CN105646144A - Preparation method of 1, 2-aliphatic diol - Google Patents
Preparation method of 1, 2-aliphatic diol Download PDFInfo
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- CN105646144A CN105646144A CN201410725107.2A CN201410725107A CN105646144A CN 105646144 A CN105646144 A CN 105646144A CN 201410725107 A CN201410725107 A CN 201410725107A CN 105646144 A CN105646144 A CN 105646144A
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- preparation
- hydrogen peroxide
- catalyzer
- aliphatic dialcohol
- alkene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method of 1, 2-aliphatic diol. The method consists of: under the condition of an organic solvent, taking the straight chain or branched chain terminal olefin of a carbon chain with a carbon atom number of 4-24 as the raw material, adding hydrogen peroxide and a catalyst, then performing stirring at 0-100DEG C for 1-6h, and conducting fractionation separation to obtain the product 1, 2-aliphatic diol. The catalyst is vanadium pentoxide or niobium pentoxide. The preparation method provided by the invention has the advantages of high yield, easy operation, and recyclability of the catalyst, etc.
Description
Technical field
The present invention relates to the preparation method of a kind of alkylol cpd, in particular to the preparation method of a kind of 1,2-aliphatic dialcohol.
Background technology
1,2-aliphatic dialcohol is very important starting raw material in organic synthesis, can be used as efficient moisture-retention agent, tensio-active agent, can be widely used in the industries such as pharmacy, weaving, agricultural chemicals, makeup, senior ink and macromolecular material; Extensively for ink, manufacture superior cosmetics, the senior sanitising agent of multi-usage of color inkjet printer, in addition, also it is applied to high-quality ink, senior paint, coating, senior glue.
Major part 1,2-aliphatic dialcohol is all be hydrolyzed obtained under acid or alkaline conditions by its epoxide, due in reaction process along with the concentration of hydrogen peroxide reduces, reactive behavior can be made decline, react incomplete. Make reaction more complete so catalyzer generally all can be added. Perosmic anhydride is the catalyzer through being commonly used for dihydroxylation, but due to perosmic anhydride costly, and toxicity is big, is unsuitable for suitability for industrialized production. International Patent Application PCT/JP2003/000593, name is called the new manufacturing method of 1,2-glycol, discloses one and has under the existence of sulfonic group macromolecular compound, makes alkene class and hydroperoxidation generate the method for 1,2-glycol. Chinese patent application 201110386229X, name is called that a kind of cyclohexene oxide prepares the method for 1,2-cyclohexanediol, discloses under oxidation reaction condition, by tetrahydrobenzene, aqueous hydrogen peroxide solution and titanium-silicon molecular sieve catalyst contact reacts in organic solvent. Above-mentioned public technology or to there is cost height, reaction process complicated, or need the problems such as acidic conditions environmental pollution is big.
Summary of the invention
It is an object of the invention to: provide a kind of soda acid that do not consume also not generate the method that salt, safety non-pollution generate 1,2-aliphatic dialcohol efficiently.
The technical scheme realizing the object of the invention is:
A kind of 1, the preparation method of 2-aliphatic dialcohol, it is characterized in that: when organic solvent, at the direct-connected of 4-24 or end of the chain position alkene is propped up as raw material taking carbochain, such as carbonatoms is 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24, add hydrogen peroxide, catalyzer, then at 0-100 DEG C, 1-6 hour is stirred, product 1 is obtained after fractionation separates, 2-aliphatic dialcohol, described catalyzer is Vanadium Pentoxide in FLAKES or Niobium Pentxoxide. After reaction terminates, separation and recovery of catalyst recycles.
Reaction formula is as follows:
The preparation method of above-mentioned 1,2-aliphatic dialcohol adds hydrogen peroxide, catalyzer, then preferably at 60 DEG C, 80 DEG C, 90 DEG C, stirs 1-6 hour.
The preparation method of above-mentioned 1,2-aliphatic dialcohol, a described direct-connected or end of the chain position alkene and hydrogen peroxide mol ratio is 2:1-1:2, it is preferable that 2:1,3:2,3:4,1:1; The mol ratio of preferred hydrogen peroxide and catalyzer is 100:1-500:1, it is preferable that 100:1,200:1,300:1,400:1,500:1.
