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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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 28
- 150000002989 phenols Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- -1 Putriscine Chemical compound 0.000 abstract description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 20
- 239000013067 intermediate product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229940017219 methyl propionate Drugs 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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| Title |
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| 抗氧抗铜剂1024的合成研究;殷伟芬等;《应用化工》;20031231;第32卷(第6期);第38-40页 * |
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| CN103508923A (en) | 2014-01-15 |
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