CN110042421B - Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical - Google Patents
Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical Download PDFInfo
- Publication number
- CN110042421B CN110042421B CN201910408541.0A CN201910408541A CN110042421B CN 110042421 B CN110042421 B CN 110042421B CN 201910408541 A CN201910408541 A CN 201910408541A CN 110042421 B CN110042421 B CN 110042421B
- Authority
- CN
- China
- Prior art keywords
- alkoxylation
- tetramethyl
- electrolytic
- nitroxide
- sebacic acid
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to the technical field of light stabilizer preparation, in particular to a preparation method of an alkoxylation intermediate based on sebacic acid diester nitroxide free radical; the method comprises the following steps: carrying out electrolytic catalytic oxidation on bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radicals in the presence of water, alcohol, alkali and HCOOH to prepare an alkoxylation intermediate; the invention has the following beneficial effects: compared with the conventional reaction, the reaction has low temperature, does not need to use a catalyst and has quick reaction; the raw materials are wide in source and low in price; and the final yield of the product is high, so that the method has economic value.
Description
Technical Field
The invention relates to the technical field of light stabilizer preparation, and particularly relates to a preparation method of an alkoxylation intermediate based on sebacic acid diester nitroxide free radicals.
Background
In order to improve the weatherability of plastic articles, light stabilizers are often added during their fabrication process. Most of the existing light stabilizers are hindered amine light stabilizers, for example, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate is a hindered amine light stabilizer. For example, Chinese patent publication No. CN106699639A discloses a method for synthesizing a light stabilizer HS-112. It should be noted that: the light stabilizer HS-112 is the trade name of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate. The patent mentions that the light stabilizer HS112, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, is obtained by reacting molybdenum trioxide as a catalyst, n-octane as a raw material and a solvent with bis (2,2,6, 6-tetramethylpiperidyl) sebacate nitroxide free radical.
Because the traditional hindered amine light stabilizer generally has high alkalinity, the high alkalinity limits the synergistic stabilization effect of the hindered amine light stabilizer in a stabilization system containing halogen resin, acidic resin and possibly breeding acidic substances. HS-112 is a hindered amine N-alkoxide made by substituting-OC 8H17 for the hydrogen atom at the nitrogen of UV-770 (bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate) to reduce its basicity through a structural change.
However, the synthesis of the N-alkoxylated hindered amine is carried out by substitution reaction under the action of a catalyst, so that the process is complicated and the yield is low. If a more complex group is used for substitution, other N-alkoxylated light stabilizers with remarkable effects are synthesized by experiments, the substitution difficulty is in direct proportion to the complexity of the substituted group, and the yield is further reduced. It is therefore necessary to prepare an alkoxylated intermediate based on sebacic acid diester nitroxides to facilitate substitution of more complex groups and thus increase the final yield of light stabilizers.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a preparation method of an alkoxylation intermediate based on sebacic acid diester nitroxide free radicals.
In order to solve the problems, the technical scheme of the invention is as follows:
a preparation method of an alkoxylation intermediate based on sebacic acid diester nitroxide radical comprises the following steps:
carrying out electrolytic catalytic oxidation on bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radicals in the presence of water, alcohol, alkali and HCOOH to prepare an alkoxylation intermediate; the structural formula of the alkoxylation intermediate is as follows:
the reaction formula is as follows:
preferably, the alcohol is any one of methanol, ethanol, ethylene glycol, propanol and propylene glycol; methanol is most preferred.
Preferably, the base is NaOH, KOH, Ba (OH)2Any one of them; KOH is most preferred.
Preferably, the mass ratio of the sebacic acid bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester nitroxide free radical to the water to the alcohol to the alkali to the HCOOH is 1-60: 1-20: 80-150: 1-5: 1-40; the weight ratio of the sebacic acid bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester nitroxide free radical to the water to the alcohol to the alkali to the HCOOH is preferably 1-20: 10-20: 120-150: 2-3: 20-40.
Preferably, the electrolysis temperature of the electrolytic catalytic oxidation is 10-70 ℃; the temperature is preferably 40-50 ℃.
Preferably, the anode material for electrolytic catalytic oxidation is any one of a BDD electrode, glassy carbon and diamond, and the BDD electrode is preferred.
Preferably, the cathode material for electrolytic catalytic oxidation is any one of titanium plate, stainless steel and lead plate, preferably titanium plate.
