CN106831423A - The synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) - Google Patents
The synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) Download PDFInfo
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- CN106831423A CN106831423A CN201710062950.0A CN201710062950A CN106831423A CN 106831423 A CN106831423 A CN 106831423A CN 201710062950 A CN201710062950 A CN 201710062950A CN 106831423 A CN106831423 A CN 106831423A
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- diethylene glycol
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- monobutyl ether
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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Abstract
The synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG), it is characterised in that be used as catalyst by anhydrous alkali material, makes the tertiary butyl ether of diethylene glycol (DEG) carry out ester exchange to synthesize the tertiary monobutyl ether acetate of diethylene glycol (DEG) with acetate.The method have the advantages that：The tertiary monobutyl ether acetate of diethylene glycol (DEG) is cheap due to its raw material, and manufacturing cost is less than butyl carbitol acetate, therefore replaces existing articles for use butyl carbitol acetate to be used as paint, printing ink coalescents by it having realistic meaning.
Description
Technical field
The present invention relates to chemical field, and in particular to the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG).
Background technology
At present, the tertiary monobutyl ether acetate of diethylene glycol (DEG) due to not finding purposes, therefore unmanned research in the past.In recent years because two is sweet
Alcohol monobutyl ether acetate makes isobutene in paint, oil film extensive use, and as preparing isobutene through dehydrogenation of iso-butane technological direction is ripe
Price significantly declines, therefore exploitation replaces butyl carbitol acetic acid by the tertiary monobutyl ether acetate of Material synthesis diethylene glycol (DEG) of isobutene
Ester has realistic meaning.Additionally, it is well known that, tertbutyl ether is unstable to acid, it is impossible to using the tertiary butyl ether of diethylene glycol (DEG) and acetic acid or
Aceticanhydride synthesizes the tertiary monobutyl ether acetate of diglycol monotertiary, the tertiary butyl ether of the similar ethylene glycol of this point can not with acetic acid or aceticanhydride into ester, because
It is that isobutene and correspondent alcohol can be resolved under acid catalysis, therefore a kind of technology production tertiary monobutyl ether acetate of diethylene glycol (DEG) of invention carrys out generation
It is our purpose for butyl carbitol acetate.
The content of the invention
The purpose of the present invention is exactly to invent a kind of technology production tertiary monobutyl ether acetate of diethylene glycol (DEG) to replace butyl carbitol acetate.
The synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG), catalyst is used as by anhydrous alkali material, makes the tertiary fourth of diethylene glycol (DEG)
Ether carries out ester exchange to synthesize the tertiary monobutyl ether acetate of diethylene glycol (DEG) with acetate.
Anhydrous alkali material is inorganic strong alkali, the metal compound of alcohol or solid alkali.
The metal compound of alcohol is the one kind in potassium alcoholate or sodium alkoxide.
Solid alkali is the one kind in solid sodium hydroxide or potassium hydroxide.
Acetate is the one kind in methyl acetate, ethyl ester, propyl ester, butyl ester, isopropyl ester or isobutyl ester.
PH value when controlling to react by anhydrous alkali material, pH value remains at more than 12.
The tertiary butyl ether of diglycol monotertiary and methyl acetate are pressed 1:6 mixed in molar ratio, adds the tertiary butyl ether weight 1% of diglycol monotertiary
Potassium methoxide, stirring heat up, by efficient still, reflux ratio 4:1, methyl acetate is constantly fractionated out with methanol azeotrope,
Until distillating tower top without azeotropic mixture, untill temperature rises to 57.8 DEG C of methyl acetate boiling point, continue to be fractionated recovery of acetic acid methyl esters, so
After be transferred to fractionating column, vacuum fractionation goes out the tertiary monobutyl ether acetate of diethylene glycol (DEG).
