CN1128796C - Process for production of 1,3-dioxolane - Google Patents
Process for production of 1,3-dioxolane Download PDFInfo
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- CN1128796C CN1128796C CN96112618A CN96112618A CN1128796C CN 1128796 C CN1128796 C CN 1128796C CN 96112618 A CN96112618 A CN 96112618A CN 96112618 A CN96112618 A CN 96112618A CN 1128796 C CN1128796 C CN 1128796C
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract
Process for production of 1,3-dioxolane. The method for producing 1,3-dioxolane comprises reacting formaldehyde or a substance generating the compound with ethylene glycol or ethylene oxide in the presence of an acid catalyst, distilling the reaction solution containing 1,3-dioxolance and water, extracting the obtained reaction mixture with a compound of the formul, distilling the extract solution to remove the water, and subsequently separating the extracting agent.
Description
The present invention relates to prepare 1, the method for 3-dioxolane, described 1, the 3-dioxolane is as raw material of the stablizer of the electroanalysis solvent of the solvent of oil ﹠ fat, extraction agent, lithium cell, chloro solvent, pharmaceutical intermediate, Derlin or the like.
As preparation 1, the method for 3-dioxolane, the cyclization of ethylene glycol and formaldehyde is known.For example, Deutsches Reichs-Patent 1914209 discloses, and obtains containing 1 of 7wt% water by the yield that formalin and ethylene glycol are reacted with 96.5% in the presence of acid catalyst, the 3-dioxolane.
Yet, in aforesaid method, 1,3-dioxolane and the water that forms as by product or in raw material contained water form azeotropic mixture, thereby, only be difficult to high level ground and remove and anhydrate by distilation steps.
In addition, when 1, when the 3-dioxolane was used as the polymeric monomer, the water of above-mentioned trace hindered reaction usually very much, thereby the dehydration of high level is essential.
At Industrial ﹠amp; Engineering Chemistry, Vol.46,787 (1954) disclose a kind of purifying 1, the method of 3-dioxolane wherein, is reacted in the presence of acid catalyst by making paraformaldehyde and ethylene glycol, the distillation reaction mixture, in the reaction distillation thing, add sodium-chlor make it be divided into two-layer and the rectifying organic layer can obtain highly purified 1, the 3-dioxolane.Yet,, need come producing apparatus with impregnating material, thereby aforesaid method is difficult to adopt as commercial run because aforesaid method needs a large amount of sodium-chlor.
On the other hand, there is a kind of currently known methods, wherein moisture 1, the 3-dioxolane is at extraction agent, for example methylene dichloride, tetraline or normal heptane extract under existing, extract dewaters by component distillation, subsequently by fractionation by distillation extraction agent and 1, and 3-dioxolane (the open 49-62469 of Japanese Patent).Yet aforesaid method in the following areas may not be satisfactory, and methylene dichloride is restricted the material of equipment, and tetraline and normal heptane show the extraction 1 of difference, the efficient of 3-dioxolane, thereby need to reclaim a large amount of extraction agents.
An object of the present invention is to provide a kind of preparation 1, the method for 3-dioxolane, it is reclaiming 1 to almost not corrosion of equipment, 3-dioxolane aspect is effectively, thereby industrial be useful.
Another object of the present invention provide a kind of preparation anhydrous basically be suitable as the monomeric 1 of preparation polyacetal resin, the method for 3-dioxolane.
The inventor studies the raw material and the ethylene glycol 1 that maybe can be produced formaldehyde by formaldehyde hardy, the method for 3-dioxolane, and the result has finished the present invention by finding following feature.When benzene that alkyl replaces extracts 1 in by the reaction distillation thing that obtains by the distillation reaction mixture, during the extraction agent of 3-dioxolane, can extract 1 expeditiously, the 3-dioxolane.In addition,, can be easily substantially anhydrous 1 at extract by separating with high yield in the extract by distillation by behind the distillation dehydration, the 3-dioxolane.
