CN103193635B - Method for preparing antioxidant bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester - Google Patents
Method for preparing antioxidant bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester Download PDFInfo
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- CN103193635B CN103193635B CN201310119217.XA CN201310119217A CN103193635B CN 103193635 B CN103193635 B CN 103193635B CN 201310119217 A CN201310119217 A CN 201310119217A CN 103193635 B CN103193635 B CN 103193635B
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- butyl
- tert
- hydroxy phenyl
- catalyzer
- methyl propionate
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- 238000000034 method Methods 0.000 title abstract description 9
- 239000003963 antioxidant agent Substances 0.000 title abstract description 3
- 230000003078 antioxidant effect Effects 0.000 title abstract description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims abstract description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940017219 methyl propionate Drugs 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- -1 propionic acid butanediol ester Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000012044 organic layer Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing an antioxidant bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester. The method comprises the steps of: reacting 3-(3,5-di-tert-butyl-4-hydroxy phenyl) methyl propionate and 1,4-butanediol which serve as materials at a certain temperature to prepare the bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester in the presence of a solvent and a catalyst. The bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester is synthetized from the 3-(3,5-di-tert-butyl-4-hydroxy phenyl) methyl propionate and 1,4-butanediol as materials; the preparation method is simple in separation and purification processes, short in reaction time and high in product yield; the catalyst can be repeatedly used for a plurality of times; the product yield can be up to over 96%; the obtained product is high in purity, small in energy consumption, small in environmental pollution, and low in cost; and the method is an ideal technology for achieving industrial preparation.
Description
Technical field
The present invention relates to a kind of preparation method of oxidation inhibitor two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester.
Background technology
Two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester is the efficient Hinered phenols antioxidant of a kind of macromolecular material.This oxidation inhibitor does not cause and fades or color stain, is effective stablizer of polyolefine, elastomerics, styrene plastic, polyacetals, petroleum products and other organic materialss.Even if there is thermal ageing also show good colour stability.Its chemical name is: two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester; Molecular formula: C
20h
30o
3; Molecular weight: 610.9.
Molecular structural formula:
Physico-chemical property: outward appearance is colourless crystallization body, fusing point 88-91 DEG C.
At present, about oxidation inhibitor two [3-(3,5-di-tert-butyl-hydroxy phenyl)] the domestic disclosed research report of the synthetic method of propionic acid butanediol ester is few, according to reported in literature, Lewis acid, alkali etc. are adopted to carry out transesterification reaction for catalyzer, catalyzer corrosive equipment, the pollution that aftertreatment produces is large, poor product quality.Adopt solid acid catalyst catalyzed transesterification, although product and catalyzer easily separated, little to the corrodibility of equipment, catalyzer recoverable, selectivity and activity low.Now with 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1,4-butyleneglycol is raw material, activated carbon supported titanic acid ester is adopted to be catalyzer, synthesize two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester in the presence of a solvent.It is short that this method has the reaction times, and temperature of reaction is low, and aftertreatment is simple, the feature that product yield is higher.
Summary of the invention
The object of the present invention is to provide the preparation method of oxidation inhibitor two [3-(3,5-di-tert-butyl-hydroxy phenyl)] the propionic acid butanediol ester that a kind of product yield is high.
Technical solution of the present invention is:
A kind of oxidation inhibitor two [3-(3,5-di-tert-butyl-hydroxy phenyl)] preparation method of propionic acid butanediol ester, with 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, BDO is for raw material, under solvent and catalyzer existent condition, solvent is normal heptane or octane, and preferred normal heptane, is heated to certain temperature, obtained two [3-(3,5-di-tert-butyl-hydroxy phenyl)] the propionic acid butanediol ester of reaction; Described catalyzer is activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester or activated carbon supported metatitanic acid orthocarbonate, preferably activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester.
3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1, the usage ratio of 4-butyleneglycol, catalyzer, solvent is by mass: 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate: BDO: catalyzer: solvent=1:0.12 ~ 0.22:0.085 ~ 0.34:1.03 ~ 1.71.
With 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1,4-butyleneglycol is raw material, under solvent and catalyzer existent condition, carry out transesterification reaction, after reaction terminates, carry out filtering, washing, separate organic layer, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester.The temperature of described reaction is 95 ~ 110 DEG C, and the reaction times is 5-10h.
The present invention 3-(3, 5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1, 4-butyleneglycol is Material synthesis two [3-(3, 5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, adopt activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester or activated carbon supported metatitanic acid orthocarbonate catalyzer, separating-purifying process is simple, reaction times is short, product yield is high, catalyzer can be reused repeatedly, the yield of product is made to reach more than 96%, obtain product purity higher, energy consumption reduces, environmental pollution is little, cost is low, the comparatively ideal technique realizing preparation of industrialization.
embodiment:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
A kind of oxidation inhibitor two [3-(3,5-di-tert-butyl-hydroxy phenyl)] preparation method of propionic acid butanediol ester, with 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1,4-butyleneglycol is raw material, under solvent and catalyzer existent condition, carry out obtained two [3-(3,5-di-tert-butyl-hydroxy phenyl)] the propionic acid butanediol ester of transesterification reaction at a certain temperature.3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1, the usage ratio of 4-butyleneglycol, catalyzer, solvent is by mass: 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate: BDO: catalyzer: solvent=1:0.12 ~ 0.22:0.085 ~ 0.34:1.03 ~ 1.71.The catalyzer of described transesterification reaction is activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester or activated carbon supported metatitanic acid orthocarbonate, and this catalyzer can reuse 3 ~ 6 times.
