CN102050760A - Catalytic preparation method for hindered phenol derivative antioxygen - Google Patents
Catalytic preparation method for hindered phenol derivative antioxygen Download PDFInfo
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Abstract
The invention discloses a catalytic preparation method for hindered phenol derivative antioxygen. In the invention, a catalytic dehydration process is adopted to prepare the hindered phenol derivative antioxygen, the reaction raw materials are subjected to acidification and monohydrazidation respectively to form two intermediates, and thionyl chloride is not used so as to reduce pollution; and then a solvent and two intermediates are added into a reactor and heated and refluxed to undergo dehydration in the presence of a catalyst, and water is separated out by a water segregator. In the invention, due to the adoption of the catalyst, the reaction temperature is lower, the raw material utilization rate is high, the reaction time is short, and the product yield is high; therefore, the method can contribute to the reduction of production cost and is suitable for industrial production. Evaluation on the use of the antioxygen in polyolefin wire and cables shows that the antioxygen prepared by the method disclosed by the invention has high antioxygen performance and metal passivating capacity.
Description
Technical field
The present invention relates to the preparation of oxidation inhibitor, specifically the catalytic preparation method of Hinered phenols derivative oxidation inhibitor.
Background technology
Oxidation inhibitor is the important auxiliary agent in polymer processing and the application process, and the oxidative degradation that can effectively suppress and slow down macromolecular material prolongs their work-ing life.In each kind antioxidant, the Hinered phenols primary antioxidant is to be most widely used a kind antioxidant maximum with consumption, and its consumption accounts for 55% of total amount, is widely used in plastics, fiber, rubber, oil, grease, makeup and foodstuffs industry.Fast development along with Plastic Additives Industry, to the demands for higher performance of Hinered phenols primary antioxidant, from its variety development trend, having multi-functional group is its principal character, not only can satisfy the high request of former Application Areas, the differentiated demand of also applicable institute Application Areas.
As macromolecular materials such as polyolefine and metal such as Cu, Mn, Fe, when Co contacts, these trace metals can cause hydroperoxide to transform the generation free radical, thereby promoted the aging of macromolecular material, even add a large amount of traditional Hinered phenols primary antioxidants this moment, also be difficult to suppress the katalysis of metal ion.For avoiding the contact action of this metal ion species, need to add the oxidation inhibitor that a class can the passive metal ionization usually, then can obtain comparatively satisfied effect.This kind antioxidant has hindered phenol and hydrazides or two kinds of functional groups of acid amides, and the hindered phenol structure can stop macromolecular material to be subjected to thermo-oxidative ageing; Hydrazides or amide structure can carry out complex reaction to metal ion, make it lose destruction, give anti-metallicity of goods and thermo oxidative aging simultaneously, and result of use is good.This kind antioxidant can be used with other phenolic antioxidant, has synergy; Therefore also can use separately, play the primary antioxidant effect, be widely used in electric wire, cable and stud with in the goods of metalwork.The structural formula of this kind antioxidant is suc as formula shown in (I):
R in the formula (I)
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different; N is 1 or 2.Described straight chained alkyl is: methyl, ethyl, propyl group, butyl, amyl group or hexyl; Described branched-chain alkyl is: the sec.-propyl or the tertiary butyl.The structure and the mechanism of action according to oxidation inhibitor most preferably are the tertiary butyl.
At present synthetic this kind antioxidant is a reaction raw materials with ester cpds, hydrazine hydrate, the thionyl chloride with hindered phenol structure mainly, adopts three-step approach synthetic.Wherein, the structural formula of ester cpds with hindered phenol structure is suc as formula shown in (II):
R in the formula (II)
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different; N is 1 or 2.
The synthesis technique step of bibliographical information is many, and one of the raw material of intermediate product preparation is thionyl chloride, unavoidably produces hydrogenchloride and sulfur dioxide gas, and environmental protection pressure is very big, and yield is lower in addition, and production cost is higher.Patent US3660438 proposes a kind of preparation method of this kind antioxidant, with β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, thionyl chloride and hydrazine hydrate are raw material, adopt three-steps process, after the purifying intermediate products, behind the reaction certain hour, filtration washing obtains antioxidant product under optimal temperature.This method purifying intermediate products complex process, yield is not high, is not suitable for suitability for industrialized production.
