CN102993008A - Preparation method of polyol alkyl ether acetate - Google Patents
Preparation method of polyol alkyl ether acetate Download PDFInfo
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- CN102993008A CN102993008A CN2011102689477A CN201110268947A CN102993008A CN 102993008 A CN102993008 A CN 102993008A CN 2011102689477 A CN2011102689477 A CN 2011102689477A CN 201110268947 A CN201110268947 A CN 201110268947A CN 102993008 A CN102993008 A CN 102993008A
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- polyol alkyl
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Abstract
The invention relates to a preparation method of polyol alkyl ether acetate. The method comprises the following steps: carrying out a contact reaction of sec-butyl acetate and polyol alkyl ether having at least one hydroxy group in the presence of an ester exchange catalyst under an ester exchange reaction condition, and separating out the polyol alkyl ether acetate from products obtained after the contact reaction. The method has the advantages of high polyol alkyl ether conversion rate and high polyol alkyl ether acetate selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of polyol alkyl ether acetic ester.
Background technology
Usually, the polyol alkyl ether acetic ester is to be reacted under the katalysis of sulfuric acid and made by polyol alkyl ether and acetic acid or diacetyl oxide.There are the following problems for this kind reaction system: (1) is because dehydration, esterification and the oxygenizement of sulfuric acid, in esterification reaction process, can cause a series of side reactions, a small amount of ether, sulfuric ester, unsaturated compound and carbonyl compound are arranged in the reacted mixture, cause making with extra care with the recovery of unreacting material of reaction product relatively more difficult; (2) aftertreatment of reaction product will be through alkali neutralization, washing to remove the sulfuric acid as catalyzer, causes that complex manufacturing, the three wastes are more, product runs off; (3) sulfuric acid and acetic acid severe corrosion equipment, production energy consumption is high, and cost is high, causes environmental pollution.
At present, although attempted to adopt the cheaper lower member ester of the prices such as methyl acetate, ethyl acetate and the polyol alkyl ether with hydroxyl to carry out transesterification reaction in the industry, with preparation polyol alkyl ether acetic ester.Yet still there are the shortcomings such as low conversion rate, product separation complexity in present Technology.
Summary of the invention
The objective of the invention is the defects that exists in order to overcome the existing method for preparing the polyol alkyl ether acetic ester, a kind of preparation method of new polyol alkyl ether acetic ester is provided.
The invention provides a kind of preparation method of polyol alkyl ether acetic ester, the method comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate with have the polyol alkyl ether contact reacts of at least one hydroxyl, isolate the polyol alkyl ether acetic ester the product that after described contact reacts, obtains.
The preparation method of polyol alkyl ether acetic ester according to the present invention can obtain the pure alkyl oxide transformation efficiency of more much higher unit and polyol alkyl ether acetic ester selectivity.
Method according to the present invention, technique is simple, and lower to the production unit requirement, raw material is easy to get, and energy consumption is low, thereby greatly reduces production cost; And, need not to use acetic acid, sulfuric acid etc. as raw material, reduced equipment corrosion and environmental pollution.
Embodiment
The preparation method of polyol alkyl ether acetic ester according to the present invention comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate with have the polyol alkyl ether contact reacts of at least one hydroxyl, isolate the polyol alkyl ether acetic ester the product that after described contact reacts, obtains.
Method according to the present invention, described transesterification reaction condition can suitably be selected in the transesterification reaction condition of routine.Under the preferable case, described transesterification reaction condition comprises: temperature of reaction is 100-200 ℃, and the reaction times is 3-10 hour.
Method according to the present invention, the mol ratio of sec-butyl acetate and described polyol alkyl ether can be 2-5: 1.
Method according to the present invention, described polyol alkyl ether can be for the conventional polyol alkyl ether that uses in this area, as long as described polyol alkyl ether can transesterification reaction can occur with sec-butyl acetate.
Under the preferable case, described polyol alkyl ether has the structural formula shown in the formula (I),
Formula (I)
Wherein, R
1, R
2And R
3Identical or different, independently of one another at least a in the hydroxyalkyl that is selected from the alkyl of hydrogen, hydroxyl, C1-C5 and C1-C5, and R
1, R
2And R
3In at least one be the hydroxyalkyl of hydroxyl or C1-C5, R
4Be the alkyl of C1-C10, n is the integer of 0-5, and t is the integer of 1-5.
Under above-mentioned preferable case, when t greater than 1, when being 2-5, a plurality of R
3Between can be identical or different, a plurality of R
4Between also can be identical or different.
Under further preferable case, in order to obtain the pure alkyl oxide transformation efficiency of more much higher unit, described polyol alkyl ether is at least a in ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, butyleneglycol monoalky lether, glycerol monoalky lether and the tetramethylolmethane monoalky lether, and the carbonatoms of described alkyl is 1-10.Carbonatoms is that the alkyl of 1-10 is such as thinking methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl etc.Concrete, what described polyol alkyl ether for example can be in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, butyleneglycol monomethyl ether, butyleneglycol list ether, glycerol monomethyl ether, the single ether of glycerol, tetramethylolmethane monomethyl ether and the tetramethylolmethane list ether is at least a.