The preparation method of above-mentioned 1,2-aliphatic dialcohol, described solvent is alcohol class or ether class.
The preparation method of above-mentioned 1,2-aliphatic dialcohol, described hydrogen peroxide is preferably the hydrogen peroxide of 30% concentration.
The present invention has positive effect: 4-24 carbon end alkene can be converted into 1,2-glycol when organic solvent by the inventive method, and catalyzer can reclaim and recycle. Not consuming soda acid and also do not generate salt, selectivity and receipts rate height, the rare transformation efficiency of its middle-end is greater than 85%, and the selectivity of glycol is greater than 90%, the hydrogen peroxide safety non-pollution of this external application 30%, and technique cost is low and environmental protection.
Embodiment
(embodiment 1)
The 100mL stainless steel reactor of glass lining adds the 50mL trimethyl carbinol having, the aqueous hydrogen peroxide solution of 5 gram 30%, 25 milligrams of catalyzer Vanadium Pentoxide in FLAKESs, add 4 to restrain oneself alkene, high degree of agitation 4 hours at 60 DEG C, cooling, gas chromatographic analysis water oil two-phase, the transformation efficiency of hydrogen peroxide is 95% by own alkene, catalyzer centrifugation. Solution steam dry after underpressure distillation, collect 220 DEG C-225 DEG C evaporate point, be 1,2-hexylene glycol by analysis. Product rate 85%.
(embodiment 2)
The 100mL stainless steel reactor of glass lining adds the 50mL trimethyl carbinol having, the aqueous hydrogen peroxide solution of 5 gram 30%, 25 milligrams of catalyzer Niobium Pentxoxides, add 2.63 to restrain oneself alkene, high degree of agitation 4 hours at 60 DEG C, cooling, gas chromatographic analysis water oil two-phase, the transformation efficiency of hydrogen peroxide is 96% by own alkene, catalyzer centrifugation. Solution steam dry after underpressure distillation, collect 220 DEG C-225 DEG C evaporate point, be 1,2-hexylene glycol by analysis. Product rate 86%.
(embodiment 3)
The 100mL stainless steel reactor of glass lining adds the 50mL trimethyl carbinol having, the aqueous hydrogen peroxide solution of 5 gram 30%, 20 milligrams of catalyzer Vanadium Pentoxide in FLAKESs, add 5 grams of amylenes, high degree of agitation 4 hours at 80 DEG C, cooling, gas chromatographic analysis water oil two-phase, the transformation efficiency of hydrogen peroxide is 97% by own alkene, catalyzer centrifugation. Solution steam dry after underpressure distillation, collect 203 DEG C-208 DEG C evaporate point, be 1,2-pentanediol by analysis. Product rate 89%.
(embodiment 4)
The 100mL stainless steel reactor of glass lining adds the 50mL trimethyl carbinol having, the aqueous hydrogen peroxide solution of 5 gram 30%, 20 milligrams of catalyzer Niobium Pentxoxides, add 5 grams of amylenes, high degree of agitation 4 hours at 80 DEG C, cooling, gas chromatographic analysis water oil two-phase, the transformation efficiency of hydrogen peroxide is 98% by own alkene, catalyzer centrifugation. Solution steam dry after underpressure distillation, collect 203 DEG C-208 DEG C evaporate point, be 1,2-pentanediol by analysis. Product rate 88%.
(embodiment 5)
The 100mL stainless steel reactor of glass lining adds the 50mL trimethyl carbinol having, the aqueous hydrogen peroxide solution of 5 gram 30%, 125 milligrams of catalyzer Niobium Pentxoxides, add 13.2 grams of amylenes, high degree of agitation 4 hours at 90 DEG C, cooling, gas chromatographic analysis water oil two-phase, the transformation efficiency of hydrogen peroxide is 97% by own alkene, catalyzer centrifugation.Solution steam dry after underpressure distillation, collect 203 DEG C-208 DEG C evaporate point, be 1,2-pentanediol by analysis. Product rate 86%.