In addition, the CN1094394 report adopts direct such antioxidant product of evaporation prepared, and the ester cpds that at first has the hindered phenol structure generates corresponding intermediates acid after hydrolysis, and the structural formula of intermediate acid is suc as formula shown in (III); Have the ester cpds and the hydrazine hydrate reaction of hindered phenol structure simultaneously, generate the single hydrazides of corresponding intermediates, the structural formula of intermediate list hydrazides is suc as formula shown in (IV); Carry out direct dehydration reaction between two kinds of intermediates then, biosynthesis block phenol derivatives antioxidant product.
R among formula (III), (IV)
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different; N is 1 or 2.
This method avoids adopting thionyl chloride, has reduced the environmental pollution that may cause, but because the ester cpds with hindered phenol structure adds excessively more than 50%, reclaims comparatively difficulty, causes product cost too high, is unfavorable for promoting the use of.
Summary of the invention
At the defective that exists in the prior art, the object of the present invention is to provide a kind of catalytic preparation method of Hinered phenols derivative oxidation inhibitor, adopt catalytic dehydration technology, avoid using thionyl chloride,, reduce temperature of reaction by adding catalyzer, shorten the reaction times, and reduce the raw material add-on, improve product yield, reduce reaction cost.
For reaching above purpose, the technical scheme that the present invention takes is as follows:
The catalytic preparation method of Hinered phenols derivative oxidation inhibitor is characterized in that may further comprise the steps:
The first step, acidification reaction:
At N
2Protection adds ester cpds and the first kind of solvent with hindered phenol structure down in a reactor, first kind of solvent is 5～20: 1 with the mol ratio with ester cpds of hindered phenol structure; Described first kind of solvent is selected from least a in following: methyl alcohol, ethanol, methanol aqueous solution, aqueous ethanolic solution;
The temperature of reaction of control acidification reaction is 30～80 ℃; Behind temperature-stable, drip alkaline solution, having the ester cpds of hindered phenol structure and the mol ratio of alkaline solution is 2～3: 1; Described alkaline solution is selected from least a in following: sodium hydroxide, potassium hydroxide;
After the dropping alkaline solution finishes, keep the previous reaction temperature and continue acidification reaction, the reaction times of whole acidification reaction is 2～10h; Obtain containing the colourless transparent liquid of intermediate acid, the gained colourless transparent liquid successively through neutralization, filtration, water washing to neutral, drying process, obtain intermediate acid;
Second step, the hydrazides reaction:
At N
2Protection adds ester cpds and the second kind of solvent with hindered phenol structure down in another reactor, second kind of solvent is 40～100: 1 with the mol ratio with ester cpds of hindered phenol structure; Described second kind of solvent is selected from least a in following: methyl alcohol, ethanol;
Add hydrazine hydrate then, having the ester cpds of hindered phenol structure and the mol ratio of hydrazine hydrate is 1: 2～5, and under agitation condition, the temperature of reaction of control hydrazides reaction is 30～80 ℃, and the reaction times is 8～48h;
Then at N
2Boil off second kind of solvent under the protection, add water washing to neutral, filter, drying obtains intermediate list hydrazides;
The 3rd step, catalytic and dehydration reaction:
At N
2Protection down, the intermediate acid and the intermediate list hydrazides that in the 3rd reactor, add the first two steps gained, add the third solvent and dehydration catalyst then, the mol ratio of intermediate list hydrazides and intermediate acid is 1～4: 1, the mol ratio of the third solvent and intermediate acid is 10～100: 1, and the dehydration catalyst consumption is 1～5mol% of intermediate acid;
Described the third solvent is selected from least a in following: toluene, dimethylbenzene, chloroform, chlorobenzene;
Described dehydration catalyst is an an acidic catalyst, is selected from least a in following: tosic acid, be tosic acid supported catalyst, sulfuric acid, phosphoric acid, the niobic acid of carrier with the gac;
The temperature of reaction of control catalytic and dehydration reaction is 50～140 ℃, and the reaction times is 6～24h, and reaction is below the 30ppm until content of water in system, leaves standstill filtration then, washed with isopropyl alcohol, and filtration, drying obtain Hinered phenols derivative oxidation inhibitor.