That is, above-mentioned purpose of the present invention is by a kind of raw material and ethylene glycol prepared in reaction 1 in the presence of an acidic catalyst of using formaldehyde or producing formaldehyde, and the method for 3-dioxolane realizes that this method comprises the steps:
(1) in the presence of the benzene that the alkyl as the following general formula (1) of extraction agent replaces by from the reaction mixture that forms, extracting 1 in the isolating reaction distillation thing by distilling, the 3-dioxolane,
(2) by distillation make generation extract dehydration and
(3) separate 1 by distilling in the extract by dehydration, the 3-dioxolane,
Wherein, R
1Be alkyl with 1 to 4 carbon atom, each R
2To R
5Be hydrogen atom or alkyl independently with 1 to 4 carbon atom.
Accompanying drawing 1 shows 1, and the benzene that 3-dioxolane and alkyl replace is as the benzene that replaces as typical alkyl, the vapor-liquid equilibrium curve of toluene and blended dimethylbenzene.
Accompanying drawing 2 demonstrations are used for 1 of comparison, the vapor-liquid equilibrium curve of 3-dioxolane and hexanaphthene or benzene.
Can find out obviously that from attached Fig. 1 and 2 according to the present invention, DOX can easily separate with the benzene that alkyl replaces by distillation.
Be used for the reaction distillation thing that the present invention contains DOX and water and can or produce formaldehydogenic raw material and ethylene glycol obtains by formaldehyde. For the preparation above-mentioned reaction distillation thing method do not have special restriction, as long as its industrial can. Usually, the reaction distillation thing can be by making formaldehyde or producing formaldehydogenic raw material and ethylene glycol and react in the presence of acidic catalyst and separate formed DOX by distillation in by reactor and water obtains.
Produce formaldehydogenic raw material (compound) and comprise Fu Er Malin, paraformaldehyde, trioxane, four oxocane and polyacetals. These compounds can be combined with individually. Paraformaldehyde or Fu Er Malin are especially preferred.
Acid catalyst can be selected from all and show acid material, especially preferably nonvolatile acid under reaction condition in liquid phase. The example of acid catalyst comprises inorganic acid, for example, and sulfuric acid, hydrochloric acid and phosphoric acid; Organic acid, for example, sulfonic acid, phosphonic acids and carboxylic acid; Solid acid catalyst, for example, strong-acid ion exchange resin, zeolite, silica, aluminium oxide and activated clay; With assorted polyphosphoric acid, for example, phosphomolybdic acid and phosphotungstic acid. In these acid catalysts, preferably sulfuric acid.
Reaction temperature is 20-200 ℃, preferred 80-150 ℃. Reaction pressure is not particularly limited, adopts under reaction temperature, to make most of raw materials and catalyst be in liquid pressure.
The quantity ratios of ethylene glycol and formaldehyde is as follows. The amount of the ethylene glycol that every moles of formaldehyde is corresponding is the 0.5-2 mole, preferred 0.7-1.7 mole. When using the formaldehydogenic raw material of product, the use amount of raw material satisfies above-mentioned scope for the amount of the formaldehyde of generation.
Reaction is for example carried out in the reactor of container, pipe or tower type at normally used reactor, reaction can discontinuous method and current method in any carrying out. The DOX that forms by reaction directly separates from reaction system by distillation or separates from reaction system by destilling tower.
Yet when reaction carried out containing the DOX product vapor with continuous outflow with normally used evaporimeter, the reaction distillation thing contained a considerable amount of impurity and unreacted raw materials as accessory substance formation, thereby was difficult to carry out purge process subsequently.
Thereby, when containing 1, when the product of 3-dioxolane separates from remaining mixture continuously, need by distillation tower separating reaction distillment.The preferred reactor that has a solution-air contact part that uses, contain 1 by what reaction mixture produced, the steam of 3-dioxolane moves up, by being condensed after the above-mentioned solution-air contact part, a part of condensation product is circulated to above-mentioned solution-air contact part, and logistics goes out remaining condensation product as reaction distillation.
Type for above-mentioned distillation tower is not particularly limited, and it can be any in tray column and the packing tower.Stage number (be theoretical plate number under the situation of packing tower: it also is applicable to following packing tower) is preferably 1 to 20.Reflux ratio is generally 0.2 to 5, is preferably 0.5 to 3.
What obtain contains 1, and the reaction distillation thing of 3-dioxolane contains 1, and 3-dioxolane and other material are as from the water and the unconverted formaldehyde that produce as the water of raw material formalin, as by product.Thereby the preferred further distillation of reaction distillation thing is to be condensed into 1,3-dioxolane-water azeotropic mixture (containing 8.5wt% water).
