3:
In the raw material C of 50g investment cell reaction bottle, then put into respectively the water of 30g, 200g methanol, 4g potassium hydroxide,
100g propionic acid, electrolysis temperature is at 60 DEG C, in 1000A/m3Catalytic and oxidative electrolysis technology under current density, anode material are graphite, cathode
Material is stainless steel, filters electrolyte after being electrolysed 12h, can obtain the ethoxy based products 90g of tetramethyl piperidine, content (GC)
99.1%, yield about 76%.
Raw material C
Embodiment 4:
The methoxy based products of tetramethyl piperidine are prepared with the method for embodiment 1, the difference is that the selection of alcohol；It is obtained
The methoxyl group product assay (GC) and yield result of tetramethyl piperidine are as follows:
| The type of alcohol | The methoxyl group product assay (GC) of tetramethyl piperidine | Yield |
| Ethyl alcohol | 98.1% | 70% |
| Propyl alcohol | 97.2% | 67% |
| Isopropanol | 98.9% | 68% |
Embodiment 5:
The methoxy based products that tetramethyl piperidine is prepared with the method for embodiment 1, the difference is that NO free radical: water:
Alcohol: alkali: the mass ratio of the material of RCOOH；The methoxyl group product assay (GC) and yield result of tetramethyl piperidine obtained are as follows:
Embodiment 6:
The methoxy based products of tetramethyl piperidine are prepared with the method for embodiment 1, the electrolysis temperature of catalytic and oxidative electrolysis technology is 20
~100 DEG C, current density is maintained at 200~3000A/m3, reacting can all go on smoothly；Wherein electrolysis temperature selection 50~60
DEG C, current density select 800~1500A/m3It is optimal.
Embodiment 7:
The methoxy based products of tetramethyl piperidine are prepared with the method for embodiment 1, the difference is that catalytic and oxidative electrolysis technology
The selection of RCOOH；The methoxyl group product assay (GC) and yield result of tetramethyl piperidine obtained are as follows:
| The type of RCOOH | The methoxyl group product assay (GC) of tetramethyl piperidine | Yield |
| R is H | 98% | 90% |
| R is C9H217 | 96% | 85% |
| R is C18H37 | 88% | 75% |
Fig. 1 be R be H when, be made product infrared spectrogram；Before and after electrolysis, there is a characteristic peak in functional group region
3250(νOH), corresponding 3405, the 3250 (ν in the infrared peak of product after electrolysisOH)；2952(νCH3)；2850(νCH2)；This result and mark
Quasi- spectrogram is consistent.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of the alkoxylated intermediate of hindered amine, which comprises the following steps:
Catalytic and oxidative electrolysis technology under the conditions of NO free radical is existing for water, alcohol, alkali, the RCOOH, be made hindered amine it is alkoxylated in
Mesosome；The alkoxylated intermediate of hindered amine is as shown in formula I, II, III:
R is CnH2n+1, n=0~18；
The NO free radical is tetramethyl piperidine nitrogen oxygen free radical, tetramethylpiperidone NO free radical, tetramethylpiperidinol
Any one in NO free radical.
2. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the alcohol is first
Alcohol, ethyl alcohol, propyl alcohol, any one in isopropanol.
3. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the alkali is
LiOH、Li2CO3、NaOH、Na2CO3、KOH、K2CO3In any one.
4. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the nitrogen oxygen is certainly
By base: water: alcohol: alkali: the mass ratio of the material of RCOOH is 1~20:1~30:50~200:1~3:10~40.
5. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the nitrogen oxygen is certainly
By base: water: alcohol: alkali: the mass ratio of the material of RCOOH is 10~15:10~20:100~150:2~3:30~40.
6. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the electrolysis is urged
The electrolysis temperature for changing oxidation is 20~100 DEG C.
7. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the electrolysis is urged
Change the anode material of oxidation as any one in graphite, DSA anode, vitreous carbon.
8. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the electrolysis is urged
Change the cathode material of oxidation as any one in graphite, stainless steel.
9. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the electrolysis is urged
The current density for changing oxidation is maintained at 200~3000A/m3。
10. the preparation method of the alkoxylated intermediate of hindered amine as described in claim 1, which is characterized in that the electrolysis
The current density of catalysis oxidation is maintained at 800~1500A/m3。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111996546A (en) * | 2020-07-28 | 2020-11-27 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN113354813A (en) * | 2021-06-02 | 2021-09-07 | 宿迁联盛科技股份有限公司 | Preparation method of low-alkalinity hindered amine light stabilizer NOR371 |
| CN116333523A (en) * | 2021-12-17 | 2023-06-27 | 天津利安隆新材料股份有限公司 | Dendritic N-alkoxy hindered amine light stabilizer, preparation method and application thereof |
| US11802209B2 (en) | 2020-02-20 | 2023-10-31 | Lg Chem, Ltd. | Adhesive composition, adhesive film, adhesive optical filter and display device |
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| CN101048378A (en) * | 2004-11-02 | 2007-10-03 | 西巴特殊化学品控股有限公司 | Process for the synthesis of n-alkoxyamines |
| EP3153605A1 (en) * | 2015-09-22 | 2017-04-12 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Method for producing a layered (semi-)conductive material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048378A (en) * | 2004-11-02 | 2007-10-03 | 西巴特殊化学品控股有限公司 | Process for the synthesis of n-alkoxyamines |
| EP3153605A1 (en) * | 2015-09-22 | 2017-04-12 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Method for producing a layered (semi-)conductive material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11802209B2 (en) | 2020-02-20 | 2023-10-31 | Lg Chem, Ltd. | Adhesive composition, adhesive film, adhesive optical filter and display device |
| CN111996546A (en) * | 2020-07-28 | 2020-11-27 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN111996546B (en) * | 2020-07-28 | 2021-06-29 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN113354813A (en) * | 2021-06-02 | 2021-09-07 | 宿迁联盛科技股份有限公司 | Preparation method of low-alkalinity hindered amine light stabilizer NOR371 |
| CN116333523A (en) * | 2021-12-17 | 2023-06-27 | 天津利安隆新材料股份有限公司 | Dendritic N-alkoxy hindered amine light stabilizer, preparation method and application thereof |
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