On the basis of technique scheme, it is characterized in that: described ester cpds structural formula with hindered phenol structure is
, R in the formula
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different, n is 1 or 2.
The catalytic preparation method of Hinered phenols derivative oxidation inhibitor of the present invention adopts catalytic dehydration technology, avoids using thionyl chloride, and the adding catalyzer, reduce temperature of reaction, shorten the reaction times, and reduce the raw material add-on, improve product yield, reduce reaction cost.Owing to dehydration reaction has adopted catalyzer, the reaction raw materials utilization ratio obviously improves, and the temperature of reaction reduction, and the reaction times shortens, and therefore helps reducing production costs, and is fit to suitability for industrialized production and promotes the use of.
Embodiment
The present invention develops a kind of preparation method of Hinered phenols derivative oxidation inhibitor, and oxidation inhibitor of the present invention is applied to verify the processing stability that it is excellent in the polypropylene cable materials processing.Ester cpds intermediate acid shown in the production (III) after hydrolysis under the acidic conditions (acidification reaction) with hindered phenol structure; Have substance reactions such as the ester cpds of hindered phenol structure and hydrazine hydrate simultaneously, intermediate list hydrazides shown in the production (IV), carry out catalytic and dehydration reaction between two kinds of intermediates then, under the effect of dehydration catalyst, under suitable temperature condition, react the Hinered phenols derivative antioxidant product shown in the production (I).Used dehydration catalyst is an an acidic catalyst, comprises tosic acid, sulfuric acid, phosphoric acid, niobic acid or supported solid acid catalyst.
Principal reaction involved in the present invention is:
(1) be the acid of raw material synthetic intermediate with the ester cpds with hindered phenol structure at first, chemical equation is as follows:
(2) be raw material synthetic intermediate list hydrazides with the ester cpds with hindered phenol structure, chemical equation is as follows:
(3) be raw material with above-mentioned intermediate, through the synthetic target product of catalytic and dehydration reaction.Chemical equation is as follows:
As mentioned above, the catalytic preparation method of Hinered phenols derivative oxidation inhibitor disclosed by the invention may further comprise the steps:
The first step, acidification reaction:
At N
2Protection adds ester cpds and the first kind of solvent with hindered phenol structure down in a reactor, first kind of solvent is 5～20: 1 with the mol ratio with ester cpds of hindered phenol structure; Described first kind of solvent is selected from least a in following: methyl alcohol, ethanol, methanol aqueous solution, aqueous ethanolic solution; For example: first kind of solvent can be 5: 1,6: 1,7: 1,8: 1,9: 1,10: 1,11: 1,12: 1,13: 1,14: 1,15: 1,16: 1,17: 1,18: 1,19: 1 or 20: 1 with the mol ratio with ester cpds of hindered phenol structure; In using methyl alcohol, ethanol, methanol aqueous solution, aqueous ethanolic solution any two kinds, two or more or when all using, its proportioning is any;
The temperature of reaction of control acidification reaction is 30～80 ℃; Behind temperature-stable, drip alkaline solution, having the ester cpds of hindered phenol structure and the mol ratio of alkaline solution is 2～3: 1; Described alkaline solution is selected from least a in following: sodium hydroxide, potassium hydroxide; For example: the temperature of reaction of acidification reaction can be 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; Have the ester cpds of hindered phenol structure and the mol ratio of alkaline solution and can be 2: 1,2.2: 1,2.4: 1,2.6: 1,2.8: 1 or 3: 1; When using sodium hydroxide, potassium hydroxide simultaneously, its proportioning is any;
After the dropping alkaline solution finishes, keep the previous reaction temperature and continue acidification reaction, the reaction times of whole acidification reaction is 2～10h; Obtain containing the colourless transparent liquid of intermediate acid, the gained colourless transparent liquid successively through neutralization, filtration, water washing to neutral, drying process, obtain intermediate acid; For example: the reaction times of acidification reaction can be 2h, 4h, 6h, 8h or 10h;
