CN104910008A - Purification method of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate - Google Patents
Purification method of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate Download PDFInfo
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- CN104910008A CN104910008A CN201510272259.6A CN201510272259A CN104910008A CN 104910008 A CN104910008 A CN 104910008A CN 201510272259 A CN201510272259 A CN 201510272259A CN 104910008 A CN104910008 A CN 104910008A
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- butyl
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention provides a purification method of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate. The purification method comprises following steps: A), a 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate crude product is subjected to rectification at a vacuum degree of -0.092MPa or higher, and is heated to 110 to 130 DEG C; B) a crude material obtained via step A) is subjected to rectification at 150 to 180 DEG C; and C) a crude reaction product is subjected to rectification at 170 to 210 DEG C so as to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate. The difference of boiling points of a plurality of substances in the 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate crude product is large, separation of the substances in 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate is realized by controlling rectification pressure and temperature, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate purified product with high purity and yield is obtained.
Description
Technical field
The present invention relates to product purification techniques field, particularly relate to the method for purification of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.
Background technology
3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate (abbreviation 3,5-methyl esters) be a kind of Hinered phenols antioxidant preferably, can be used in the processing of rubber and plastics, simultaneously its be again synthesis antioxidant 1010,1076, the important intermediate of 259 etc., therefore, the research of 3,5-methyl esters synthesis technique is particularly important.3,5-methyl esters be with 2,6 di t butyl phenol (be called for short 2,6-phenol) with methyl acrylate for raw material, under the effect of catalyzer, there is addition reaction obtained.The crude product of what but above-mentioned synthesis technique obtained is 3,5-methyl esters, and the general purity of 3 of industrial employing, 5-methyl esters is higher, therefore 3,5-methyl esters can need use through recrystallization or rectifying.
Obtain 3,5-methyl esters sterling many employings lower alcohols as methyl alcohol, ethanol etc. by 3,5-methyl esters crude product at present, as crystallization and purification solvent, but use the method 3,5-methyl esters product loss large, and produce a large amount of waste liquid.Thus, this application provides the method for purification of a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.
Summary of the invention
The technical problem that the present invention solves is to provide the method for purification of a kind of purity and higher 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of yield.
In view of this, this application provides the method for purification of a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, comprise the following steps:
A), 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product is started rectifying under vacuum tightness is not less than-0.092MPa, and is warming up to 110 DEG C ~ 130 DEG C;
B), by steps A) crude product that obtains carries out rectifying at temperature is 150 DEG C ~ 180 DEG C;
C), by step B) crude product that obtains carries out rectifying at temperature is 170 DEG C ~ 210 DEG C, obtains 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.
Preferably, described 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product comprises 2 of 0.001wt% ~ 5wt%, 6-DI-tert-butylphenol compounds, the methyl acrylate of 0.001wt% ~ 10wt%, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of 80wt% ~ 99.99wt%.
Preferably, steps A) described in the reflux ratio of rectifying be 0:9 ~ 6:1.
Preferably, step B) described in the reflux ratio of rectifying be 2:9 ~ 7:1.
Preferably, step C) described in the reflux ratio of rectifying be 3:9 ~ 9:1.
Preferably, step C) in also comprise after rectifying:
Detect the purity distillating product, start to receive product after qualified, the reflux ratio receiving product is 1:9 ~ 5:2.
Preferably, the purity of described 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product is 80% ~ 99.99%.
This application provides the method for purification of a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.At 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate purification process in, first by 3,5-methyl esters starts rectifying under vacuum tightness is not less than the condition of-0.092MPa, and being warming up to 110 DEG C ~ 130 DEG C gradually, this stage mainly distillates light constituent methyl acrylate, then the crude product obtained is carried out rectifying at 150 DEG C ~ 180 DEG C, mainly distillate light constituent 2,6 di t butyl phenol; Finally the crude product obtained is carried out rectifying at 170 DEG C ~ 210 DEG C, obtain 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate sterling.The application carries out rectifying being not less than under-0.092MPa pressure, and by controlling the temperature of rectifying, the light constituent in 3,5-methyl esters crude product is removed one by one, finally obtain purity and higher 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of yield.Experimental result shows, the present invention purifies the yield of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate obtained can to more than 96%, and purity can reach more than 99%.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses the method for purification of a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, comprise the following steps:
A), 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product is started rectifying under vacuum tightness is not less than-0.092MPa, and is warming up to 110 DEG C ~ 130 DEG C;
B), by steps A) crude product that obtains carries out rectifying at temperature is 150 DEG C ~ 180 DEG C;
C), by step B) crude product that obtains carries out rectifying at temperature is 170 DEG C ~ 210 DEG C, obtains 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.