Strong alkali catalyst is loaded into fixed bed Dn 50 × 1200, by the tertiary butyl ether of diethylene glycol (DEG) and methyl acetate in molar ratio
1:2 mixing, are preheating to 80 DEG C, by fixed bed under 0.4MPa pressure, air speed 1h-1, diethylene glycol (DEG) conversion ratio of tertiary butyl ether is
20%, the mixture of generation is cooled to 40 DEG C and fractionates out low boiling into fractionating column, then with methyl acetate in molar ratio 1:2 mixing, in advance
To 80 DEG C, into fixed bed reactors, secondary conversion rate is 40% to heat, so obtains the tertiary butyl ether conversion ratio of diethylene glycol (DEG) after 5 times repeatedly
95%, product is cooled to 40 DEG C, and low-boiling-point substance is fractionated out into fractionating column（Mainly methyl acetate and methyl alcohol）, Ran Houjin
Enter azeotrope column and isolate the tertiary butyl ether of diglycol monotertiary and the tertiary monobutyl ether acetate azeotropic mixture of diethylene glycol (DEG), then the tertiary fourth of diethylene glycol (DEG) is obtained through weight-removing column
Ether acetate.
The method have the advantages that：The tertiary monobutyl ether acetate of diethylene glycol (DEG) is cheap due to its raw material, and manufacturing cost is less than diethylene glycol (DEG) fourth
Ether acetate, therefore replace existing articles for use butyl carbitol acetate to be used as paint, printing ink coalescents by it having realistic meaning.
Specific embodiment
Catalyst is used as by anhydrous alkali material, the tertiary butyl ether of diethylene glycol (DEG) is carried out ester exchange with acetate sweet to synthesize two
The tertiary monobutyl ether acetate of alcohol.
Anhydrous alkali material is inorganic strong alkali, the metal compound of alcohol or solid alkali.
The metal compound of alcohol is the one kind in potassium alcoholate or sodium alkoxide.
Solid alkali is the one kind in solid sodium hydroxide or potassium hydroxide.
Acetate is the one kind in methyl acetate, ethyl ester, propyl ester, butyl ester, isopropyl ester or isobutyl ester.
PH value when controlling to react by anhydrous alkali material, pH value remains at more than 12.
The tertiary butyl ether of diglycol monotertiary and methyl acetate are pressed 1:6 mixed in molar ratio, adds the tertiary butyl ether weight 1% of diglycol monotertiary
Potassium methoxide, stirring heat up, by efficient still, reflux ratio 4:1, methyl acetate is constantly fractionated out with methanol azeotrope,
Until distillating tower top without azeotropic mixture, untill temperature rises to 57.8 DEG C of methyl acetate boiling point, continue to be fractionated recovery of acetic acid methyl esters, so
After be transferred to fractionating column, vacuum fractionation goes out the tertiary monobutyl ether acetate of diethylene glycol (DEG).
Strong alkali catalyst is loaded into fixed bed Dn 50 × 1200, by the tertiary butyl ether of diethylene glycol (DEG) and methyl acetate in molar ratio
1:2 mixing, are preheating to 80 DEG C, by fixed bed under 0.4MPa pressure, air speed 1h-1, diethylene glycol (DEG) conversion ratio of tertiary butyl ether is
20%, the mixture of generation is cooled to 40 DEG C and fractionates out low boiling into fractionating column, then with methyl acetate in molar ratio 1:2 mixing, in advance
To 80 DEG C, into fixed bed reactors, secondary conversion rate is 40% to heat, so obtains the tertiary butyl ether conversion ratio of diethylene glycol (DEG) after 5 times repeatedly
95%, product is cooled to 40 DEG C, and low-boiling-point substance is fractionated out into fractionating column（Mainly methyl acetate and methyl alcohol）, Ran Houjin
Enter azeotrope column and isolate the tertiary butyl ether of diglycol monotertiary and the tertiary monobutyl ether acetate azeotropic mixture of diethylene glycol (DEG), then the tertiary fourth of diethylene glycol (DEG) is obtained through weight-removing column
Ether acetate.Reaction equation：
Example 1
The tertiary butyl ether of diglycol monotertiary and methyl acetate are pressed 1:6 mixed in molar ratio, adds the first of the tertiary butyl ether weight 1% of diglycol monotertiary
Potassium alcoholate, stirring heats up, by efficient still（Reflux ratio 4:1）, methyl acetate is constantly fractionated out with methanol azeotrope, until
Tower top is distillated without azeotropic mixture, untill temperature rises to 57.8 DEG C of methyl acetate boiling point, continues to be fractionated recovery of acetic acid methyl esters, Ran Houzhuan
Enter fractionating column, vacuum fractionation goes out the tertiary monobutyl ether acetate of diethylene glycol (DEG)（Content >=99.5%）.The tertiary butyl ether conversion ratio 99% of diethylene glycol (DEG), receives
Rate 95%.