Second step, the hydrazides reaction:
At N
2Protection adds ester cpds and the second kind of solvent with hindered phenol structure down in another reactor, second kind of solvent is 40～100: 1 with the mol ratio with ester cpds of hindered phenol structure; Described second kind of solvent is selected from least a in following: methyl alcohol, ethanol; For example: second kind of solvent can be 40: 1,45: 1,50: 1,55: 1,60: 1,65: 1,70: 1,75: 1,80: 1,85: 1,90: 1,95: 1 or 100: 1 with the mol ratio with ester cpds of hindered phenol structure; When using methyl alcohol, ethanol simultaneously, its proportioning is any;
Add hydrazine hydrate then, having the ester cpds of hindered phenol structure and the mol ratio of hydrazine hydrate is 1: 2～5, and under agitation condition, the temperature of reaction of control hydrazides reaction is 30～80 ℃, and the reaction times is 8～48h; For example: having the ester cpds of hindered phenol structure and the mol ratio of hydrazine hydrate can be 1: 2,1: 3,1: 4 or 1: 5; The temperature of reaction of hydrazides reaction can be 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h for 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ of reaction times;
Then at N
2Boil off second kind of solvent under the protection, add water washing to neutral, filter, drying obtains intermediate list hydrazides;
The 3rd step, catalytic and dehydration reaction:
At N
2Protection down, the intermediate acid and the intermediate list hydrazides that in the 3rd reactor, add the first two steps gained, add the third solvent and dehydration catalyst then, the mol ratio of intermediate list hydrazides and intermediate acid is 1～4: 1, the mol ratio of the third solvent and intermediate acid is 10～100: 1, and the dehydration catalyst consumption is 1～5mol% of intermediate acid; For example: the mol ratio of intermediate list hydrazides and intermediate acid can be 1: 1,2: 1,3: 1 or 4: 1; The mol ratio of the third solvent and intermediate acid can be 10: 1,20: 1,30: 1,40: 1,50: 1,60: 1,70: 1,80: 1,90: 1 or 100: 1; The dehydration catalyst consumption can be 1mol%, 2mol%, 3mol%, 4mol% or the 5mol% of intermediate acid;
Described the third solvent is selected from least a in following: toluene, dimethylbenzene, chloroform, chlorobenzene; In using toluene, dimethylbenzene, chloroform, chlorobenzene any two kinds, two or more or when all using, its proportioning is any;
Described dehydration catalyst is an an acidic catalyst, is selected from least a in following: tosic acid, be tosic acid supported catalyst, sulfuric acid, phosphoric acid, the niobic acid of carrier with the gac; When using tosic acid, being any two kinds in the tosic acid supported catalyst of carrier, sulfuric acid, phosphoric acid, the niobic acid, two or more or when all using, its proportioning is any with gac;
The temperature of reaction of control catalytic and dehydration reaction is 50～140 ℃, and the reaction times is 6～24h, and reaction is below the 30ppm until content of water in system, leaves standstill filtration then, washed with isopropyl alcohol, and filtration, drying obtain Hinered phenols derivative oxidation inhibitor.For example: the temperature of reaction of catalytic and dehydration reaction can be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃; Reaction times can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.
On the basis of technique scheme, it is characterized in that: described ester cpds structural formula with hindered phenol structure is
, R in the formula
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different, n is 1 or 2.
Beneficial effect of the present invention: the present invention adopts catalytic dehydration prepared hindered phenol derivative oxidation inhibitor, owing to adopt catalyzer, therefore temperature of reaction reduces, raw material availability improves, reaction times shortens, and product yield improves, and later separation is purified and simplified, help production cost and reduce, be fit to suitability for industrialized production.Applicating evaluating in polyolefin electric wire and cable shows that oxidation inhibitor of the present invention has good antioxygen property and metal passivation ability.
