CN103508923B - A kind of preparation method of Hinered phenols antioxidant - Google Patents
A kind of preparation method of Hinered phenols antioxidant Download PDFInfo
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- CN103508923B CN103508923B CN201210216214.3A CN201210216214A CN103508923B CN 103508923 B CN103508923 B CN 103508923B CN 201210216214 A CN201210216214 A CN 201210216214A CN 103508923 B CN103508923 B CN 103508923B
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Abstract
The preparation method that the present invention relates to a kind of new Hinered phenols antioxidant, solves reactions steps in prior art problem many, the difficult problems such as product yield is relatively low, and environmental protection pressure is big.The present invention, to have the ester of hindered phenol structure and hydrazine hydrate or diamidogen such as ethylenediamine, 1,3 propane diamine, Putriscine, pentanediamine or hexamethylene diamine for raw material, adopts " one-step method " technique synthesis target product, by adding base catalyst, makes reaction be smoothed out.During product of the present invention is widely used in electric wire, cable and studs with the goods of metalwork.
Description
Technical field
The preparation method that the present invention relates to a kind of Hinered phenols antioxidant, relate more specifically to a kind of suitable in the goods such as electric wire, cable, the preparation method with the Hinered phenols antioxidant of passive metal effect.
Background technology
Antioxidant is the important auxiliary agent in Polymer Processing and application process, it is possible to effectively suppresses and slows down the oxidative degradation of macromolecular material, extend their service life.In each kind antioxidant, Hinered phenols antioxidant is to be most widely used a kind antioxidant maximum with consumption, and its consumption figure accounts for the 55% of total amount, is widely used in plastics, fiber, rubber, oil, oils and fats, cosmetics and food industry.Fast development along with Plastic Additives Industry, the performance of Hinered phenols antioxidant is had higher requirement, and from its variety development trend, having multi-functional group is its principal character, not only can meet the high request of former application, it is possible to be suitable for the differentiated demand of application.When such as Cu, Mn, Fe, Co contact for the macromolecular materials such as polyolefin and metal, these trace meters can cause that hydroperoxides are converted into free radical, thus promoted the aging of macromolecular material, even if now adding Hinered phenols antioxidant traditional in a large number, it is also difficult to suppress the catalytic action of metal ion.For avoiding the contact action of this metal ion species, generally need to add a class can the antioxidant of passive metal ionization, then can obtain comparatively satisfied effect.This kind antioxidant has hindered phenol and hydrazides Liang Zhong functional group, and hindered phenol structure can stop macromolecular material to be subject to thermo-oxidative ageing；Metal ion can be carried out complex reaction by hydrazide structure so that it is lose destruction；This antioxidant gives goods anti-metal and thermal oxidative aging simultaneously, and result of use is good.This kind antioxidant can with other phenolic antioxidant with the use of, there is synergism；Can also be used alone, play primary antioxidant effect, in being therefore widely used in electric wire, cable and studding with the goods of metalwork.The structural formula of this kind antioxidant can be expressed as follows:
Wherein R1And R2Selected from hydrogen atom, straight or branched alkyl containing 1 ~ 6 carbon atom, n is 1 or 2, m is the integer of 0 ~ 6.
The base stock of current biosynthesis block phenolic antioxidant specifically includes that ester (II), hydrazine hydrate or diamidogen and the thionyl chloride etc. with hindered phenol structure, adopts " three-step approach " technique to synthesize described Hinered phenols antioxidant.Wherein the structural formula of base stock (II) is as follows:
Wherein, n, R1And R2Definition and formula I in identical.
In the above prior art, one of raw material necessary to biosynthesis block phenolic antioxidant three-steps process is thionyl chloride.But because of the use of thionyl chloride, unavoidably producing hydrogen chloride and sulfur dioxide gas during reaction, environmental pollution is comparatively serious；In addition this three-step approach product yield is relatively low, and production cost is higher.Such as the patent US3660438 preparation method proposing this kind antioxidant a kind of, with β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, thionyl chloride and hydrazine hydrate be raw material, adopt three-steps process, after purifying intermediate products, and under preference temperature after reaction certain time, filtration washing obtains antioxidant product, this method purifying intermediate products complex process, product yield is not high, is not suitable for industrialized production.
