CN103193602B - Method for preparing antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol) - Google Patents
Method for preparing antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol) Download PDFInfo
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- CN103193602B CN103193602B CN201310119227.3A CN201310119227A CN103193602B CN 103193602 B CN103193602 B CN 103193602B CN 201310119227 A CN201310119227 A CN 201310119227A CN 103193602 B CN103193602 B CN 103193602B
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- Prior art keywords
- tert
- ethylene
- butylphenol
- catalyzer
- paraldehyde
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- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 10
- 239000003963 antioxidant agent Substances 0.000 title abstract description 3
- 230000003078 antioxidant effect Effects 0.000 title abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 18
- 229960003868 paraldehyde Drugs 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000012074 organic phase Substances 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 9
- -1 2, 6-DI-tert-butylphenol compounds Chemical class 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
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000009835 boiling Methods 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
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing an antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol). The method comprises the steps of: taking 2,6-di-tert-butylphenol and metaacetaldehyde as materials, and reacting at a certain temperature to prepare the 4,4'-ethylene bi(2,6-di-tert-butylphenol) in the presence of a solvent and a catalyst. The 4,4'-ethylene bi(2,6-di-tert-butylphenol) is synthetized from the 2,6-di-tert-butylphenol and the metaacetaldehyde as materials; the method is simple in separation and purification processes, short in reaction time, high in product yield, high in product purity, low in energy consumption, small in environmental pollution and low in cost; the yield of the product can be up to over 91%; and the method is an ideal production technology for achieving industrialization.
Description
Technical field
The present invention relates to a kind of oxidation inhibitor 4, the preparation method of 4 '-ethylene two (2,6 di t butyl phenol).
Background technology
4,4 '-ethylene two (2,6 di t butyl phenol) is the efficient Hinered phenols antioxidant of a kind of macromolecular material.This oxidation inhibitor does not cause and fades or color stain, and this product is applicable to effective stablizer of polyethylene, polypropylene, polystyrene, ABS resin and polyester and other organic materialss.Even if there is thermal ageing also show good colour stability.Its chemical name is: 4,4 '-ethylene two (2,6 di t butyl phenol); Molecular formula: C
30h
46o
2; Molecular weight: 438.7.
Molecular structural formula:
At present, about oxidation inhibitor 4,4 '-ethylene two (2,6-DI-tert-butylphenol compounds) the domestic disclosed research report of synthetic method seldom, according to reported in literature, adopt highly basic etc. to carry out condensation reaction for catalyzer, catalyzer corrosive equipment, the pollution that aftertreatment produces is large, poor product quality.Adopt solid base catalyst catalyzed reaction, although product and catalyzer easily separated, little to the corrodibility of equipment, catalyzer recoverable, selectivity and activity low.Now with 2,6 di t butyl phenol, paraldehyde for raw material, employing organic bases is catalyzer, has synthesized 4 in the presence of a solvent, 4 '-ethylene two (2,6 di t butyl phenol).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 oxidation inhibitor 4 that a kind of product yield is high, the preparation method of 4 '-ethylene two (2,6 di t butyl phenol).
Technical solution of the present invention is:
A kind of oxidation inhibitor 4, the preparation method of 4 '-ethylene two (2,6 di t butyl phenol) is with 2,6-DI-tert-butylphenol compounds, paraldehyde are raw material, under solvent and catalyzer existent condition, solvent is sherwood oil or normal heptane or octane, preferred sherwood oil, be heated to certain temperature, reaction obtained 4,4 '-ethylene two (2,6 di t butyl phenol); Described catalyzer is sodium methylate or sodium ethylate or Lithamide, particular methanol sodium.
The usage ratio of 2,6 di t butyl phenol, paraldehyde, catalyzer, solvent is by mass: 2,6 di t butyl phenol: paraldehyde: catalyzer: solvent=1:0.11 ~ 0.32:0.012 ~ 0.05:0.98 ~ 1.95.
With 2,6-DI-tert-butylphenol compounds, paraldehyde are raw material, under solvent and catalyzer existent condition, carry out transesterification reaction, after reaction terminates, wash, separate organic layer, separate organic phase solution to carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol).The temperature of described reaction is 110 ~ 125 DEG C, and the reaction times is 4-8h.
The present invention's 2,6 di t butyl phenol, paraldehyde are Material synthesis 4,4 '-ethylene two (2,6-DI-tert-butylphenol compounds), adopt sodium methylate or sodium ethylate or lithium amide catalysts, separating-purifying process is simple, reaction times is short, product yield is high, and make the yield of product reach more than 91%, product purity is high, energy consumption is low, environmental pollution is little, and cost is low, is 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 4,4 '-ethylene two (2,6-DI-tert-butylphenol compounds) preparation method, with 2,6-DI-tert-butylphenol compounds, paraldehyde are raw material, under solvent and catalyzer existent condition, carry out condensation reaction obtained 4 at a certain temperature, 4 '-ethylene two (2,6 di t butyl phenol); The usage ratio of 2,6 di t butyl phenol, paraldehyde, catalyzer, solvent is by mass: 2,6 di t butyl phenol: paraldehyde: catalyzer: solvent=1:0.11 ~ 0.32:0.012 ~ 0.05:0.98 ~ 1.95; Described catalyzer is sodium methylate or sodium ethylate or Lithamide; Solvent is sherwood oil or normal heptane or octane, preferred sherwood oil; The temperature of reaction is 110 ~ 125 DEG C, and the reaction times is 4-8h.
