CN105646144B - A kind of preparation method of 1,2 aliphatic glycols - Google Patents
A kind of preparation method of 1,2 aliphatic glycols Download PDFInfo
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- CN105646144B CN105646144B CN201410725107.2A CN201410725107A CN105646144B CN 105646144 B CN105646144 B CN 105646144B CN 201410725107 A CN201410725107 A CN 201410725107A CN 105646144 B CN105646144 B CN 105646144B
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- hydrogen peroxide
- aliphatic glycols
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to one kind 1, the preparation method of 2 aliphatic glycols, under the conditions of organic solvent, using carbochain 4 24 direct-connected or branch end of the chain position alkene as raw material, hydrogen peroxide, catalyst are added, when then stirring 16 is small at 0 100 DEG C, product 1 is obtained after being fractionated into separation, 2 aliphatic glycols, the catalyst are vanadic anhydride or niobium pentaoxide.The present invention has the advantages that yield is high, and easy to operate, catalyst can be recycled and recycled.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method of alcoholic compound, more particularly to one kind 1,2- aliphatic glycols.
Background technology
1,2- aliphatic glycol is critically important starting material in organic synthesis, can be used as efficient moisture-retention agent, surface-active
Agent, can be widely applied to the industries such as pharmacy, weaving, pesticide, cosmetics, advanced ink and high molecular material；It is widely used in colour
Ink, manufacture superior cosmetics, the multipurpose advanced cleaning agents of ink-jet printer, in addition, being also applied to high-quality ink, special oil
Paint, coating, advanced glue.
Most of 1,2- aliphatic glycols be all hydrolyzed under acid or alkaline conditions by its epoxides it is obtained, due to
Reduced in reaction process with the concentration of hydrogen peroxide, reactivity can be declined, reaction is incomplete.So generally it can all add
Catalyst make it that reaction is more complete.Osmium tetroxide is the catalyst for being commonly used as dihydroxylated, but since osmium tetroxide is relatively more high
It is expensive, and toxicity is big, is unsuitable for industrialized production.International Patent Application PCT/JP2003/000593, entitled 1,2- glycol
New manufacturing method, discloses one kind in the presence of with sulfonic group high-molecular compound, gives birth to olefines and hydroperoxidation
Into the method for 1,2- glycol.Chinese patent application 201110386229X, a kind of entitled cyclohexene oxide prepare 1,2- hexamethylenes two
The method of alcohol, discloses under oxidation reaction condition, and cyclohexene, aqueous hydrogen peroxide solution and titanium-silicon molecular sieve catalyst are being had
Haptoreaction in solvent.Technology disclosed above or there are it is of high cost, reaction process is complicated, or need acid condition environmental pollution
The problems such as big.
The content of the invention
The purpose of the present invention is：One kind is provided and does not consume that soda acid does not generate salt yet, safety non-pollution efficiently generates 1,2-
The method of aliphatic glycol.
Realizing the technical solution of the object of the invention is：
The preparation method of one kind 1,2- aliphatic glycols, it is characterised in that：Under the conditions of organic solvent, with carbochain 4-24's
Direct-connected or branch end of the chain position alkene is raw material, for example, carbon number is 4,5,6,7,8,9,10,11,12,13,14,15,16,17,
18th, 19,20,21,22,23,24, add hydrogen peroxide, catalyst, then stirred at 0-100 DEG C 1-6 it is small when, be fractionated into point
Product 1,2- aliphatic glycols are obtained from after, the catalyst is vanadic anhydride or niobium pentaoxide.After reaction, catalyst
Separation and recovery recycles.
Reaction equation is as follows：
In the preparation method of above-mentioned 1,2- aliphatic glycols add hydrogen peroxide, catalyst, then preferably 60 DEG C, 80
DEG C, stir at 90 DEG C 1-6 it is small when.
The preparation method of above-mentioned 1,2- aliphatic glycols, the described direct-connected or molar ratio of branch end of the chain position alkene and hydrogen peroxide
It is 2：1-1：2, preferably 2:1、3:2、3:4、1:1；It is preferred that the molar ratio of hydrogen peroxide and catalyst is 100：1-500：1, preferably
100:1、200:1、300:1、400:1、500:1。
The preparation method of above-mentioned 1,2- aliphatic glycols, the solvent are alcohols or ethers.
The preparation method of above-mentioned 1,2- aliphatic glycols, the hydrogen peroxide are preferably the hydrogen peroxide of 30% concentration.
The present invention has positive effect：The method of the present invention can be direct by 4-24 carbon teminal alkene under conditions of organic solvent
1,2- glycol is converted into, catalyst can be recycled and recycled.Soda acid is not consumed does not generate salt, selectivity and high income yet,
The dilute conversion ratio of its middle-end is more than 85%, and the selectivity of glycol is more than 90%, the hydrogen peroxide safety non-pollution of this external application 30%,
Process costs are low and environmentally protective.