Above-mentioned enrichment step carries out in upgrading tower continuously.With above-mentioned reaction distillation thing input upgrading tower, obtain from cat head thick 1, the 3-dioxolane, it is 1,3 dioxolane-water azeotropic mixture (containing 8.5wt% water).And separate at the bottom of the tower and obtain water and formaldehyde.Can be used as part material by isolating formalin at the bottom of the tower after concentrating reuses.
The upgrading tower that uses in enrichment step is common board-like or packing tower.Preferably the stage number at concentrating part is 1 to 40, is 2 to 55 in stripping stage number partly.Reflux ratio is preferably 0.5 to 10.
In the present invention, contain 1,3-dioxolane and water, or above-mentioned thick 1, the benzene extraction that the reaction distillation thing of 3-dioxolane replaces with alkyl, extract are by distillation dehydration, subsequently by fractionation by distillation 1, the 3-dioxolane, thus obtain with high yield substantially anhydrous 1, the 3-dioxolane.
The benzene of the alkyl replacement of using in the present invention refers to the compound of following general formula (1):
Wherein, R
1Be alkyl with 1 to 4 carbon atom, each R
2To R
5Be hydrogen atom or alkyl independently with 1 to 4 carbon atom.
The special case of the benzene that alkyl replaces comprise toluene, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, sec-butylbenzene, tert.-butylbenzene, ortho-xylene ,-dimethylbenzene, right-dimethylbenzene, 4-sec.-propyl-1-methylbenzene, 1,1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,3,5-triethyl-benzene, 1,2,3,4-durene and 1,2,3, the 5-durene.Preferred toluene, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, sec-butylbenzene, tert.-butylbenzene, ortho-xylene ,-dimethylbenzene, right-dimethylbenzene, 4-sec.-propyl-1-methylbenzene, 1,2,4-trimethylbenzene or 1,2,5-trimethylbenzene.Especially preferred toluene, ortho-xylene ,-dimethylbenzene or right-dimethylbenzene.The benzene that abovementioned alkyl replaces can separately or be used in combination.
The usage quantity of the benzene that alkyl replaces, based on a (weight) 1, the 3-dioxolane is preferably 0.01 to 100 part (weight), and more preferably 0.1 to 10 part (weight) most preferably is 0.5 to 3 part (weight).
Type for the equipment that uses in extraction step has no particular limits, as long as it can industrially use.It can be intermittently, multistage, successive, and the equipment of stream or reverse flow type.For example, it is selected from mixer-settlers, spray quinoline tower, perforated plate tower, baffle-plate column, packing tower, pulse-column or has the extraction column of agitator.
Reaction distillation thing or thick 1, the mixing time of 3-dioxolane and extraction agent is 0.1 to 180 minute in discontinuous method and continuation method.In addition, in discontinuous method and continuation method, leave standstill and be 0.5 to 180 minute.
Organic layer after the extraction (extract) contains three components, as 1, and benzene and a spot of water that 3-dioxolane, alkyl replace, extract is transfused to dehydrating step subsequently.On the other hand, water layer (raffinate) contains 1, and 3-dioxolane, water layer can be removed or by distilling as 1,3-dioxolane-water azeotropic product reclaims.
In dehydrating step, by 1, the component distillation of 3-dioxolane and water removes and anhydrates.Thereby in dehydrating step, in leaching process, organic layer is imported dehydration tower continuously, distills out 1 from cat head, 3-dioxolane-water azeotropic product, and 1, benzene and mixture that 3-dioxolane and alkyl replace obtain at the bottom of tower.Bottom stream input separating step subsequently.And the distillment of cat head is also capable of circulation to extraction step or the concentrated and recovery with the water layer of extraction step.
The dehydration tower that uses in dehydrating step is common board-like or packing tower.Preferably the stage number at concentrating part is 5 to 90, is 1 to 30 in stripping stage number partly.In addition, reflux ratio is preferably 0.5 to 30.
Separating step carries out in purification column, and 1, the mixture of the benzene that 3-dioxolane and alkyl replace is transfused to purification column, obtains 1 of purifying from cat head, and the 3-dioxolane is by obtaining the benzene that alkyl replaces at the bottom of the tower.The benzene that the alkyl that obtains replaces is circulated to extraction step.