Additionally, also there is bibliographical information to adopt Direct Dehydration method technique to prepare such antioxidant product.First base stock (II) generates corresponding intermediate acid (III) after hydrolysis；Simultaneous reactions raw material (II) and hydrazine hydrate or diamine reactant, generate corresponding intermediate list hydrazides or monoamides (IV), then carry out Direct Dehydration between (III) and (IV) two kind of intermediate and Hinered phenols derivant antioxidant product is synthesized.This method is avoided adopting thionyl chloride, decreases the environmental pollution being likely to result in, but owing to raw material adds excessive more than 50%, reclaims comparatively difficulty, cause product cost too high, be unfavorable for promoting the use of.
In formula III and (IV), n, m, R1And R2Definition and formula I in identical.
Summary of the invention
In order to overcome the deficiency of preparation method in prior art, the invention provides the improvement preparation method of a kind of Hinered phenols antioxidant, can not only avoid using thionyl chloride, reduce potential environmental pollution, and adopt " one-step method " directly preparation technology, improve raw material utilization rate, shorten the response time, reduce reaction cost, it is simple to industrialized production.
The preparation method technical scheme of the present invention is: with the ester (II) with hindered phenol structure and hydrazine hydrate or diamine compound for raw material, adopts " one-step method " technique synthesis target product, by adding catalyst, makes reaction be smoothed out；Used catalyst is base catalyst, is such as specifically one or more in sodium hydroxide, potassium hydroxide, Feldalat NM and sodium tert-butoxide, wherein preferred Feldalat NM.After having reacted, directly filtering, filter cake is washed with water to neutrality, obtains target product after drying, and products obtained therefrom adopts infrared, mass spectrum, nuclear-magnetism and liquid chromatograph can confirm as target product.
Dominant response involved in the present invention is:
Wherein, n, m, R1And R2Definition and formula I in identical.Wherein, the straight or branched alkyl containing 1 ~ 6 carbon atom is such as methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group or hexyl, the structurally and functionally mechanism according to antioxidant, it is most preferred that R1And R2For the tert-butyl group.
In reaction involved in the present invention, reaction raw materials ester (II) and hydrazine hydrate or diamine compound mol ratio are preferably 2 ~ 6:1；Reaction temperature is preferably 60 ~ 120 DEG C, and the response time is 6 ~ 12h.Wherein diamidogen is such as ethylenediamine, 1,3 propane diamine, 1,4-butanediamine, pentanediamine or hexamethylene diamine.
At N2Under protection, in the reactor equipped with stirring, condensing tube and thermometer boss, add a certain amount of reaction raw materials ester and hydrazine hydrate or diamine compound, add catalysts and solvents, heat to assigned temperature.When, after temperature stabilization, maintaining certain response time, after having reacted, gained material, after operations such as filtering, wash and be dry, obtains Hinered phenols antioxidant product.
The essential distinction of the present invention and prior art is in that: prior art is to have the ester (II) of hindered phenol structure, hydrazine hydrate or diamidogen, and thionyl chloride etc. is base stock, first synthetic mesophase product, after separated purification, resynthesis target product, whole building-up process does not adopt catalyst.The reaction raw materials of the present invention does not have thionyl chloride, adopts " one-step method " technique, and intermediate product, without separating-purifying, needs in building-up process to use catalyst.
The invention has the beneficial effects as follows: the reaction raw materials of the present invention is avoided using thionyl chloride, decreases potential environmental pollution pressure；Adopting " one-step method " technique synthesis target product, intermediate product is without separating-purifying；Course of reaction uses catalyst, improves raw material service efficiency, shorten the response time, reduce reaction cost, it is simple to industrialized production.
Accompanying drawing explanation
Fig. 1 is the infrared figure of product antioxidant (I) in embodiment 1；
Fig. 2 is the mass spectrum of product antioxidant (I) in embodiment 1.