Embodiment
(embodiment 1)
The 50mL tert-butyl alcohols are added in the 100mL stainless steel reactors for have glass bushing, 5 gram 30% of hydrogen peroxide is water-soluble
Liquid, 25 milligrams of catalyst vanadic anhydrides, add 4 and restrain oneself alkene, when high degree of agitation 4 is small at 60 DEG C, cooling, and gas chromatographic analysis water
Oily two-phase, hexene are 95% to the conversion ratio of hydrogen peroxide, and catalyst centrifuges.Solution is evaporated under reduced pressure after being evaporated, and collects 220
DEG C -225 DEG C of cut, is 1,2- hexylene glycols through analysis.Yield 85%.
(embodiment 2)
The 50mL tert-butyl alcohols are added in the 100mL stainless steel reactors for have glass bushing, 5 gram 30% of hydrogen peroxide is water-soluble
Liquid, 25 milligrams of catalyst niobium pentaoxides, add 2.63 and restrain oneself alkene, when high degree of agitation 4 is small at 60 DEG C, cooling, and gas-chromatography point
Water phase and an oil phase is analysed, hexene is 96% to the conversion ratio of hydrogen peroxide, and catalyst centrifuges.Solution is evaporated under reduced pressure after being evaporated, and is received
The cut of 220 DEG C -225 DEG C of collection, is 1,2- hexylene glycols through analysis.Yield 86%.
(embodiment 3)
The 50mL tert-butyl alcohols are added in the 100mL stainless steel reactors for have glass bushing, 5 gram 30% of hydrogen peroxide is water-soluble
Liquid, 20 milligrams of catalyst vanadic anhydrides, add 5 grams of amylenes, when high degree of agitation 4 is small at 80 DEG C, cooling, and gas chromatographic analysis water
Oily two-phase, hexene are 97% to the conversion ratio of hydrogen peroxide, and catalyst centrifuges.Solution is evaporated under reduced pressure after being evaporated, and collects 203
DEG C -208 DEG C of cut, is 1,2- pentanediols through analysis.Yield 89%.
(embodiment 4)
The 50mL tert-butyl alcohols are added in the 100mL stainless steel reactors for have glass bushing, 5 gram 30% of hydrogen peroxide is water-soluble
Liquid, 20 milligrams of catalyst niobium pentaoxides, add 5 grams of amylenes, when high degree of agitation 4 is small at 80 DEG C, cooling, and gas chromatographic analysis water
Oily two-phase, hexene are 98% to the conversion ratio of hydrogen peroxide, and catalyst centrifuges.Solution is evaporated under reduced pressure after being evaporated, and collects 203
DEG C -208 DEG C of cut, is 1,2- pentanediols through analysis.Yield 88%.
(embodiment 5)
The 50mL tert-butyl alcohols are added in the 100mL stainless steel reactors for have glass bushing, 5 gram 30% of hydrogen peroxide is water-soluble
Liquid, 125 milligrams of catalyst niobium pentaoxides, add 13.2 grams of amylenes, when high degree of agitation 4 is small at 90 DEG C, cooling, and gas-chromatography point
Water phase and an oil phase is analysed, hexene is 97% to the conversion ratio of hydrogen peroxide, and catalyst centrifuges.Solution is evaporated under reduced pressure after being evaporated, and is received
The cut of 203 DEG C -208 DEG C of collection, is 1,2- pentanediols through analysis.Yield 86%.
Above-mentioned example shows, using oxidizer catalytic hydroperoxidation provided by the present invention, is provided according to reaction
Condition, can be efficient, high selectivity will end alkene be converted into glycol, after reaction separate recycle catalyst, be
A kind of simple and effective technology path.
Particular embodiments described above, has carried out the purpose of the present invention, technical solution and beneficial effect further in detail
Describe in detail it is bright, it should be understood that the foregoing is merely the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done, should be included in the guarantor of the present invention
Within the scope of shield.
Claims (3)
1. one kind 1, the preparation method of 2- aliphatic glycols, it is characterised in that：Under the conditions of organic solvent, with carbochain in the straight of 4-24
Even or branch end of the chain position alkene is raw material, adds hydrogen peroxide, catalyst, when then stirring 1-6 is small at 0-100 DEG C, is fractionated into
Product 1,2- aliphatic glycols are obtained after separation, the catalyst is vanadic anhydride or niobium pentaoxide；Described direct-connected or side chain
The molar ratio for holding position alkene and hydrogen peroxide is 2：1-1：2；The molar ratio of hydrogen peroxide and catalyst is 100：1-500：1；Institute
The hydrogen peroxide stated is 30% concentration.
2. the preparation method of 1,2- aliphatic glycols according to claim 1, it is characterised in that：Add hydrogen peroxide, catalysis
Agent, when then stirring 1-6 is small at 60 DEG C.
3. the preparation method of 1,2- aliphatic glycols according to claim 1, it is characterised in that：The solvent for alcohols or
Ethers.
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| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410725107.2A CN105646144B (en) | 2014-12-03 | 2014-12-03 | A kind of preparation method of 1,2 aliphatic glycols |
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| Publication Number | Publication Date |
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| CN105646144A CN105646144A (en) | 2016-06-08 |
| CN105646144B true 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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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903146B (en) * | 2017-11-23 | 2020-06-16 | 大连理工大学 | Method for preparing 1, 2-hexanediol by catalytic oxidation of 1-hexene |
| 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 of 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 of 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 |
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