This application provides a kind of 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate (3,5-methyl esters) method of purification, it is first by 3,5-methyl esters crude product starts rectifying under-0.092MPa and heats up being not less than, treat that the temperature of rectifying rises to 110 DEG C ~ 130 DEG C, methyl acrylate lower for boiling point mainly distillates by this stage, at 150 DEG C ~ 180 DEG C, carry out rectifying again, mainly 2,6 di t butyl phenol is distillated, finally carry out rectifying at 170 DEG C ~ 210 DEG C, testing product purity is more than 99% start to receive product, obtains 3,5-methyl esters sterling.Experimental result shows, the yield of 3,5-methyl esters can reach more than 96%, and purity can reach more than 99%.
3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product comprises 2,6 di t butyl phenol, methyl acrylate, 3,5-methyl esters sterlings and other impurity; Wherein the content of 2,6 di t butyl phenol is 0.001wt% ~ 5wt%, and the content of methyl acrylate is the content of 0.001wt% ~ 10wt%, 3,5-methyl esters sterling is 80% ~ 99.99wt%, and the content of other impurity is 0.001wt% ~ 10wt%.
At 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate purify process in, the application is first by 3,5-methyl esters crude product starts to carry out first time rectifying be not less than the condition of-0.092MPa in vacuum tightness under, and temperature is risen to gradually 110 DEG C ~ 130 DEG C, be preferably 120 DEG C, this stage constantly distillates light constituent in the process heated up, be 110 ~ 130 DEG C to temperature, the light constituents such as methyl acrylate lower for boiling point are distillated.The reflux ratio of described first time rectifying is preferably 0:9 ~ 6:1, is more preferably 2:3 ~ 5:3.The vacuum tightness that described in the application, first time rectifying starts to control is not less than-0.092MPa and is less than-0.1MPa, if vacuum tightness is too small, cause each component boiling point in 3,5-methyl esters crude product higher, rectification temperature is higher, likely causes 3,5-methyl esters to decompose or side reaction occurs.Described in the application, the purity of 3,5-methyl esters is preferably 80% ~ 99.99%.
According to the present invention, after distillating light constituent methyl acrylate, the application then carries out second time rectifying at temperature 150 ~ 180 DEG C, to distillate the light constituents such as 2,6 di t butyl phenol.The temperature of described second time rectifying is preferably 160 DEG C ~ 170 DEG C.The reflux ratio of described second time rectifying is preferably 2:9 ~ 7:1, is more preferably 3:5 ~ 6:3.The all rectifying of the application is all carried out under pressure is not less than-0.092MPa.
The application after distillating light constituent methyl acrylate and 2,6 di t butyl phenol, then carries out rectifying again, for 3, the 5-methyl esters obtaining purity higher are prepared.The temperature of this time rectifying is preferably 170 DEG C ~ 210 DEG C, and the reflux ratio of described rectifying is preferably 3:9 ~ 9:1, is more preferably 4:2 ~ 8:2.Now detect the purity distillating sample, if product purity reaches more than 99%, then start to receive product.In order to ensure the purity of product, while reception product, adjustment reflux ratio is 1:9 ~ 5:2, is more preferably 2:8 ~ 3:7, finally obtains 3,5-methyl esters.
The application, in the process of purification 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, is utilized each boiling point substance to differ comparatively large, is achieved the separation of different substances in 3,5-methyl esters by the temperature controlling rectifying.Experimental result shows, the yield of the present invention 3,5-methyl esters can reach more than 96%, and purity can reach more than 99%.
In order to understand the present invention further, be described in detail below in conjunction with the method for purification of embodiment to 3-provided by the invention (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Get purity be 90.2% 3,5-methyl esters crude product 450.0g join in 1000mL there-necked flask, open vacuum pump, controls vacuum tightness be-0.098MPa, and arranging reflux ratio is 3:4, unlatching heat, column temperature rises to 120 DEG C gradually, distillates light constituent methyl acrylate etc.After about 1h, arranging column temperature is 170 DEG C, and arranging reflux ratio is 6:3, distillates light constituent 2,6 di t butyl phenol etc.After about 1h, arranging column temperature is 190 DEG C, and reflux ratio is 8:2, get instantaneous sample to detect, treat that product purity is more than 99%, change receiving bottle and start to receive product, adjustment reflux ratio is 3:8, after about 8h, distillates very slow, a small amount of residue is remained in flask, stop heating, rectifying terminates, and obtain that 392.5g purity is 99.5% 3,5-methyl esters product, calculating separation yield is 96.7%.