Above-mentioned example shows, adopts oxidizer catalytic hydroperoxidation provided by the present invention, the condition provided according to reaction, can be efficient, highly selective end alkene is converted into glycol, reaction separable recycles catalyzer after terminating, and is a kind of simple and effective technological line.
Above-described specific embodiment; the object of the present invention, technical scheme and useful effect have been further described; it is it should be understood that; the foregoing is only specific embodiments of the invention; it is not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. the preparation method of a 2-aliphatic dialcohol, it is characterized in that: when organic solvent, at the direct-connected of 4-24 or end of the chain position alkene is propped up as raw material taking carbochain, add hydrogen peroxide, catalyzer, then at 0-100 DEG C, 1-6 hour is stirred, obtaining product 1,2-aliphatic dialcohol after fractionation separates, described catalyzer is Vanadium Pentoxide in FLAKES or Niobium Pentxoxide.
2. the preparation method of 1,2-aliphatic dialcohol according to claim 1, it is characterised in that: add hydrogen peroxide, catalyzer, then at 60 DEG C, stir 1-6 hour.
3. the preparation method of 1,2-aliphatic dialcohol according to claim 1 and 2, it is characterised in that: a described direct-connected or end of the chain position alkene and hydrogen peroxide mol ratio is 2:1-1:2; The mol ratio of hydrogen peroxide and catalyzer is 100:1-500:1.
4. the preparation method of 1,2-aliphatic dialcohol according to claim 1 and 2, it is characterised in that: described solvent is alcohol class or ether class.
5. the preparation method of 1,2-aliphatic dialcohol as claimed in claim 1 or 2, it is characterised in that: described hydrogen peroxide is the concentration of 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410725107.2A CN105646144B (en) | 2014-12-03 | 2014-12-03 | A kind of preparation method of 1,2 aliphatic glycols |
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| CN201410725107.2A CN105646144B (en) | 2014-12-03 | 2014-12-03 | A kind of preparation method of 1,2 aliphatic glycols |
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| CN105646144A true CN105646144A (en) | 2016-06-08 |
| CN105646144B CN105646144B (en) | 2018-04-20 |
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| CN201410725107.2A Expired - Fee Related CN105646144B (en) | 2014-12-03 | 2014-12-03 | A kind of preparation method of 1,2 aliphatic glycols |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903146A (en) * | 2017-11-23 | 2018-04-13 | 大连理工大学 | A kind of method that 1 hexene of catalysis oxidation prepares 1,2 hexylene glycols |
| CN110590507A (en) * | 2018-06-12 | 2019-12-20 | 北京旭阳科技有限公司 | Method for preparing 1, 2-hexanediol by oxidizing 1-hexene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622927A (en) * | 2002-01-24 | 2005-06-01 | 独立行政法人产业技术综合研究所 | Novel process for producing 1,2-diol |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
| CN101279892A (en) * | 2007-04-03 | 2008-10-08 | 微宏科技（湖州）有限公司 | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene |
| CN102010293A (en) * | 2010-11-02 | 2011-04-13 | 云南大学 | Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite |
| CN103130614A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing 1,2-cyclohexanediol through oxidation of cyclohexene |
-
2014
- 2014-12-03 CN CN201410725107.2A patent/CN105646144B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622927A (en) * | 2002-01-24 | 2005-06-01 | 独立行政法人产业技术综合研究所 | Novel process for producing 1,2-diol |
| CN101279892A (en) * | 2007-04-03 | 2008-10-08 | 微宏科技（湖州）有限公司 | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
| CN102010293A (en) * | 2010-11-02 | 2011-04-13 | 云南大学 | Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite |
| CN103130614A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing 1,2-cyclohexanediol through oxidation of cyclohexene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903146A (en) * | 2017-11-23 | 2018-04-13 | 大连理工大学 | A kind of method that 1 hexene of catalysis oxidation prepares 1,2 hexylene glycols |
| CN110590507A (en) * | 2018-06-12 | 2019-12-20 | 北京旭阳科技有限公司 | Method for preparing 1, 2-hexanediol by oxidizing 1-hexene |
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| CN105646144B (en) | 2018-04-20 |
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Granted publication date: 20180420 Termination date: 20181203 |