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.All steps of not describing in detail (for example: filtration, washing etc.) among following each embodiment all can adopt known prior art or conventional techniques in this area to realize that this paper no longer describes in detail.
Embodiment 1
β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionates (ester cpds that promptly has the hindered phenol structure) and the 500ml methyl alcohol of 1mol are added in the 1L four-hole bottle logical N
2, to open and stir, heating in water bath when homo(io)thermism is 60 ℃, begins to drip the 30%NaOH solution of 220ml.After dropwising, slowly be heated to 65 ℃, reacting balance is carried out.Behind the reaction 4h, change beaker over to, add the 2N dilute hydrochloric acid neutralization of 1600mL then, separate out white precipitate, stirred 2 hours, filter, water washing obtains the acid of 290g intermediate to neutrality, drying.
β-(3 with 1mol, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 2000ml methyl alcohol add in the 5L there-necked flask, add the 350g hydrazine hydrate, open and stir, be heated to 40 ℃, after keeping 30h, begin distillation and remove solvent methanol, add water washing then, filter to neutral, drying obtains intermediate list hydrazides 291g.
Acid of 10g intermediate and 20g intermediate list hydrazides are added in the 500ml four-hole bottle, the catalyzer tosic acid and the 100ml solvent xylene that add 2mol% then, the reheat reflux dewatering, when treating that moisture is reduced to 30ppm in the system, the reaction times is 12h, stop heating, after temperature is reduced to room temperature, filter, add washed with isopropyl alcohol, filter, drying obtains 15g Hinered phenols derivative oxidation inhibitor.Test by analysis, the product fusing point is 239 ℃, and results of elemental analyses is consistent with calculated value, and N content is 5.0%, and C content 73.3%, H content are 9.6%, O content is 12.2%.
Embodiment 2
β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionates (ester cpds that promptly has the hindered phenol structure) and the 600ml methyl alcohol of 1mol are added in the 1L four-hole bottle logical N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the 30%NaOH solution of 200ml.After dropwising, slowly be heated to 60 ℃, reacting balance is carried out.Behind the reaction 5h, change beaker over to, add the 2N dilute hydrochloric acid of 1400mL then, separate out white precipitate, stirred 2 hours, filter, obtain the acid of 290g intermediate after washing, the drying.
β-(3 with 1mol, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 3000ml methyl alcohol add in the 5L there-necked flask, add the 254g hydrazine hydrate, open and stir, be heated to 50 ℃, after keeping 22h, begin distillation and remove solvent methanol, add water washing then, filter to neutral, drying obtains intermediate list hydrazides 291g.
Acid of 8g intermediate and 17g intermediate list hydrazides are added in the four-hole bottle, add 3mol% catalyzer niobic acid then, add 80ml solvent chlorobenzene, reflux dehydration then, when treating that moisture is reduced to 30ppm in the system, reaction times is 8h, stops heating, after temperature is chilled to room temperature, filter, add washed with isopropyl alcohol, filter, drying obtains the 15g product.Test by analysis, the product fusing point is 240 ℃, and results of elemental analyses is consistent with calculated value, and N content is 5.1%, and C content 73.2%, H content are 9.7%, O content is 12.1%.
Embodiment 3
β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and the 1000ml ethanol of 1mol are added in the 5L four-hole bottle logical N
2, to open and stir, heating in water bath when homo(io)thermism is 65 ℃, begins to drip the 30%NaOH solution of 300ml.After dropwising, slowly be heated to 80 ℃, reacting balance is carried out.Behind the reaction 3h, change beaker over to, add the 2N dilute hydrochloric acid of 2100mL then, separate out white precipitate, stirred 2 hours, filter, obtain 290g acidified product (intermediate acid) after washing, the drying.
