CN105294441B - [the β of antioxidant eight（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester synthetic method - Google Patents
[the β of antioxidant eight（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester synthetic method Download PDFInfo
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- CN105294441B CN105294441B CN201510909615.0A CN201510909615A CN105294441B CN 105294441 B CN105294441 B CN 105294441B CN 201510909615 A CN201510909615 A CN 201510909615A CN 105294441 B CN105294441 B CN 105294441B
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- butyl
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- tripentaerythritol
- propionic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Abstract
The present invention relates to a kind of [β of antioxidant eight（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester synthetic method, this method is by β（The hydroxy phenyl of 3,5 di-t-butyl 4）With tripentaerythritol ester exchange reaction occurs for methyl acrylate, obtains the solid antioxidants with eight antioxidant groups.[the β of antioxidant eight that the present invention is synthesized（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester, embedded substantial amounts of phenols antioxidant groups in structure, with good antioxidation outside.Meanwhile, [the β of antioxidant eight that the present invention is synthesized（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester product, as ester type compound, with higher biodegradability, more conforms to the requirement of environmental protection.It is widely used in the fields such as general-purpose plastics, engineering plastics, synthetic rubber, coating, oil product.
Description
Technical field
The present invention relates to a kind of antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] tripentaerythritol ester
Synthetic method.
Background technology
Tripentaerythritol is fine-chemical intermediate, senior lubricant and its additive, polyurethane, PVC heat stabilizer,
Had a wide range of applications in terms of plasticizer, fireproof agent and coating, ink, cosmetics, particularly bipentaerythrite and three seasons
Penta tetrol has the incomparable advantage of monopentaerythritol in terms of senior aeroengine oil, photoactive coating and ink.Three seasons
Penta 4 alcohol fatty acid esters are a kind of advanced lubrication oil base oils, are had a wide range of applications in terms of Aero-Space, precision instrument.
Oxidation deterioration phenomenon can all occur for most of industrial organic materials such as lubricating oil, cutting fluid.Lubricating oil was being used
Cheng Zhong, due to often or for a long time ingress of air at relatively high temperatures, can oxidation deterioration cause viscosity to increase and produce gel
And impurity, greasy property is reduced, accelerates the corrosion and abrasion of equipment.Antioxidant can eliminate generation during lubricating oil use
Free radical and free radical, effectively delay oil ageing go bad, extend machinery equipment service life.2,6- di-t-butyls pair
Cresols (antioxidant T501) is most popular phenolic antioxidant kind, and consumption is 0.1%-1.0%.The letter of its manufacturing process
Single, cost is low but volatile, and antioxidant effect can not be lasting, and thermal weight loss temperature is low, should not use at high temperature.This is also current
The shortcoming of most of hindered phenol anti-oxidants.Polyphenol antioxidation agent in the present invention can form macromolecular compound, and reduction is waved
Hair property, improves thermal weight loss temperature, can use at high temperature, while the formation of deposit in oil product can be preferably controlled, consumption
Also it is larger.Meanwhile, phenolic ester type antioxidant not polluted water is biodegradable, is a kind of environment-friendly antioxidant.
The content of the invention
It is an object of the invention to provide a kind of antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] three seasons
The synthetic method of Doutrate, this method is by β-(3,5- di-tert-butyl-hydroxy phenyl) methyl acrylate and tripentaerythritol
Generation ester exchange reaction, obtains the solid antioxidants with eight antioxidant groups.Antioxidant eight that the present invention is synthesized [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] tripentaerythritol ester, embedded substantial amounts of phenols antioxidant groups, tool in structure
Have outside good antioxidation.Meanwhile, [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight of the method for the invention synthesis
Base phenyl) propionic acid] tripentaerythritol ester product is as ester type compound, with higher biodegradability, more conforms to green
The requirement that colour circle is protected.
A kind of antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] tripentaerythritol of the present invention
The synthetic method of ester, follows these steps to carry out：
A, by β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate, tripentaerythritol and catalyst be sodium methoxide,
Potassium tert-butoxide or dibutyltin oxide are mixed in the reactor, and stirring is warming up to 100-190 DEG C, control reactor pressure 650Pa,
Reaction 4-8 hours, obtains mixture；
B, the mixture for obtaining step a cool, and with recrystallizing methanol, are filtrated to get [the β-(3,5- bis- uncles of antioxidant eight
Butyl -4- hydroxy phenyls) propionic acid] tripentaerythritol ester.
The mol ratio of β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate and tripentaerythritol is in step a
8.5:1。
Catalyst accounts for the 0.3%-1.0% of total quality of material in step a.