Embodiment 1:
In the four-hole boiling flask of 250mL that thermometer is housed, add normal heptane 70g, 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate 58.5g, 1,4-butyleneglycol 9g, catalyzer 7g, loads onto prolong, start agitator, when being warming up to 95-110 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 5-10h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, product yield is 96.12%.
Embodiment 2:
In the four-hole boiling flask of 250mL that thermometer is housed, add normal heptane 70g, 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate 58.5g, 1,4-butyleneglycol 10g, catalyzer 7g, loads onto prolong, start agitator, when being warming up to 95-110 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 5-10h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, product yield is 96.86%.
Embodiment 3:
In the four-hole boiling flask of 250mL that thermometer is housed, add normal heptane 70g, 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate 58.5g, 1,4-butyleneglycol 10g, catalyzer 9g, loads onto prolong, start agitator, when being warming up to 95-110 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 5-10h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, product yield is 97.05%.
Embodiment 4:
In the four-hole boiling flask of 250mL that thermometer is housed, add normal heptane 90g, 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate 58.5g, 1,4-butyleneglycol 9g, catalyzer 8g, loads onto prolong, start agitator, when being warming up to 95-110 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 5-10h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, product yield is 96.74%.
Embodiment 5:
In the four-hole boiling flask of 250mL that thermometer is housed, add normal heptane 40g, 3-(3,5-di-tert-butyl-hydroxy phenyl)] methyl propionate 58.5g, BDO 10.8g, catalyzer 8g, this catalyzer is reuse for the 5th time.Load onto prolong, start agitator, when being warming up to 95-110 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 5-10h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain two [3-(3,5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, product yield is 96.37%.
The present invention 3-(3, 5-di-tert-butyl-hydroxy phenyl)] methyl propionate, 1, 4-butyleneglycol is Material synthesis two [3-(3, 5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, adopt activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester or activated carbon supported metatitanic acid orthocarbonate catalyzer, separating-purifying process is simple, reaction times is short, product yield is high, catalyzer can be reused repeatedly, the yield of product is made to reach more than 96%, obtain product purity higher, energy consumption reduces, environmental pollution is little, cost is low, the comparatively ideal technique realizing preparation of industrialization.
Claims (1)
1. an oxidation inhibitor two [3-(3, 5-di-tert-butyl-hydroxy phenyl)] preparation method of propionic acid butanediol ester, it is characterized in that: with 3-(3, 5-di-tert-butyl-hydroxy phenyl) methyl propionate, 1, 4-butyleneglycol is raw material, react under catalysts and solvents existent condition, after reaction terminates, filter, washing, separate organic layer, separate organic phase solution to dewater, decolouring, the organic layer obtained carries out cooling down, crystallization, filter to obtain two [3-(3, 5-di-tert-butyl-hydroxy phenyl)] propionic acid butanediol ester, 3-(3, 5-di-tert-butyl-hydroxy phenyl) methyl propionate, 1, 4-butyleneglycol, catalyzer, the usage ratio of solvent is by mass: 3-(3, 5-di-tert-butyl-hydroxy phenyl)] methyl propionate: 1, 4-butyleneglycol: catalyzer: solvent=1:0.12 ~ 0.22:0.085 ~ 0.34:1.03 ~ 1.71, described solvent is normal heptane or octane, the catalyzer of described transesterification reaction is activated carbon supported two (acetylacetone based) metatitanic acid diisopropyl ester or activated carbon supported metatitanic acid orthocarbonate, the temperature of described reaction is 95 ~ 110 DEG C, reaction times is 5-10h.
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| CN201310119217.XA CN103193635B (en) | 2013-04-08 | 2013-04-08 | Method for preparing antioxidant bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester |
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| CN201310119217.XA CN103193635B (en) | 2013-04-08 | 2013-04-08 | Method for preparing antioxidant bi[3-(3,5-di-tert-butyl-4-hydroxy phenyl)] N-butyl glycol ester |
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| CN103193635B true CN103193635B (en) | 2015-06-03 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1103145A (en) * | 1964-06-02 | 1968-02-14 | Geigy Ag J R | Process for the preparation of organic esters |
| CN1583247A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparation for composite titanium oxide catalyst of ester interchange synthetic phenyl ester oxalate |
| CN101687984A (en) * | 2007-06-28 | 2010-03-31 | 巴斯夫欧洲公司 | Solid state polymerization process for polyester |
| CN103012150A (en) * | 2012-12-27 | 2013-04-03 | 江南大学 | Method for preparing plasticizer 1, 2, 4-benzenetricarboxylicacid tris(2-propyl heptyl) ester |
-
2013
- 2013-04-08 CN CN201310119217.XA patent/CN103193635B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1103145A (en) * | 1964-06-02 | 1968-02-14 | Geigy Ag J R | Process for the preparation of organic esters |
| CN1583247A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparation for composite titanium oxide catalyst of ester interchange synthetic phenyl ester oxalate |
| CN101687984A (en) * | 2007-06-28 | 2010-03-31 | 巴斯夫欧洲公司 | Solid state polymerization process for polyester |
| CN103012150A (en) * | 2012-12-27 | 2013-04-03 | 江南大学 | Method for preparing plasticizer 1, 2, 4-benzenetricarboxylicacid tris(2-propyl heptyl) ester |
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