β-(3 with 1mol, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 3000ml methyl alcohol add in the 5L there-necked flask, add the 400g hydrazine hydrate, open and stir, be heated to 30 ℃, after keeping 45h, begin distillation and remove solvent methanol, add water washing then, filter, drying obtains single hydrazides product (intermediate list hydrazides) 289g.
Above-mentioned gained two kinds of intermediate acidified products 15g and single hydrazides product 40g are added (that is: with in acid of 15g intermediate and the 40g intermediate list hydrazides adding four-hole bottle) in the four-hole bottle successively, add 5% catalyzer niobic acid then, add the 150ml solvent xylene, then reflux, when treating that moisture is reduced to 30ppm in the system, reaction times is 6h, stops heating, after temperature is chilled to room temperature, filter, add washed with isopropyl alcohol, filter, drying obtains the 28g product.Test by analysis, the product fusing point is 238 ℃, and results of elemental analyses is consistent with calculated value, and N content is 5.3%, and C content 73.0%, H content are 9.6%, O content is 12.2%.
Embodiment 4
β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl acetate and the 500ml methanol aqueous solution of 1mol are added in the 1L four-hole bottle logical N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the 30%NaOH solution of 200ml.After dropwising, slowly be heated to 60 ℃, reacting balance is carried out.Behind the reaction 5h, change beaker over to, add the 2N dilute hydrochloric acid of 1400mL then, separate out white precipitate, stirred 2 hours, filter, obtain the 282g acidified product after washing, the drying.
β-(3 with 1mol, the 5-di-tert-butyl-hydroxy phenyl) methyl acetate and 2800ml ethanol add in the 5L there-necked flask, add the 244g hydrazine hydrate, open and stir, be heated to 50 ℃, after keeping 22h, begin distillation and remove solvent methanol, add water washing then, filter, drying obtains single hydrazides product 278g.
Above-mentioned two kinds of intermediate 10g acid and the single hydrazides of 20g are added in the 500ml four-hole bottle, the catalyzer niobic acid and the 100ml solvent benzol that add 2mol% then, the reheat reflux dewatering is kept 20h, when treating that moisture is reduced to 30ppm in the system, stop heating, after temperature is reduced to room temperature, filter, add washed with isopropyl alcohol, filter, drying obtains the 16g product.Test by analysis, the product fusing point is 225 ℃, and results of elemental analyses is consistent with calculated value, and N content is 5.4%, and C content 73.2%, H content are 9.1%, O content is 12.3%.
Embodiment 5
In β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 500ml methyl alcohol and alcohol mixed solution adding 1L four-hole bottle with 1mol, logical N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the 30%NaOH solution of 200ml.After dropwising, slowly be heated to 60 ℃, reacting balance is carried out.Behind the reaction 5h, change beaker over to, add the 2N dilute hydrochloric acid of 1400mL then, separate out white precipitate, stirred 2 hours, filter, obtain the 292g acidified product after washing, the drying.
β-(3 with 1mol, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 2800ml ethanol add in the 5L there-necked flask, add the 244g hydrazine hydrate, open and stir, be heated to 50 ℃, after keeping 22h, begin distillation and remove etoh solvent, add water washing then, filter, drying obtains single hydrazides product 281g.
Above-mentioned two kinds of intermediate 10g acid and the single hydrazides of 20g are added in the 500ml four-hole bottle, the catalyzer tosic acid and the 100ml solvent xylene that add 2mol% then, the reheat reflux dewatering is kept 24h, when treating that moisture is reduced to 30ppm in the system, stop heating, after temperature is reduced to room temperature, filter, add washed with isopropyl alcohol, filter, drying obtains the 16.5g product.Test by analysis, the product fusing point is 238 ℃, and results of elemental analyses is consistent with calculated value, and N content is 4.9%, and C content 73.2%, H content are 10.2%, O content is 11.8%.