Preferably, the current density of the electrolytic catalytic oxidation is kept between 300 and 2600A/m2(ii) a The preferred current density is 600-1200A/m2。
More specifically, the method of the present invention is recommended to be performed according to the following steps: 100g of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radical are put into an electrolytic reaction bottle, and 30g of water, 60g of methanol, 16g of sodium hydroxide and 30g of formic acid are respectively put into the electrolytic reaction bottle at a rate of 800A/m2Electrolyzing and catalyzing and oxidizing under current density, wherein an anode material is a BDD electrode, a cathode material is a titanium plate, and filtering the electrolyte after 24 hours of electrolysis to obtain the NOH type hindered amine light stabilizer intermediate of the sebacic acid di (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester nitroxide free radical.
Compared with the prior art, the invention has the advantages that,
(1) the invention synthesizes the alkoxylation intermediate of diester sebacate nitroxide free radical by electrolytic catalytic oxidation for the first time, the intermediate is the simplest NOH type hindered amine light stabilizer intermediate, and H groups in the intermediate are easily substituted by other more complex R groups, thereby further synthesizing the NOR type hindered amine light stabilizer intermediate. In the process, an NOH type hindered amine light stabilizer intermediate is prepared in advance in a high yield in an electrolytic catalytic oxidation mode, so that H groups in the prepared NOH type hindered amine light stabilizer intermediate are easily substituted by other complex groups R, and the NOR type hindered amine light stabilizer intermediate is synthesized in a high yield;
(2) compared with the conventional reaction, the reaction has low temperature, does not need to use a catalyst and has quick reaction;
(3) the raw materials are wide in source and low in price; and the final yield of the product is high, so that the method has economic value.
Drawings
FIG. 1 is an infrared spectrum of the product made in formic acid environment;
the lower curve in the figure is the nitroxide radical of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate;
the upper curve in the figure is the alkoxylation intermediate of the electrolysis product bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide radical.
Detailed Description
Example 1:
100g of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radical are put into an electrolytic reaction bottle, and 30g of water, 60g of methanol, 16g of sodium hydroxide and 30g of formic acid are respectively put into the electrolytic reaction bottle at a rate of 800A/m2Electrolyzing and catalyzing and oxidizing under current density, wherein an anode material is a BDD electrode, a cathode material is a titanium plate, and after 24 hours of electrolysis, filtering the electrolyte to obtain 97g of an alkoxylation intermediate product of sebacic acid diester nitroxide free radicals, wherein the content (GC) of the product is 97.40%, and the yield is about 89%.
FIG. 1 is an infrared spectrum of a product made in a formic acid environment; before electrolysis, a hydroxyl (V OH) characteristic peak does not exist in a functional group area, and an infrared peak of an electrolyzed product corresponds to 3405 (V OH) and has a hydroxyl characteristic peak; it is shown that nitroxide radicals are electrolyzed into hydroxyl radicals (. nu.OH) in the electrolysis reaction.
The method is used for preparing the alkoxylation intermediate product of the sebacic acid diester nitroxide free radical, the electrolysis temperature of the electrolytic catalytic oxidation is 10-70 ℃, and the current density is kept at 200-2600A/m2The reaction can be smoothly carried out; wherein the electrolysis temperature is selected from 40-50 deg.C, and the current density is selected from 600-1200A/m2Is optimal.
Example 2:
100g of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide radicalPutting into an electrolysis reaction bottle, and respectively adding 15g of water, 40g of methanol, 8g of sodium hydroxide and 30g of formic acid at a concentration of 300A/m2Electrolyzing and catalyzing and oxidizing under current density, wherein an anode material is a BDD electrode, a cathode material is a titanium plate, and after 24 hours of electrolysis, filtering the electrolyte to obtain 88g of a product of an alkoxylation intermediate of sebacic acid diester nitroxide free radicals, wherein the content (GC) of the product is 88.35%, and the yield is about 82%.
Example 3:
100g of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radical are put into an electrolytic reaction bottle, and 45g of water, 50g of methanol, 6g of potassium hydroxide and 50g of formic acid are respectively put into the electrolytic reaction bottle at a rate of 600A/m2Electrolyzing and catalyzing and oxidizing under current density, wherein an anode material is a BDD electrode, a cathode material is a titanium plate, and after 24 hours of electrolysis, filtering the electrolyte to obtain 93g of an alkoxylation intermediate product of sebacic acid diester nitroxide free radical, wherein the content (GC) of the product is 93.25%, and the yield is about 85%.