Detailed description of the invention
Embodiment 1
β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 120g, 85wt% hydrazine hydrate 12g, methanol 220ml, 30wt% caustic lye of soda 30ml, is mixed and heated to boiling, keep 10h, it is cooled to room temperature, filters, add deionized water wash to neutral, 110 DEG C of dry 4h of filter cake, obtain white solid 89g, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that for target product.
Embodiment 2
β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 120g, 85wt% hydrazine hydrate 12g, methanol 220ml, Feldalat NM 2g, be mixed and heated to boiling, keep 8h, it is cooled to room temperature, filters, add deionized water wash to neutral, 110 DEG C of dry 4h of filter cake, obtain white solid 95g, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that for target product.
Embodiment 3
β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 120g, 85wt% hydrazine hydrate 12g, dimethylbenzene 220ml, sodium tert-butoxide 2g, be mixed and heated to boiling, keep 8h, it is cooled to room temperature, filters, add deionized water wash to neutral, 110 DEG C of dry 4h of filter cake, obtain white solid 98g, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that for target product.Comparative example 1
β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 58.5g, 85wt% hydrazine hydrate 30g, methanol 150ml, it is mixed and heated to boiling, keeps 10h, be cooled to room temperature, filter, add deionized water wash to neutral, 110 DEG C of dry 4h of filter cake, obtain white solid 56g, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that the such as single hydrazides shown in above-mentioned formula IV for intermediate product.
β-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 58.5g, thionyl chloride 12g, toluene 100ml, it is slowly heated to 60 DEG C after mixing, maintains 4h, purge with nitrogen, it is then heated to boiling, boil off solvent, add washed with isopropyl alcohol 2 times, obtain white solid, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that for intermediate product propionyl chloride.
Being mixed by two kinds of intermediate products, add dimethylbenzene, heating is boiling extremely, maintains 10h, is cooled to room temperature, filters, and adds washed with isopropyl alcohol 2 times, obtains white solid, through fusing point test, infrared and mass spectrometric measurement, it was demonstrated that for target product.
Claims (7)
1. a preparation method for Hinered phenols antioxidant, ester and hydrazine hydrate including using as shown in formula II are raw material, generate described Hinered phenols antioxidant (I) through a step catalytic reaction under base catalyst exists；
In formula I and (II), R1And R2Selected from hydrogen atom, straight or branched alkyl containing 1～6 carbon atom, n is 1 or 2, m is 0；
Wherein, reaction temperature is 60-120 DEG C, and the response time is 6-12h；
Described base catalyst is one or more in sodium hydroxide, potassium hydroxide, Feldalat NM and sodium tert-butoxide.
2. method according to claim 1, it is characterised in that the described straight or branched alkyl containing 1～6 carbon atom is methyl, ethyl, propyl group, butyl, amyl group or hexyl.
3. method according to claim 2, it is characterised in that described propyl group is isopropyl.
4. method according to claim 2, it is characterised in that described R1 and R2 is the tert-butyl group.
5. method according to claim 1, it is characterised in that the mol ratio of the ester shown in raw material formula II and hydrazine hydrate is 2～6:1.
6. method according to claim 1, it is characterised in that the solvent using methanol or dimethylbenzene to be reaction.
7. the method according to any one in claim 1-6, it is characterised in that described base catalyst is Feldalat NM.
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| CN104496842B (en) * | 2014-12-30 | 2017-01-25 | 天津利安隆新材料股份有限公司 | preparation method of hindered phenol antioxidant 1019 |
| 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 |
| 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 |
| CN118006026B (en) * | 2024-04-10 | 2024-06-18 | 安徽和盛新材料科技有限公司 | Anti-aging polyethylene color master batch and preparation method thereof |
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| CH540954A (en) * | 1970-12-07 | 1973-08-31 | Ciba Geigy Ag | Stabilizer system for polyamides |
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| CN1032646C (en) * | 1990-08-03 | 1996-08-28 | 黑蒙特股份公司 | Process for preparing organic esters and amides and used catalyst system |
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