Example 2
By example 1, potassium methoxide is replaced using equimolar potassium tert-butoxide, it is as a result same as Example 1.
Example 3
By example 1, potassium methoxide is replaced using anhydrous potassium hydroxide, as a result the tertiary butyl ether conversion ratio 95% of diethylene glycol (DEG), the tertiary butyl ether of diethylene glycol (DEG)
Acetate yield 90%.
Example 4
The tertiary butyl ether of diglycol monotertiary and methyl acetate proportioning are changed to by 1:4 mixed in molar ratio, other conditions are same as Example 1, knot
The tertiary butyl ether conversion ratio 80% of fruit diethylene glycol (DEG), the tertiary monobutyl ether acetate yield 77% of diethylene glycol (DEG).
Example 5
Replace the tertiary butyl ether of diethylene glycol (DEG) to implement by example 1,2,3 the tertiary butyl ether of ethylene glycol, obtain the tertiary monobutyl ether acetate of ethylene glycol, as a result second two
The tertiary butyl ether conversion ratio 98% of alcohol, tertiary monobutyl ether acetate content >=99.5% of ethylene glycol, the tertiary monobutyl ether acetate yield 96% of ethylene glycol.
Example 6
Change methyl acetate into ethyl acetate, potassium methoxide changes potassium ethoxide into, implement by example 1, the tertiary butyl ether conversion ratio 95% of diglycol monotertiary
, the tertiary monobutyl ether acetate content 99.2% of diethylene glycol (DEG), the tertiary monobutyl ether acetate yield 94% of diethylene glycol (DEG).
Example 7
Strong alkali catalyst is loaded into fixed bed Dn 50 × 1200, by the tertiary butyl ether of diethylene glycol (DEG) and methyl acetate in molar ratio 1:2 mix
Close, be preheating to 80 DEG C, fixed bed is passed through under 0.4MPa pressure（Air speed 1h-1）, conversion ratio of the tertiary butyl ether of diethylene glycol (DEG) is 20%,
The mixture of generation is cooled to 40 DEG C and fractionates out low boiling into fractionating column, then with methyl acetate in molar ratio 1:2 mixing, are preheating to
80 DEG C, into fixed bed reactors, secondary conversion rate is 40%, so obtains the tertiary butyl ether conversion ratio 95% of diethylene glycol (DEG) after 5 times repeatedly,
Product is cooled to 40 DEG C, and low-boiling-point substance is fractionated out into fractionating column（Mainly methyl acetate and methyl alcohol）, subsequently into altogether
Boiling tower isolates the tertiary butyl ether of diglycol monotertiary and the tertiary monobutyl ether acetate azeotropic mixture of diethylene glycol (DEG), then obtains the tertiary butyl ether vinegar of diethylene glycol (DEG) through weight-removing column
Acid esters（Content ＞ 99.5%）, the tertiary monobutyl ether acetate total recovery 94% of diethylene glycol (DEG)（In terms of the tertiary butyl ether of diglycol monotertiary for consuming）.