Example 4:
the procedure of example 1 was followed to prepare the product of the alkoxylation intermediate of sebacic acid diester nitroxide radical, except for the choice of alcohol; the product content (GC) and yield results were as follows:
example 5:
the preparation of an alkoxylated intermediate product of sebacic acid diester nitroxide radical was performed as in example 1, except for the mass ratio of nitroxide radical: water: alcohol: base: HCOOH; the results of the content (GC) and yield of the product of the alkoxylation intermediate of the diester sebacate nitroxide radical obtained were as follows:
comparative example 1:
the procedure of example 1 was followed to prepare the product of the alkoxylation intermediate of sebacic acid diester nitroxide radical, with the difference in the choice of anode material; the product content (GC) and yield results were as follows:
glassy carbon was used as anode: the by-products are more, the passivation is easy, the current is obviously reduced under the condition of constant voltage, and the electrolytic current density can be improved only by frequently cleaning the glass carbon pole plate.
Platinum was used as the anode: after 12 hours of electrolysis, the current is obviously reduced, and the product yield is low.
Using a lead-silver alloy as anode: almost no current and almost no product formation.
Comparative example 2:
the procedure of example 1 was followed to prepare the product of the alkoxylation intermediate of sebacic acid diester nitroxide radical, except for the choice of cathode material; the product content (GC) and yield results were as follows:
stainless steel was used as cathode: the stainless steel polar plate is easy to be corroded by electrolysis in the same time of electrolysis, and the products are less.
Using a lead plate as cathode: the surface of the lead plate is easy to corrode to form irregular concave-convex surfaces, the service life of the polar plate is shortened, and long-time use is not recommended.
Nickel plates were used as cathodes: almost no current and almost no product formation.
Cadmium plate was used as cathode: almost no current and almost no product formation.
Comparative example 3:
the procedure of example 1 was followed to prepare the product of the alkoxylation intermediate of sebacic acid diester nitroxide radical, except for the choice of electrolyte concentration; the product content (GC) and yield results were as follows:
the mass ratio of the nitroxide free radicals to the water to the alcohol to the base to the HCOOH is 20: 10: 40: 3: at 20, since the electrolytic solvent is a mixture of methanol and water, the amount of alcohol is small, and the nitroxide radical is not easily dissolved, resulting in reduction of electrolytic products.
The mass ratio of the nitroxide free radicals to the water to the alcohol to the base to the HCOOH is 20: 10: 240: 3: at 20, although the amount of alcohol used was 2 times the optimum charge ratio, the nitroxide radical was completely dissolved at this time, but the amount of methanol increased, which decreased the water content in the electrolyte, and resulted in a decrease in electrolysis efficiency and a decrease in electrolysis product.
The mass ratio of the nitroxide free radicals to the water to the alcohol to the base to the HCOOH is 20: 10: 120: 20: at 20 hours, in the feed ratio, the pH value of the electrolyte is higher due to excessive alkali, the polar plate can be seriously corroded in a short time of electrolysis, the electrolysis efficiency is reduced, and the generation of products is less.
Comparative example 4:
the procedure of example 1 was followed to prepare the product of the alkoxylation intermediate of sebacic acid diester nitroxide radical, except for the choice of current density; the product content (GC) and yield results were as follows:
the current density is low, which reduces the yield.
When the current density is large, the anode is broken down, electrolysis cannot be carried out, so that the electrolytic pole plate is unstable, and the quality of the anode is influenced.
The key conditions for the technical scheme to be successful are as follows: selecting a specific electrode material, namely selecting a BDD electrode as an anode material and a titanium plate as a cathode material; the concentration of the electrolyte is precisely controlled, namely the mass ratio of alkali to HCOOH is 20: 10: 120: 3: 20; under the conditions of specific current density, electrolysis temperature, etc., i.e. current density A/m2Is 800A/m2. The highest yield can be obtained.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (6)
1. A preparation method of an alkoxylation intermediate based on sebacic acid diester nitroxide radical is characterized by comprising the following steps:
carrying out electrolytic catalytic oxidation on bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radicals in the presence of water, alcohol, alkali and HCOOH to prepare an alkoxylation intermediate; the structural formula of the alkoxylation intermediate is as follows:
the alcohol is any one of methanol, ethanol, ethylene glycol, propanol and propylene glycol;
the mass ratio of the sebacic acid bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester nitroxide free radical to the water to the alcohol to the alkali to the HCOOH is 1-60: 1-20: 80-150: 1-5: 1-40;
the anode material for electrolytic catalytic oxidation is any one of BDD electrode, glassy carbon and diamond;
the cathode material for electrolytic catalytic oxidation is any one of a titanium plate, stainless steel and a lead plate.
2. The method of claim 1, wherein the base is NaOH, KOH, Ba (OH)2Any one of them.
3. The method according to claim 1, wherein the ratio of the bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide radical to the water, the alcohol, the base and the HCOOH is 1-20: 10-20: 120-150: 2-3: 20-40.