Embodiment 1:
In the four-hole boiling flask of 250mL that thermometer is housed, add sherwood oil 60g, 2,6 di t butyl phenol 41.2g, paraldehyde 5.3g, catalyzer 0.8g, loads onto prolong, start agitator, when being warming up to 110-125 DEG C, reaction times 4-8h (with gas-chromatography monitoring reaction).Reaction terminate after, wash, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol), product yield is 91.63%.
Embodiment 2:
In the four-hole boiling flask of 250mL that thermometer is housed, add sherwood oil 70g, 2,6 di t butyl phenol 41.2g, paraldehyde 7.9g, catalyzer 0.8g, loads onto prolong, start agitator, when being warming up to 110-125 DEG C, reaction times 4-8h (with gas-chromatography monitoring reaction).Reaction terminate after, wash, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol), product yield is 91.42%.
Embodiment 3:
In the four-hole boiling flask of 250mL that thermometer is housed, add sherwood oil 70g, 2,6 di t butyl phenol 41.2g, paraldehyde 13.2g, catalyzer 0.8g, loads onto prolong, start agitator, when being warming up to 110-125 DEG C, reaction times 4-8h (with gas-chromatography monitoring reaction).Reaction terminate after, wash, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol), product yield is 91.84%.
Embodiment 4:
In the four-hole boiling flask of 250mL that thermometer is housed, add sherwood oil 70g, 2,6 di t butyl phenol 41.2g, paraldehyde 13.2g, catalyzer 1.2g, loads onto prolong, start agitator, when being warming up to 110-125 DEG C, reaction times 4-8h (with gas-chromatography monitoring reaction).Reaction terminate after, wash, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol), product yield is 92.07%.
Embodiment 5:
In the four-hole boiling flask of 250mL that thermometer is housed, add sherwood oil 80g, 2,6 di t butyl phenol 41.2g, paraldehyde 13.2g, catalyzer 2.0g.Load onto prolong, start agitator, when being warming up to 110-125 DEG C, reaction times 4-8h (with gas-chromatography monitoring reaction).Reaction terminate after, wash, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4,4 '-ethylene two (2,6 di t butyl phenol), product yield is 92.67%.
The present invention's 2,6 di t butyl phenol, paraldehyde are Material synthesis 4,4 '-ethylene two (2,6-DI-tert-butylphenol compounds), adopt sodium methylate or sodium ethylate or lithium amide catalysts, separating-purifying process is simple, reaction times is short, product yield is high, and make the yield of product reach more than 91%, product purity is high, energy consumption is low, environmental pollution is little, and cost is low, is the comparatively ideal technique realizing preparation of industrialization.
Claims (1)
1. an oxidation inhibitor 4, 4 '-ethylene two (2, 6-DI-tert-butylphenol compounds) preparation method, it is characterized in that: with 2, 6-DI-tert-butylphenol compounds, paraldehyde is raw material, react under catalysts and solvents existent condition, after reaction terminates, wash, separate organic layer, separate organic phase solution to dewater, decolouring, the organic layer obtained carries out cooling down, crystallization, filter 4, 4 '-ethylene two (2, 6-DI-tert-butylphenol compounds), 2, 6-DI-tert-butylphenol compounds, paraldehyde, catalyzer, the usage ratio of solvent is by mass: 2, 6-DI-tert-butylphenol compounds: paraldehyde: catalyzer: solvent=1:0.11 ~ 0.32:0.012 ~ 0.05:0.98 ~ 1.95, described solvent is sherwood oil, described catalyzer is sodium methylate, the temperature of described reaction is 110 ~ 125 DEG C, reaction times is 4-8h.
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| CN201310119227.3A CN103193602B (en) | 2013-04-08 | 2013-04-08 | Method for preparing antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol) |
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| CN103193602B true CN103193602B (en) | 2015-05-06 |
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| CN105503535B (en) * | 2015-08-03 | 2017-08-11 | 中国科学院宁波材料技术与工程研究所 | The preparation method and application of bis-phenol kind antioxidant based on mixed base catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO104972B1 (en) * | 1989-08-09 | 1994-12-19 | Combinatul Petrochimic Teleaje | Antioxidizing admixture and producing process thereof |
| CN1994993A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Cleaning production method for preparing bisphenol compound antioxidant product |
| CN102838459A (en) * | 2012-09-04 | 2012-12-26 | 江苏昊华精细化工有限公司 | Production method of ethylene-bis-di-tert-butylphenol |
-
2013
- 2013-04-08 CN CN201310119227.3A patent/CN103193602B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO104972B1 (en) * | 1989-08-09 | 1994-12-19 | Combinatul Petrochimic Teleaje | Antioxidizing admixture and producing process thereof |
| CN1994993A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Cleaning production method for preparing bisphenol compound antioxidant product |
| CN102838459A (en) * | 2012-09-04 | 2012-12-26 | 江苏昊华精细化工有限公司 | Production method of ethylene-bis-di-tert-butylphenol |
Non-Patent Citations (2)
| Title |
|---|
| 2,2′-亚乙基双(4,6-二叔戊基苯酚)的清洁化合成工艺;杜飞等;《化工进展》;20081231;第27卷(第4期);第602-605页 * |
| Chemistry on the Decay of the Phenoxy Radical from Butylated Hydroxytoluene;Kanji Omura;《JAOCS》;19920531;第69卷(第5期);第461-465页 * |
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