The application testing example
Add 0.2 part of embodiment 1 product, 0.1 part of antioxidant 1010,1 part of copper powder in 100 parts of poly-ethylene cable materials, make aging test piece behind the mixing, after 110 ℃ of thermo-oxidative ageings that carried out 4 days were tested, test-results showed that sample still remains intact.Under same condition, if do not add the embodiment product, then sample becomes fragile, and it is green that copper powder turns.Embodiment 2, embodiment 3, embodiment 4 and embodiment 5 products are carried out same test, can obtain similar result.
Claims (2)
1. the catalytic preparation method of Hinered phenols derivative oxidation inhibitor is characterized in that may further comprise the steps:
The first step, acidification reaction:
At N
2Protection adds ester cpds and the first kind of solvent with hindered phenol structure down in a reactor, first kind of solvent is 5～20: 1 with the mol ratio with ester cpds of hindered phenol structure; Described first kind of solvent is selected from least a in following: methyl alcohol, ethanol, methanol aqueous solution, aqueous ethanolic solution;
The temperature of reaction of control acidification reaction is 30～80 ℃; Behind temperature-stable, drip alkaline solution, having the ester cpds of hindered phenol structure and the mol ratio of alkaline solution is 2～3: 1; Described alkaline solution is selected from least a in following: sodium hydroxide, potassium hydroxide;
After the dropping alkaline solution finishes, keep the previous reaction temperature and continue acidification reaction, the reaction times of whole acidification reaction is 2～10h; Obtain containing the colourless transparent liquid of intermediate acid, the gained colourless transparent liquid successively through neutralization, filtration, water washing to neutral, drying process, obtain intermediate acid;
Second step, the hydrazides reaction:
At N
2Protection adds ester cpds and the second kind of solvent with hindered phenol structure down in another reactor, second kind of solvent is 40～100: 1 with the mol ratio with ester cpds of hindered phenol structure; Described second kind of solvent is selected from least a in following: methyl alcohol, ethanol;
Add hydrazine hydrate then, having the ester cpds of hindered phenol structure and the mol ratio of hydrazine hydrate is 1: 2～5, and under agitation condition, the temperature of reaction of control hydrazides reaction is 30～80 ℃, and the reaction times is 8～48h;
Then at N
2Boil off second kind of solvent under the protection, add water washing to neutral, filter, drying obtains intermediate list hydrazides;
The 3rd step, catalytic and dehydration reaction:
At N
2Protection down, the intermediate acid and the intermediate list hydrazides that in the 3rd reactor, add the first two steps gained, add the third solvent and dehydration catalyst then, the mol ratio of intermediate list hydrazides and intermediate acid is 1～4: 1, the mol ratio of the third solvent and intermediate acid is 10～100: 1, and the dehydration catalyst consumption is 1～5mol% of intermediate acid;
Described the third solvent is selected from least a in following: toluene, dimethylbenzene, chloroform, chlorobenzene;
Described dehydration catalyst is an an acidic catalyst, is selected from least a in following: tosic acid, be tosic acid supported catalyst, sulfuric acid, phosphoric acid, the niobic acid of carrier with the gac;
The temperature of reaction of control catalytic and dehydration reaction is 50～140 ℃, and the reaction times is 6～24h, and reaction is below the 30ppm until content of water in system, leaves standstill filtration then, washed with isopropyl alcohol, and filtration, drying obtain Hinered phenols derivative oxidation inhibitor.