4. The method according to claim 1, wherein the electrolytic catalytic oxidation is carried out at an electrolytic temperature of 10 to 70 ℃.
5. The method according to claim 1, wherein the current density of the electrolytic catalytic oxidation is maintained in the range of 300 to 2600A/m2。
6. The method of claim 1, comprising the steps of:
100g of bis (2,2,6, 6-tetramethyl-4-hydroxypiperidine) sebacate nitroxide free radical are put into an electrolytic reaction bottle, and 30g of water, 60g of methanol, 16g of sodium hydroxide and 30g of formic acid are respectively put into the electrolytic reaction bottle at a rate of 800A/m2Electrolyzing and catalyzing and oxidizing under current density, wherein an anode material is a BDD electrode, a cathode material is a titanium plate, and filtering the electrolyte after 24 hours of electrolysis to obtain the NOH type hindered amine light stabilizer intermediate of the sebacic acid di (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester nitroxide free radical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910408541.0A CN110042421B (en) | 2019-05-16 | 2019-05-16 | Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910408541.0A CN110042421B (en) | 2019-05-16 | 2019-05-16 | Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110042421A CN110042421A (en) | 2019-07-23 |
| CN110042421B true CN110042421B (en) | 2020-06-02 |
Family
ID=67282325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910408541.0A Active CN110042421B (en) | 2019-05-16 | 2019-05-16 | Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110042421B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850596B (en) * | 2020-07-13 | 2021-04-20 | 万华化学(四川)有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| 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 |
| CN112609201B (en) * | 2020-12-11 | 2023-09-19 | 万华化学(四川)有限公司 | Method for synthesizing carbonic acid diester and sebacic acid diester in pair |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5611932A (en) * | 1979-07-12 | 1981-02-05 | Adeka Argus Chem Co Ltd | Stabilized polymer composition |
| EP2113519A1 (en) * | 2008-04-28 | 2009-11-04 | Construction Research and Technology GmbH | Method of initiating radical polymerisations |
| CN101298486B (en) * | 2008-06-13 | 2010-06-02 | 中国科学院上海有机化学研究所 | Polyallene nitroxyl radical |
| CN106699639A (en) * | 2016-12-22 | 2017-05-24 | 甘肃省化工研究院 | Synthesis method of light stabilizer HS-112 |
-
2019
- 2019-05-16 CN CN201910408541.0A patent/CN110042421B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110042421A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110042421B (en) | Preparation method of alkoxylation intermediate based on sebacic acid diester nitroxide free radical | |
| US4714530A (en) | Method for producing high purity quaternary ammonium hydroxides | |
| CN88100844A (en) | Carry out the electrochemical method of halogen atom exchange in the organic compound | |
| CN111188053B (en) | Method for preparing carbonate by utilizing Kolbe reaction by-product | |
| US10934242B2 (en) | Electrochemical method for producing valeric acid | |
| JPH0730475B2 (en) | Method for producing 1-aminoanthraquinones | |
| JP3260145B2 (en) | Method for producing quaternary ammonium hydroxide aqueous solution | |
| CN113416969A (en) | Electrochemical synthesis method of dimethyl sebacate | |
| JP4587329B2 (en) | Method for producing primary amines having a primary amino group and a cyclopropyl unit bonded to an aliphatic or alicyclic C-atom | |
| US3193475A (en) | Coupling cyclic olefins by electrolysis | |
| JPH01312094A (en) | Production of hydroxycarboxylic ester | |
| CN113354813B (en) | Preparation method of low-alkalinity hindered amine light stabilizer NOR371 | |
| KR890002864B1 (en) | Process for the preparation of m-hydroxy benzyl alcohol | |
| CN111996546B (en) | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester | |
| CN1641071A (en) | Alkyl hydroxylamine and its salt electrochemical synthesis method | |
| JPS6112886A (en) | Manufacture of phthalaldehyde acetal | |
| US6020520A (en) | Process for the preparation of tetraalkyl 1,2,3,4-butanetetracarboxylates | |
| JP2000503343A (en) | Method for producing tetraalkyl-1,2,3,4-butanetetracarboxylate | |
| EP0896642B1 (en) | Process for the preparation of tetraalkyl 1,2,3,4-butanetetracarboxylates | |
| JP2902755B2 (en) | Method for producing m-hydroxybenzyl alcohol | |
| CN116555787A (en) | Electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and electrolysis method | |
| JPS62294191A (en) | Production of alkoxy acetate | |
| JPS6141501B2 (en) | ||
| CN113668002A (en) | Method for preparing acetone from formic acid | |
| JPS63157891A (en) | Production of m-hydroxybenzyl alcohol |
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 |