CN102060701B - Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate - Google Patents
Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate Download PDFInfo
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Abstract
The invention relates to a method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate. The technical scheme comprises the following steps of: adding 2,6-di-tert-butyl phenol into a reaction kettle, vacuumizing, displacing hydrogen for more than three times, raising the temperature to be between 55 and 60 DEG C, adding a catalyst, stirring, continuously raising the temperature to be between 90 and 115 DEG C, and dehydrating to obtain slurry; reducing the temperature of the obtained slurry to be between 90 and 97 DEG C, dripping methyl acrylate into the reaction kettle by using an annular dropper which is inserted into the bottom of the reaction kettle, controlling the temperature to be between 95 and 105 DEG C, filling the nitrogen until pressure is between 0.4 and 0.6MPa after dripping is finished, controlling the temperature to be between 95 and 105 DEG C, preserving heat and reacting for 1.5 to 2.5 hours; and reducing the temperature to be between 75 and 85 DEG C, vacuumizing, adding organic acid, reacting for 10 to 20 minutes, filtering, and purifying to obtain a product. By the method, the reaction temperature can be reduced, reaction time is shortened, side reaction is reduced, and the quality and yield of the product are improved.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of compound method of producing midbody β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of Hinered phenols antioxidant particularly.
Background technology
Oxidation inhibitor can delay or stop synthetic materials oxidation or autoxidation process, thereby prolongs the work-ing life of material, and it is used and almost relates to all polymer products.The general consumption of oxidation inhibitor is less, and is less to the polymer machinery performance impact after adding.Polyphenol antioxidant 1010 and 1076 is present better oxidation inhibitor leading product, and its consumption accounts for about 40 % of oxidation inhibitor aggregate consumption.
β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is the anti-agent of a kind of good Hinered phenols, to plastics such as Vilaterm, Vestolen PP 7052, SE, animal oil, multiple organic high molecular compound such as the rubber anti-aging function that all tool is good.In addition; β-(3; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate is not only the main intermediate of producing antioxidant 1010, also is the main intermediate of producing high-grade oxidation inhibitor such as oxidation inhibitor 259,1035,1076,1098 and 3125, therefore also can be used as commodity selling.
But the synthetic but relative complex of midbody β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, and reaction time is long, and it is very easily oxidized to control bad reaction product, thereby influences next step reaction.The subject matter that exists in the existing compound method is: added solvent in the 1. addition reaction technology, increased cost to reaction, and difficult solvent recovery, cause environmental pollution easily.2. the catalyzer cost that is adopted is high, like potassium tert.-butoxide, has improved production cost.3. owing to the restriction of catalyst activity condition, temperature of reaction is controlled between 80-130 ℃, skilled in the art will recognize that; Autohemagglutination takes place in methyl acrylate easily, forms dimer or polymer, this dipolymer and 2; The reaction of 6-DI-tert-butylphenol compounds generates diester, has increased by product, along with temperature rising speed of response can be accelerated; But after temperature is raised to certain value, can causes generating to side reactions such as phenol, paraquinones aggravation, thereby influence midbody β-(3; The 5-di-tert-butyl-hydroxy phenyl) quality of methyl propionate and productive rate, and further influence the quality and the yield of follow-up transesterification reaction and antioxidant 1010 product.4. be to make 2 in the reversible reaction in reaction process; The 6-DI-tert-butylphenol compounds fully reacts, and adopts excessive methyl acrylate more, and excessive common minimum is 1.08:1 [mol ratio]; This has increased possibility and production cost that side reaction takes place undoubtedly, and influences product gas purity and ultimate yield.
Therefore, how controlling the side reaction of addition reaction effectively, reduce by product, is the key of improving the quality of products, improving product yield, reduce production costs.
Summary of the invention
In order to overcome the above problems, the present invention provides the method for a kind of synthetic β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate.Adopt this method can reduce temperature of reaction, reduce the reaction times, and then reduce the generation of side reaction, improve the quality of products and yield.