Method according to the present invention, described transesterification catalyst can use with the catalytic amount of routine.Under the preferable case, with respect to the consumption of the described polyol alkyl ether of 100 weight parts, the consumption of described transesterification catalyst is the 1-5 weight part.
Method according to the present invention, described transesterification catalyst can be the conventional various transesterification catalysts that use in this area, for example can be in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, cesium carbonate, tosic acid, zinc acetate, lead acetate, cadmium acetate, calcium oxide, zinc oxide, plumbous oxide, sodium methylate, tetrabutyl titanate, stannous octoate, sulfuric acid, phosphoric acid, polyphosphoric acid, acidic molecular sieve and the ion exchange resin at least a.Described acidic molecular sieve for example can be ZSM-5 molecular sieve, Y zeolite and H beta-molecular sieve.Described ion exchange resin can be acidic ion exchange resin or deacidite, and described acidic ion exchange resin for example can be styrene type cation exchange resin (such as commercially available D001 type, D201 type and D732 type Zeo-karb) or sulfonic group Zeo-karb (such as commercially available DWN type Zeo-karb); The anionite-exchange resin that described deacidite for example can obtain after the sodium hydroxide solution pre-treatment for quaternary ammonium group anionite-exchange resin, tertiary amine fundamental mode anionite-exchange resin or these anionite-exchange resin is such as 201 * 4 commercially available types, 201 * 4H type, D201 type and D301 type anionite-exchange resin.
Method according to the present invention, isolating the method for polyol alkyl ether acetic ester the product that obtains after described contact reacts can implement according to the separation method of routine, for example can adopt the method for distillation to separate, concrete, for example can comprise that the product that will obtain after the described contact reacts injects distillation tower, control top gaseous phase reflux temperature, to remove unreacted sec-butyl acetate in the described product and newly-generated sec-butyl alcohol, then by tower bottoms being carried out atmospheric flashing or the polyol alkyl ether acetic ester is collected in vacuum flashing.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the selectivity of the transformation efficiency of polyol alkyl ether and polyol alkyl ether acetic ester calculates according to following calculating formula respectively:
The charging capacity of the transformation efficiency of polyol alkyl ether=(residual volume of polyol alkyl ether in the charging capacity-reaction product of polyol alkyl ether)/polyol alkyl ether * 100%
The mole number of the polyol alkyl ether of the mole number of the polyol alkyl ether acetic ester of the selectivity of polyol alkyl ether acetic ester=generation/be converted * 100%
Embodiment 1
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and ethylene glycol monoethyl ether (available from rich ground, east, Shenzhen Chemical trade company limited) are added in the tank reactor as 4: 1 take mol ratio, and with respect to the consumption of the described ethylene glycol monoethyl ether of 100 weight parts, to the tetrabutyl titanate that wherein adds 5 weight parts as catalyzer, under normal pressure, 120 ℃ of lower reactions 4 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects ethylene glycol monoethyl ether acetate.
Learn by calculating, the selectivity of ethylene glycol monoethyl ether acetate is 100%, and the transformation efficiency of ethylene glycol monoethyl ether is 99.6%.
Comparative Examples 1
Method according to embodiment 1 prepares ethylene glycol monoethyl ether acetate, and difference is to replace sec-butyl acetate with methyl acetate.
Learn by calculating, the selectivity of ethylene glycol monoethyl ether acetate is 89.6%, and the transformation efficiency of ethylene glycol monoethyl ether is 85.7%.
Embodiment 2
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and propylene glycol monomethyl ether (available from rich ground, east, Shenzhen Chemical trade company limited) are added in the tank reactor as 3: 1 take mol ratio, and with respect to the consumption of the described propylene glycol monomethyl ether of 100 weight parts, to the sodium methylate that wherein adds 2 weight parts as catalyzer, under normal pressure, 135 ℃ of lower reactions 5 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects propylene glycol methyl ether acetate.
Learn by calculating, the selectivity of propylene glycol methyl ether acetate is 100%, and the transformation efficiency of propylene glycol monomethyl ether is 99.4%.
Embodiment 3
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and butyleneglycol list ether (available from HONEST JOY HOLDINGS LIMITED) are added in the tank reactor as 5: 1 take mol ratio, and with respect to the consumption of the described butyleneglycol list ether of 100 weight parts, to the styrene type cation exchange resin that wherein adds 1 weight part (available from Changsha Da Yu chemical industry company limited, trade mark D001) as catalyzer, under normal pressure, 150 ℃ of lower reactions 3 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects the butyleneglycol monoethyl ether acetate.
Learn by calculating, the selectivity of butyleneglycol monoethyl ether acetate is 100%, and the transformation efficiency of butyleneglycol list ether is 99.5%.