[β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] three seasons penta of antioxidant eight that the method for the invention is obtained
The structural formula of four alcohol esters is：
Antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] tripentaerythritol ester of the present invention
Synthetic method, this method by β -3,5- di-tert-butyl-hydroxy phenyl methyl propionates and tripentaerythritol by ester exchange reaction,
Synthesize polyphenol antioxidation agent.[β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] three seasons of antioxidant eight of this method synthesis
Doutrate, with outstanding feature：1. antioxidant groups are more, and 8 antioxidant groups, energy are contained in an antioxidant structure
Preferably play antioxidant effect；2. molecular weight is big, and heat endurance is good, is more suitable for using under hot conditions, is a kind of excellent
High-temperature anti-oxidant.3. antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] tripentaerythritol synthesized
Ester has the structure of synthetic ester, biodegradable, is a kind of good hindered phenol anti-oxidants of new, feature of environmental protection.
Brief description of the drawings
Fig. 1 is infrared spectrogram of the present invention, it can be seen that in 3648cm-1Place occurs in that the feature of phenolic hydroxyl group is inhaled
Peak is received, in 1746cm-1Place occurs in that the stretching vibration absworption peak of C=O bond in ester group.3000cm-1-3500cm-1Place does not occur
Any absworption peak, the alcoholic extract hydroxyl group that this explanation is passed through in ester exchange reaction, tripentaerythritol has had completely reacted.
Embodiment
Following example is that the present invention is further illustrated, rather than is limited the invention.
Embodiment 1
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent sodium methoxide 0.086g, is mixed in the reactor, and stirring is warming up to 100 DEG C, controls reactor pressure 650Pa, is reacted 8 hours,
Obtain mixture
By the cooling of obtained mixture, with recrystallizing methanol, [the β-(3,5- di-t-butyl -4- of antioxidant eight is filtrated to get
Hydroxy phenyl) propionic acid] tripentaerythritol ester.
Embodiment 2
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent potassium tert-butoxide 0.086g, after mixing in the reactor, stirring is warming up to 120 DEG C, controls reactor pressure 650Pa, and reaction 7 is small
When, obtain mixture；
By the cooling of obtained mixture, with recrystallizing methanol, [the β-(3,5- di-t-butyl -4- of antioxidant eight is filtrated to get
Hydroxy phenyl) propionic acid] tripentaerythritol ester.
Embodiment 3
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent sodium methoxide 0.114g, after mixing in the reactor, stirring is warming up to 130 DEG C, controls reactor pressure 650Pa, and reaction 6.5 is small
When, obtain mixture
By the cooling of obtained mixture, with recrystallizing methanol, [the β-(3,5- di-t-butyl -4- of antioxidant eight is filtrated to get
Hydroxy phenyl) propionic acid] tripentaerythritol ester.
Embodiment 4
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent dibutyltin oxide 0.114g, after mixing in the reactor, stirring is warming up to 150 DEG C, controls reactor pressure 650Pa, instead
Answer 6 hours, obtain mixture；
By the cooling of obtained mixture, with recrystallizing methanol, [the β-(3,5- di-t-butyl -4- of antioxidant eight is filtrated to get
Hydroxy phenyl) propionic acid] tripentaerythritol ester.
Embodiment 5
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent dibutyltin oxide 0.2854g, after mixing in the reactor, stirring is warming up to 145 DEG C, controls reactor pressure 650Pa, instead
Answer 6 hours, obtain mixture；
Obtained mixture cooling, with recrystallizing methanol, is filtrated to get [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Base phenyl) propionic acid] tripentaerythritol ester.
Embodiment 6
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent dibutyltin oxide 0.21g, after mixing in the reactor, stirring is warming up to 155 DEG C, controls reactor pressure 650Pa, reaction
5.5 hours, obtain mixture.
Obtained mixture cooling, with recrystallizing methanol, is filtrated to get [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Base phenyl) propionic acid] tripentaerythritol ester.
Embodiment 7
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent dibutyltin oxide 0.18g, after mixing in the reactor, stirring is warming up to 170 DEG C, controls reactor pressure 650Pa, reaction
5 hours, obtain mixture；
Obtained mixture cooling, with recrystallizing methanol, is filtrated to get [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Base phenyl) propionic acid] tripentaerythritol ester.
Embodiment 8
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent potassium tert-butoxide 0.18g, after mixing in the reactor, stirring is warming up to 190 DEG C, controls reactor pressure 650Pa, and reaction 4 is small
When, obtain mixture；
Obtained mixture cooling, with recrystallizing methanol, is filtrated to get [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Base phenyl) propionic acid] tripentaerythritol ester.