Example 8
Preceding boiling thing methyl acetate and methanol azeotropic mixture, are fractionated using differential pressure, fractionate out pure methyl acetate, then normal pressure is fractionated out
Methyl acetate and methanol azeotrope, remaining methyl alcohol can be sold as commodity.
Claims (8)
1. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG), it is characterised in that catalyst is used as by anhydrous alkali material, makes two
The tertiary butyl ether of glycol carries out ester exchange to synthesize the tertiary monobutyl ether acetate of diethylene glycol (DEG) with acetate.
2. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) according to claim 1, it is characterised in that anhydrous alkali material
It is inorganic strong alkali, the metal compound of alcohol or solid alkali.
3. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) according to claim 1, it is characterised in that the metal compound of alcohol
It is the one kind in potassium alcoholate or sodium alkoxide.
4. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) according to claim 2, it is characterised in that solid alkali is solid
One kind in body NaOH or potassium hydroxide.
5. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) according to claim 1, it is characterised in that acetate is acetic acid
One kind in methyl esters, ethyl ester, propyl ester, butyl ester, isopropyl ester or isobutyl ester.
6. the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) according to claim 1-5, it is characterised in that by anhydrous alkali
Property material control reaction when pH value, pH value remains at more than 12.
7. according to the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) described in claim 1, it is characterised in that by the tertiary fourth of diglycol monotertiary
Ether presses 1 with methyl acetate:6 mixed in molar ratio, adds the potassium methoxide of the tertiary butyl ether weight 1% of diglycol monotertiary, and stirring heats up, passes through
Efficient still, reflux ratio 4:1, methyl acetate is constantly fractionated out with methanol azeotrope, until tower top is distillated without azeotropic mixture, temperature
Untill degree rises to 57.8 DEG C of methyl acetate boiling point, continue to be fractionated recovery of acetic acid methyl esters, be then transferred to fractionating column, vacuum fractionation goes out
The tertiary monobutyl ether acetate of diethylene glycol (DEG).
8. according to the synthetic method of the tertiary monobutyl ether acetate of diethylene glycol (DEG) described in claim 1, it is characterised in that by strong alkali catalyst
Load fixed bed Dn 50 × 1200, by the tertiary butyl ether of diethylene glycol (DEG) and methyl acetate in molar ratio 1:2 mixing, are preheating to 80 DEG C,
By fixed bed under 0.4MPa pressure, air speed 1h-1, conversion ratio of the tertiary butyl ether of diethylene glycol (DEG) is 20%, and the mixture of generation is cooled to
40 DEG C fractionate out low boiling into fractionating column, then with methyl acetate in molar ratio 1:2 mixing, are preheating to 80 DEG C, anti-into fixed bed
Answer device, secondary conversion rate is 40%, so obtain the tertiary butyl ether conversion ratio 95% of diethylene glycol (DEG) after 5 times repeatedly, product is cooled to
40 DEG C, low-boiling-point substance is fractionated out into fractionating column, the tertiary butyl ether of diglycol monotertiary and the tertiary butyl ether of diethylene glycol (DEG) are isolated subsequently into azeotrope column
Acetate azeotropic mixture, then obtain the tertiary monobutyl ether acetate of diethylene glycol (DEG) through weight-removing column.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197790A (en) * | 1997-04-30 | 1998-11-04 | 石伟 | Preparation of acetate product |
| CN101475478A (en) * | 2009-01-20 | 2009-07-08 | 江苏怡达化工有限公司 | Method for synthesizing ethylene glycol monobutyl ether acetate |
| CN102993003A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Acetate preparation method |
-
2017
- 2017-02-03 CN CN201710062950.0A patent/CN106831423A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197790A (en) * | 1997-04-30 | 1998-11-04 | 石伟 | Preparation of acetate product |
| CN101475478A (en) * | 2009-01-20 | 2009-07-08 | 江苏怡达化工有限公司 | Method for synthesizing ethylene glycol monobutyl ether acetate |
| CN102993003A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Acetate preparation method |
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Application publication date: 20170613 |