Embodiment 4
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and glycerol monomethyl ether (available from Shanghai uncut jade light Industrial Co., Ltd.) are added in the tank reactor as 2: 1 take mol ratio, and with respect to the consumption of the described glycerol monomethyl ether of 100 weight parts, to the CaO that wherein adds 3 weight parts as catalyzer, under normal pressure, 160 ℃ of lower reactions 6 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects the glycerol methyl ether acetate.
Learn by calculating, the selectivity of glycerol methyl ether acetate is 100%, and the transformation efficiency of glycerol monomethyl ether is 99.1%.
Embodiment 5
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and tetramethylolmethane monomethyl ether (available from Guangzhou big uncle chemical industry company limited) are added in the tank reactor as 3: 1 take mol ratio, and with respect to the consumption of the described tetramethylolmethane monomethyl ether of 100 weight parts, to the D301 anionite-exchange resin that wherein adds 4 weight parts (available from Langfang prosperous chemical building material of prosperous Sheng company limited) as catalyzer, under normal pressure, 170 ℃ of lower reactions 6 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects the tetramethylolmethane methyl ether acetate.
Learn by calculating, the selectivity of tetramethylolmethane methyl ether acetate is 100%, and the transformation efficiency of tetramethylolmethane monomethyl ether is 99.2%.
Embodiment 6
The present embodiment is used for illustrating the preparation method of described polyol alkyl ether acetic ester of the present invention.
Sec-butyl acetate and tetramethylolmethane list ether (available from Guangzhou big uncle chemical industry company limited) are added in the tank reactor as 3: 1 take mol ratio, and with respect to the consumption of the described tetramethylolmethane list ether of 100 weight parts, to the ZSM-5 molecular sieve that wherein adds 3 weight parts (available from Nanjing Ji Cang nanosecond science and technology company limited) as catalyzer, under normal pressure, 180 ℃ of lower reactions 8 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out atmospheric flashing, collects the tetramethylolmethane monoethyl ether acetate.
Learn by calculating, the selectivity of tetramethylolmethane monoethyl ether acetate is 100%, and the transformation efficiency of tetramethylolmethane list ether is 99.0%.
Result by above-described embodiment can find out, method according to the present invention can obtain the pure alkyl oxide transformation efficiency of more much higher unit and polyol alkyl ether acetic ester selectivity.Particularly, embodiment 1 is compared and can find out with Comparative Examples 1, with respect to transformation efficiency and the reaction preference of using methyl acetate and polyol alkyl ether to carry out transesterify, by selecting sec-butyl acetate and polyol alkyl ether to carry out transesterification reaction, obtained polyol alkyl ether transformation efficiency and the polyol alkyl ether acetic ester selectivity of obvious raising among the present invention.
Claims (8)
1. the preparation method of a polyol alkyl ether acetic ester, the method comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate with have the polyol alkyl ether contact reacts of at least one hydroxyl, isolate the polyol alkyl ether acetic ester the product that after described contact reacts, obtains.
2. method according to claim 1, wherein, described transesterification reaction condition comprises: temperature of reaction is 100-200 ℃, the reaction times is 3-10 hour.
3. method according to claim 1, wherein, the mol ratio of sec-butyl acetate and described polyol alkyl ether is 2-5: 1.
4. according to claim 1 or 3 described methods, wherein, described polyol alkyl ether has the structural formula shown in the formula (I),
Formula (I)
Wherein, R
1, R
2And R
3Identical or different, independently of one another at least a in the hydroxyalkyl that is selected from the alkyl of hydrogen, hydroxyl, C1-C5 and C1-C5, and R
1, R
2And R
3In at least one be the hydroxyalkyl of hydroxyl or C1-C5, R
4Be the alkyl of C1-C10, n is the integer of 0-5, and t is the integer of 1-5.
5. method according to claim 4, wherein, described polyol alkyl ether is at least a in ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, butyleneglycol monoalky lether, glycerol monoalky lether and the tetramethylolmethane monoalky lether, and the carbonatoms of described alkyl is 1-10.
6. method according to claim 5, wherein, described polyol alkyl ether is at least a in the single ether of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, butyleneglycol monomethyl ether, butyleneglycol list ether, glycerol monomethyl ether, glycerol, tetramethylolmethane monomethyl ether and the tetramethylolmethane list ether.
7. method according to claim 1, wherein, with respect to the consumption of the described polyol alkyl ether of 100 weight parts, the consumption of described transesterification catalyst is the 1-5 weight part.
8. according to claim 1 or 7 described methods, wherein, described transesterification catalyst is at least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, cesium carbonate, tosic acid, zinc acetate, lead acetate, cadmium acetate, calcium oxide, zinc oxide, plumbous oxide, sodium methylate, tetrabutyl titanate, stannous octoate, sulfuric acid, phosphoric acid, polyphosphoric acid, acidic molecular sieve and the ion exchange resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
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