Embodiment 8
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent sodium methoxide 0.155g, after mixing in the reactor, stirring is warming up to 180 DEG C, controls reactor pressure 650Pa, and reaction 4.5 is small
When, obtain mixture；
Cool after the completion of obtained mixture, with recrystallizing methanol, be filtrated to get [the β-(3,5- bis- tertiary fourths of antioxidant eight
Base -4- hydroxy phenyls) propionic acid] tripentaerythritol ester.
Embodiment 9
Weigh β-(3,5- di-tert-butyl-hydroxy phenyls) methyl acrylate 24.82g, tripentaerythritol 3.72g, catalysis
Agent dibutyltin oxide 0.13g, after mixing in the reactor, stirring is warming up to 175 DEG C, controls reactor pressure 650Pa, reaction
5 hours, obtain mixture；
Obtained mixture cooling, with recrystallizing methanol, is filtrated to get [the β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Base phenyl) propionic acid] tripentaerythritol ester.
Antioxidant eight [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] tripentaerythritol ester of the present invention
Synthetic method, this method is from infrared spectrum it can be seen from the figure that：In 3648cm-1Place occurs in that the characteristic absorption peak of phenolic hydroxyl group,
1746cm-1Place occurs in that the stretching vibration absworption peak of C=O bond in ester group；3000cm-1-3500cm-1Place does not occur any suction
Peak is received, the alcoholic extract hydroxyl group that this explanation is passed through in ester exchange reaction, tripentaerythritol has had completely reacted.
Infrared absorpting light spectra can prove that the inventive method prepares the [β-(3,5- di-t-butyl -4- hydroxyls of antioxidant eight
Phenyl) propionic acid] tripentaerythritol ester is feasible.
Claims (1)
1. a kind of antioxidant eight [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] tripentaerythritol ester synthetic method,
It is characterized in that following these steps to carry out：
A, by β-（3,5- di-tert-butyl-hydroxy phenyls）Methyl propionate, tripentaerythritol and catalyst are sodium methoxide, the tert-butyl alcohol
Potassium or dibutyltin oxide are mixed in the reactor, and stirring is warming up to 100-190 DEG C, control reactor pressure 650Pa, react 4-
8 hours, obtain mixture, wherein β-（3,5- di-tert-butyl-hydroxy phenyls）The mol ratio of methyl propionate and tripentaerythritol
For 8.5:1；Catalyst accounts for the 0.3%-1.0% of total quality of material；
B, the mixture for obtaining step a cool, with recrystallizing methanol, be filtrated to get antioxidant eight [β-（The tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls）Propionic acid] tripentaerythritol ester.
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| CN201510909615.0A CN105294441B (en) | 2015-12-10 | 2015-12-10 | [the β of antioxidant eight（The hydroxy phenyl of 3,5 di-t-butyl 4）Propionic acid] tripentaerythritol ester synthetic method |
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| CN110862317B (en) * | 2019-12-02 | 2022-04-22 | 山东省临沂市三丰化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN111334300A (en) * | 2020-04-01 | 2020-06-26 | 辽宁石化职业技术学院 | Preparation method of double-effect antioxidant |
| CN112266531A (en) * | 2020-09-24 | 2021-01-26 | 句容市百事特复合材料有限公司 | Low-odor long fiber reinforced polypropylene granule composition and preparation method thereof |
| CN114149846B (en) * | 2021-10-29 | 2022-11-29 | 东风商用车有限公司 | Short-mileage diesel engine lubricating oil and preparation method thereof |
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| JPH0710807B2 (en) * | 1987-02-03 | 1995-02-08 | 吉富製薬株式会社 | Method for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
| JPH0745437B2 (en) * | 1988-03-18 | 1995-05-17 | 吉富製薬株式会社 | Method for producing ester |
| US5136082A (en) * | 1990-08-03 | 1992-08-04 | Himont Incorporated | Process for preparing organic esters and amides and catalyst system therefor |
| ES2259325T3 (en) * | 2000-06-23 | 2006-10-01 | Ciba Specialty Chemicals Holding Inc. | PROCEDURE FOR OBTAINING ESTERS OF HYDROXYPHENYL CARBOXYL ACIDS. |
| CN102492524B (en) * | 2011-11-15 | 2013-12-11 | 中国科学院新疆理化技术研究所 | Synthesis method for liquid phenolic ester type antioxidants |
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| Title |
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| Synthesis and characterisation of antioxidant-modified esters of dipentaerythritol as lubricating base oil;Letao Zhang等;《LUBRICATION SCIENCE》;20130329;第25卷;329-337 * |
| Synthesis and characterization of novel liquid ester-phenolic antioxidant based on dipentaerythritol;Letao Zhang;《LUBRICATION SCIENCE》;20120912;第25卷;209-216 * |
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