The present invention realizes through following technical scheme: the method for a kind of synthetic β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is characterized in that: in reaction kettle, add 2,6 di t butyl phenol; Vacuumize, nitrogen replacement is warming up to 55 ~ 60 ℃ more than 3 times, adds catalyzer; Stir, continue to be warmed up to 90-115 ℃, dewater slurries, the slurries that obtain are cooled to 90-97 ℃; Through annular dropper dropwise addition of acrylic acid methyl esters in reaction kettle of insertion reaction still bottom, temperature is controlled between 95-105 ℃, and charging into nitrogen to pressure after being added dropwise to complete is 0.4MP-0.6MP, and controlled temperature is between 95-105 ℃; Insulation reaction 1.5-2.5 hour, cool to 75-85 ℃, vacuumize, add organic acid; Reaction 10-20min filters, and purifies, and gets product.
The mol ratio of described methyl acrylate and 2,6 di t butyl phenol is 1:1～1.1:1.Preferably, the mol ratio of methyl acrylate and 2,6 di t butyl phenol is 1.02:1～1.05:1.
Described catalyzer is an alkali metal hydroxide, and its consumption is 0.5% ~ 2% of a 2,6 di t butyl phenol weight.Preferably, alkali metal hydroxide is a Pottasium Hydroxide.Choosing is more arranged, and alkali metal hydroxide is 50% potassium hydroxide aqueous solution.
Described organic acid is formic acid or acetate, and its mole dosage is 1.05 ~ 1.1 times of catalyzer.
Reaction mechanism of the present invention is: in the presence of catalyzer, adopt nitrogen pressure and methyl acrylate directly to be distributed to the mode in the liquid-phase system of 2,6 di t butyl phenol; Make 2,6 di t butyl phenol and methyl acrylate carry out addition reaction, after reaction finishes; Add the organic acid neutralization and remove catalyzer; Filter, purifying obtains β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate.
The invention has the beneficial effects as follows: compared with prior art, the mode of nitrogen pressure provided by the invention is carried out addition reaction, can reduce temperature of reaction, reduces the reaction times; Can reduce the generation of side reaction, improve the quality of products and yield, catalyzer adopts Pottasium Hydroxide simultaneously; Raw material is easy to get, and price is low, has practiced thrift production cost; The β that obtains-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate finished product, the GC display result; Product yield can reach more than 98%, and the content of β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate can be up to more than 99.5% in the product after purifying with the method for rectification and purification.
Description of drawings
Fig. 1 is the structural representation of annular dropper.
Fig. 2 is the upward view of Fig. 1.
Embodiment
Further specify the present invention through concrete exemplifying embodiment below, these exemplifying embodiments are only used for the usefulness of explanation more in detail particularly, limit the present invention in any form and be not used in.It will be apparent to those skilled in the art that hereinafter if any specified otherwise, raw material that the present invention selected for use and working method are that those skilled in the art are known.
In 1 liter stainless steel cauldron of the airtight annular dropper as depicted in figs. 1 and 2 that has reflux exchanger, mechanical stirring, trap, nitrogen gas tube, vacuum pipe and insertion reaction still bottom (label 1 is for dripping the hole among the figure), add 309g (1.5mol) 2,6 di t butyl phenol, vacuumize; Nitrogen replacement is heated between 55 ~ 60 ℃ to reaction kettle more than 3 times, continues to vacuumize; Under negative pressure, and adding 3.71g (0.033mol, weight is about 2; The 6-DI-tert-butylphenol compounds 0.6%) 50% the KOH aqueous solution, open and stir, continue to be warmed up to 90-115 ℃ again; Deviate from the water (do not effluent be as the criterion with water) that the reaction of reaction system and catalyzer and 2.6-DI-tert-butylphenol compounds generated and collect in the cold-trap, resulting slurries in the reaction kettle are cooled to 95 ℃, and begin in reaction kettle, to drip 131.6g (1.53mol) methyl acrylate; Methyl acrylate is distributed in the slurries through insertion reaction still base circle dropper, and the control drop rate drips off in 30min; Thermopositive reaction is in the dropping process, and temperature is controlled between 95-105 ℃, after being added dropwise to complete; Charging into nitrogen to pressure is 0.5MP, and controlled temperature insulation reaction 2 hours between 95-105 ℃, cools to about 80 ℃ to reaction system; System is evacuated to-0.1Mp, adds 1.6 (0.035gmol) formic acid, neutralization reaction 15min; Continue to be warmed up to 120 ℃, excessive unreacted methyl acrylate of vacuum removal and excessive formic acid, about 20 ~ 30min; Not slipping with liquid is as the criterion, and removes the organic salt compound that dereaction generates through filtering method, thick product.