2. the catalytic preparation method of Hinered phenols derivative oxidation inhibitor as claimed in claim 1 is characterized in that: described ester cpds structural formula with hindered phenol structure is
, R in the formula
1And R
2For: hydrogen atom, carbon atom are that 1～6 straight chained alkyl or carbon atom are 1～6 branched-chain alkyl, R
1And R
2Identical or different, n is 1 or 2.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557991A (en) * | 2011-12-21 | 2012-07-11 | 蓬莱红卫化工有限公司 | Spandex anti-yellowing agent, and preparation method and application thereof |
| CN104211616A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method for antioxidant |
| CN104447395A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | N,N'-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl]hydrazine production method |
| CN108350271A (en) * | 2015-11-12 | 2018-07-31 | 尤尼吉可株式会社 | Amilan polyamide resin composition and the formed body being molded with |
| CN108409930A (en) * | 2018-03-07 | 2018-08-17 | 中国铁道科学研究院铁道建筑研究所 | One kind is in supercritical CO2The polyalcohol of middle grafting antioxygen agent molecule |
| CN108484434A (en) * | 2018-03-15 | 2018-09-04 | 江苏极易新材料有限公司 | The synthesis technology of antioxidant 1024 |
| CN110177839A (en) * | 2017-02-03 | 2019-08-27 | 尤尼吉可株式会社 | Amilan polyamide resin composition and the formed body being molded with |
| CN110959800A (en) * | 2019-11-28 | 2020-04-07 | 梁山新翔新材料有限公司 | Preparation method of compound antioxidant |
| CN114671777A (en) * | 2022-03-18 | 2022-06-28 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN117362821A (en) * | 2023-09-21 | 2024-01-09 | 江西兴联晶鼎电子有限公司 | High-temperature-resistant polypropylene cable material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094394A (en) * | 1993-04-20 | 1994-11-02 | 天津市合成材料工业研究所 | The preparation method of bishydrazide derivative |
| CN1964936A (en) * | 2004-04-29 | 2007-05-16 | 科聚亚公司 | Method for the preparation of a hydroxyalkyl hindered phenolic antioxidant |
-
2009
- 2009-10-29 CN CN2009102095452A patent/CN102050760A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094394A (en) * | 1993-04-20 | 1994-11-02 | 天津市合成材料工业研究所 | The preparation method of bishydrazide derivative |
| CN1964936A (en) * | 2004-04-29 | 2007-05-16 | 科聚亚公司 | Method for the preparation of a hydroxyalkyl hindered phenolic antioxidant |
Non-Patent Citations (1)
| Title |
|---|
| 崔洪光: "受阻酚衍生物双酰肼（双酰胺）类抗氧剂合成新方法的研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑 2002年》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557991A (en) * | 2011-12-21 | 2012-07-11 | 蓬莱红卫化工有限公司 | Spandex anti-yellowing agent, and preparation method and application thereof |
| CN104211616A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method for antioxidant |
| CN104211616B (en) * | 2013-06-05 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of preparation method of antioxidant |
| CN104447395A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | N,N'-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl]hydrazine production method |
| CN108350271B (en) * | 2015-11-12 | 2020-11-03 | 尤尼吉可株式会社 | Polyamide resin composition and molded article obtained by molding same |
| CN108350271A (en) * | 2015-11-12 | 2018-07-31 | 尤尼吉可株式会社 | Amilan polyamide resin composition and the formed body being molded with |
| CN110177839B (en) * | 2017-02-03 | 2022-03-01 | 尤尼吉可株式会社 | Polyamide resin composition and molded article obtained by molding same |
| CN110177839A (en) * | 2017-02-03 | 2019-08-27 | 尤尼吉可株式会社 | Amilan polyamide resin composition and the formed body being molded with |
| CN108409930A (en) * | 2018-03-07 | 2018-08-17 | 中国铁道科学研究院铁道建筑研究所 | One kind is in supercritical CO2The polyalcohol of middle grafting antioxygen agent molecule |
| CN108484434A (en) * | 2018-03-15 | 2018-09-04 | 江苏极易新材料有限公司 | The synthesis technology of antioxidant 1024 |
| CN108484434B (en) * | 2018-03-15 | 2019-03-26 | 江苏极易新材料有限公司 | The synthesis technology of antioxidant 1024 |
| CN110959800A (en) * | 2019-11-28 | 2020-04-07 | 梁山新翔新材料有限公司 | Preparation method of compound antioxidant |
| CN114671777A (en) * | 2022-03-18 | 2022-06-28 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN114671777B (en) * | 2022-03-18 | 2023-09-19 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN117362821A (en) * | 2023-09-21 | 2024-01-09 | 江西兴联晶鼎电子有限公司 | High-temperature-resistant polypropylene cable material and preparation method thereof |
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