Embodiment 2
Get purity be 90.2% 3,5-methyl esters crude product 450.0g join in 1000mL there-necked flask, open vacuum pump, control vacuum tightness is more than-0.099MPa, and arranging reflux ratio is 5:3, opens heating, column temperature rises to 120 DEG C gradually, distillates light constituent methyl acrylate etc.After about 1h, arranging column temperature is 150 DEG C, and arranging reflux ratio is 4:3, distillates light constituent 2,6 di t butyl phenol etc.After about 1h, arranging column temperature is 170 DEG C, and reflux ratio is 7:3, get instantaneous sample to detect, treat that product purity is more than 99%, change receiving bottle and start to receive product, adjustment reflux ratio is 3:7, after about 10h, distillates very slow, a small amount of residue is remained in flask, stop heating, rectifying terminates, and obtain that 394.1g purity is 99.3% 3,5-methyl esters product, calculating separation yield is 97.1%.
Embodiment 3
Get purity be 90.2% 3,5-methyl esters crude product 450.0g join in 1000mL there-necked flask, open vacuum pump, controls vacuum tightness be-0.092MPa, and arranging reflux ratio is 2:3, unlatching heat, column temperature rises to 120 DEG C gradually, distillates light constituent methyl acrylate etc.After about 1h, arranging column temperature is 180 DEG C, and arranging reflux ratio is 3:5, distillates light constituent 2,6 di t butyl phenol etc.After about 1h, arranging column temperature is 210 DEG C, and reflux ratio is 4:2, gets instantaneous sample and detects, treat that product purity is more than 99%, change receiving bottle and start to receive product, adjustment reflux ratio is 2:8, after about 7h, distillate very slow, remain a small amount of residue in flask, stop heating, rectifying terminates.Obtain 3, the 5-methyl esters products that 390.5g purity is 99.2%, calculating separation yield is 96.2%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. the method for purification of 3-(3, a 5-di-tert-butyl-hydroxy phenyl) methyl propionate, comprises the following steps:
A), 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product is started rectifying under vacuum tightness is not less than-0.092MPa, and is warming up to 110 DEG C ~ 130 DEG C;
B), by steps A) crude product that obtains carries out rectifying at temperature is 150 DEG C ~ 180 DEG C;
C), by step B) crude product that obtains carries out rectifying at temperature is 170 DEG C ~ 210 DEG C, obtains 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate.
2. method of purification according to claim 1, it is characterized in that, described 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product comprises 2 of 0.001wt% ~ 5wt%, 6-DI-tert-butylphenol compounds, the methyl acrylate of 0.001wt% ~ 10wt%, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of 80wt% ~ 99.99wt%.
3. method of purification according to claim 1 and 2, is characterized in that, steps A) described in the reflux ratio of rectifying be 0:9 ~ 6:1.
4. method of purification according to claim 1 and 2, is characterized in that, step B) described in the reflux ratio of rectifying be 2:9 ~ 7:1.
5. method of purification according to claim 1 and 2, is characterized in that, step C) described in the reflux ratio of rectifying be 3:9 ~ 9:1.
6. method of purification according to claim 1 and 2, is characterized in that, step C) in also comprise after rectifying:
Detect the purity distillating product, start to receive product after qualified, the reflux ratio receiving product is 1:9 ~ 5:2.
7. method of purification according to claim 1, is characterized in that, the purity of described 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate crude product is 80% ~ 99.99%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733691A (en) * | 2004-08-12 | 2006-02-15 | 天津市晨光化工有限公司 | Industrial synthesis method of 3,5-di tertiary butyl-4-hydroxyl phenyl methyl propionate |
| CN101092362A (en) * | 2007-07-06 | 2007-12-26 | 上海金海雅宝精细化工有限公司 | Method for preparing 3,5 - di-tert-butyl - hydroxy phenyl methyl propionate |
| CN102060701A (en) * | 2010-12-27 | 2011-05-18 | 营口市风光化工有限公司 | Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate |
| CN104387274A (en) * | 2014-11-21 | 2015-03-04 | 黄峰 | Process for preparing beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate |
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- 2015-05-25 CN CN201510272259.6A patent/CN104910008A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733691A (en) * | 2004-08-12 | 2006-02-15 | 天津市晨光化工有限公司 | Industrial synthesis method of 3,5-di tertiary butyl-4-hydroxyl phenyl methyl propionate |
| CN101092362A (en) * | 2007-07-06 | 2007-12-26 | 上海金海雅宝精细化工有限公司 | Method for preparing 3,5 - di-tert-butyl - hydroxy phenyl methyl propionate |
| CN102060701A (en) * | 2010-12-27 | 2011-05-18 | 营口市风光化工有限公司 | Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate |
| CN104387274A (en) * | 2014-11-21 | 2015-03-04 | 黄峰 | Process for preparing beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate |
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Application publication date: 20150916 |