Product detects through ir spectra, at 1710cm
-1, 2500-3300cm
-1The narrow peak at place judges it is the C=O absorption peak, 3630cm
-1And 1216cm
-1Be the phenolic hydroxyl group absorption peak, 876 cm
-1Be phenyl ring 1,2,3,5 four substituent absorption peaks.Therefore, verify that the product that makes is β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate; With GC assay products component, the content of β in the result product-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is 98.9%; The content of 2,6 di t butyl phenol is 1.04%.Crude product is carried out rectification and purification, analyze the sample after purifying with GC, wherein the content of β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate can reach more than 99.5%.
Embodiment 2
In 1 liter stainless steel cauldron of the airtight annular dropper that has reflux exchanger, mechanical stirring, trap, nitrogen gas tube, vacuum pipe and insertion reaction still bottom, add 400g (1.94mol) 2,6 di t butyl phenol, vacuumize; Nitrogen replacement is heated between 55 ℃ ~ 60 to reaction kettle more than 3 times, continues to vacuumize, under negative pressure; Add 5g (0.045mol, weight be about 2,6 di t butyl phenol 0.625%) 50% the KOH aqueous solution; Open to stir, continue again to be warmed up to 90-110 ℃, deviate from reaction system and catalyzer and 2.6-DI-tert-butylphenol compounds and react the water that generated (do not effluent be as the criterion with water) and collect in the cold-trap; Resulting slurries in the reaction kettle are cooled to 95 ℃, and begin to drip 175g (2.03 mol) methyl acrylate, the control drop rate to reaction kettle; In 30min, drip off, thermopositive reaction is in the dropping process, and temperature is controlled between 95-105 ℃; Charging into nitrogen to pressure after being added dropwise to complete is 0.4MP, and controlled temperature insulation reaction 3 hours between 95-105 ℃, cools to about 80 ℃ to reaction system; System is evacuated to-0.1Mp, adds 2.82g (0.047mol) acetate, neutralization reaction 15min; Continue to be warmed up to 120 ℃, excessive unreacted methyl acrylate of vacuum removal and excessive acetate, about 20 ~ 30min; Not slipping with liquid is as the criterion, and removes the organic salt compound that dereaction generates through filtering method, thick product.
Product detects through ir spectra, at 1710cm
-1, 2500-3300cm
-1The narrow peak at place judges it is the C=O absorption peak, 3630cm
-1And 1216cm
-1Be the phenolic hydroxyl group absorption peak, 876 cm
-1Be phenyl ring 1,2,3,5 four substituent absorption peaks.Therefore, verify that the product that makes is β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate; With GC assay products component, the content of β in the result product-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is 98.32%; The content of 2,6 di t butyl phenol is 1.17%.Crude product is carried out rectification and purification, analyze the sample after purifying with GC, wherein the content of β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate can reach more than 99.5%.
Embodiment 3
In 1 liter stainless steel cauldron of the airtight annular dropper that has reflux exchanger, mechanical stirring, trap, nitrogen gas tube, vacuum pipe and insertion reaction still bottom, add 309g (1.5 mol) 2,6 di t butyl phenol, vacuumize; Nitrogen replacement is heated between 55 ~ 60 ℃ to reaction kettle more than 3 times, continues to vacuumize, under negative pressure; Add 6.18g (0.055mol, weight be about 2,6 di t butyl phenol 1%) 50% the KOH aqueous solution; Open to stir, continue again to be warmed up to 90-115 ℃, deviate from reaction system and catalyzer and 2.6-DI-tert-butylphenol compounds and react the water that generated (do not effluent be as the criterion with water) and collect in the cold-trap; Resulting slurries in the reaction kettle are cooled to 90 ℃, and begin to drip 135g (1.57mol) methyl acrylate, the control drop rate to reaction kettle; In 30min, drip off, thermopositive reaction is in the dropping process, and temperature is controlled between 95-105 ℃; Charging into nitrogen to pressure after being added dropwise to complete is 0.6MP, and controlled temperature insulation reaction 3 hours between 90-100 ℃, cools to about 80 ℃ to reaction system; System is evacuated to-0.1Mp, adds 2.67g (0.058mol) formic acid, neutralization reaction 15min; Continue to be warmed up to 115 ℃, excessive unreacted methyl acrylate of vacuum removal and excessive formic acid, about 20 ~ 30min; Not slipping with liquid is as the criterion, and removes the organic salt compound that dereaction generates through filtering method, thick product.
Product detects through ir spectra, at 1710cm
-1, 2500-3300cm
-1The narrow peak at place judges it is the C=O absorption peak, 3630cm
-1And 1216cm
-1Be the phenolic hydroxyl group absorption peak, 876 cm
-1Be phenyl ring 1,2,3,5 four substituent absorption peaks.Therefore, verify that the product that makes is β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate; With GC assay products component, the content of β in the result product-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is 98.51%; The content of 2,6 di t butyl phenol is 1.36%.Crude product is carried out rectification and purification, analyze the sample after purifying with GC, wherein the content of β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate can reach more than 99.5%.
Claims (2)
1. the method for synthetic β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is characterized in that: in reaction kettle, add 2,6 di t butyl phenol; Vacuumize, nitrogen replacement is warming up to 55～60 ℃ more than 3 times, adds the catalyzer alkali metal hydroxide; Stir, continue to be warmed up to 90-115 ℃, dewater slurries, the slurries that obtain are cooled to 90-97 ℃; Through annular dropper dropwise addition of acrylic acid methyl esters in reaction kettle of insertion reaction still bottom, temperature is controlled between 95-105 ℃, and charging into nitrogen to pressure after being added dropwise to complete is 0.4MP-0.6MP, and controlled temperature is between 95-105 ℃; Insulation reaction 1-3 hour, cool to 75-85 ℃, vacuumize, add organic acid; Reaction 10-20min filters, and purifies, and gets product.
2. according to the method for the described synthetic β of claim 1-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: the mol ratio of methyl acrylate and 2,6 di t butyl phenol is 1:1～1.1:1.
3. according to the method for the described synthetic β of claim 2-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: the mol ratio of methyl acrylate and 2,6 di t butyl phenol is 1.02:1～1.05:1.
4. according to the method for the described synthetic β of claim 1-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: described catalyzer alkali metal hydroxide, its consumption are 0.5%～2% of 2,6 di t butyl phenol weight.
5. according to the method for the described synthetic β of claim 4-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: described alkali metal hydroxide is a Pottasium Hydroxide.
6. according to the method for the described synthetic β of claim 5-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: described alkali metal hydroxide is 50% potassium hydroxide aqueous solution.
7. according to the method for the described synthetic β of claim 1-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is characterized in that: described organic acid is formic acid or acetate, and its mole dosage is 1.05～1.1 times of catalyzer.
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| CN104387274A (en) * | 2014-11-21 | 2015-03-04 | 黄峰 | Process for preparing beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate |
| CN104910007A (en) * | 2015-04-24 | 2015-09-16 | 新乡市瑞丰新材料股份有限公司 | 3-(3, 5-ditertiary butyl-4-hydroxy phenyl) methyl propionate synthesis process |
| CN104910008A (en) * | 2015-05-25 | 2015-09-16 | 新乡市瑞丰新材料股份有限公司 | Purification method of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate |
| CN106518687A (en) * | 2016-09-09 | 2017-03-22 | 华东理工大学 | Efficient preparation method of high-purity tetraethyl ammonium chloride |
| CN112538204A (en) * | 2020-12-02 | 2021-03-23 | 广州市奇胜电线电缆有限公司 | Wear-resistant and tensile-resistant halogen-free wire and cable and manufacturing method thereof |
| CN113429659A (en) * | 2021-07-12 | 2021-09-24 | 安徽瑞丰管业有限公司 | Production process of high-wear-resistance glass steel tube |
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| 刘涛等.3 5-二叔丁基-4-羟基苯基丙酸甲酯的合成与工艺改进.《化工技术与开发》.2010 |
| 刘涛等.3,5-二叔丁基-4-羟基苯基丙酸甲酯的合成与工艺改进.《化工技术与开发》.2010,第39卷(第5期),25-27. * |
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Address after: 115005, Yingkou, Liaoning Province, the old border road south Zhenjiang home Patentee after: Yingkou scenery new material Limited by Share Ltd Address before: 115005, 519, Jiang Jia village, old border area, Liaoning, Yingkou Patentee before: Yingkou Viewchem Co., Ltd. |