The purification column of using in separating step is common board-like or packing tower.Preferably the stage number at concentrating part is 10 to 100, is 1 to 20 in stripping stage number partly.Reflux ratio is preferably 0.5 to 30.
Embodiment
To explain the present invention with reference to the following examples and comparing embodiment, and these embodiment do not limit the scope of the invention.
In 3 liters of reactors of thermometer, agitator and condenser are housed, add 537.5g70wt% formalin, 662.5g ethylene glycol and 12g98% sulfuric acid, make mixture be warming up to about 100 ℃.Temperature is that 85 to 90 ℃ reaction vapor is discharged from condenser.Simultaneously, begin distillation, the mixture of 70wt% formalin and ethylene glycol (weight ratio 1: 1.23) is with the rate input reactor of 600g/hr, and control adds heat with balance feeding rate and distillment rate of discharge.
Reaction distillation thing: 600g/hr
Form:
1,3-dioxolane 65.8wt%
Water 29.2wt%
Formaldehyde 5.0wt%
In addition, the reaction distillation thing is with the flow input glass orifice plate continuous still battery tower (internal diameter 50mm, 10 column plates of stripping stage, 5 column plates of enriching section) of 600g/h.Reflux ratio is adjusted to 2.After the distillation tower temperature begins to stablize, obtain having overhead stream and bottom stream as down-off and composition.
(1) overhead stream: 433g/hr
Form:
1,3-dioxolane 91.2wt%
Water 8.6wt%
(2) bottom stream: 167g/hr
Form:
1,3-dioxolane 0.0wt%
Water 83.1wt%
Formaldehyde 16.5wt%
98.0g above-mentioned obtain contain 1 of 8.6wt% water, 3-dioxolane azeotropic mixture and 102.0g toluene add and have in the 500ml glass flask of agitator, violent stirring is 1 minute in 30 ℃ water-bath.Subsequently, mixture was left standstill 20 minutes, measure the weight and the composition of isolating organic layer (extract) and water layer (raffinate).Table 1 demonstrates the result.
The above-mentioned organic layer that obtains (toluene 53.7wt%, 1,3-dioxolane 45.6wt%, water 0.7wt%) is with the flow input glass orifice plate continuous still battery tower (internal diameter 50mm, 10 column plates of stripping stage, 20 column plates of enriching section) of 600g/h.Reflux ratio is adjusted to 15.After the distillation tower temperature begins to stablize, obtain having overhead stream and bottom stream as down-off and composition.
(1) overhead stream: 56g/hr
Form:
1,3-dioxolane 92.4wt%
Water 7.5wt%
Toluene 0.1wt%
(2) bottom stream: 544g/hr
Form:
1,3-dioxolane 40.9wt%
Water 10ppm
Toluene 59.1wt%
The above-mentioned bottom stream (2) that obtains is transfused to glass orifice plate continuous still battery tower (internal diameter 50mm, 5 column plates of stripping stage, 40 column plates of enriching section) with the flow of 544g/h.Reflux ratio is adjusted to 10.After the distillation tower temperature begins to stablize, obtain having as 1 of down-off and composition the 3-dioxolane.
(1) overhead stream: 219g/hr
Form:
1,3-dioxolane 99.9wt%
Toluene 0.01wt%
Water 25ppm
(2) bottom stream: 325g/hr
Form:
1,3-dioxolane 0.99wt%
Toluene 99.0wt%
Embodiment 2
In 3 liters of reactors of thermometer and agitator are housed, add 537.5g70wt% formalin, 662.5g ethylene glycol and 12g98% sulfuric acid, make mixture be warming up to about 115 ℃.Temperature be 85 to 95 ℃ reaction vapor by having 5 orifice plates glass distillation tower (internal diameter 50mm) and return channel after liquefy, subsequently, liquid is discharged with reflux ratio 1.24.Simultaneously, open pregnant distillation, the mixture of 70wt% formalin and ethylene glycol (weight ratio 1: 1.42) is with the rate input reactor of 600g/hr, and control adds heat with balance feeding rate and distillment rate of discharge.
Reaction distillation thing: 600g/hr
Form:
1,3-dioxolane 70.0wt%
Water 29.4wt%
Formaldehyde 0.5wt%
In addition, the reaction distillation thing is with the flow input glass orifice plate continuous still battery tower (internal diameter 50mm, 10 column plates of stripping stage, 5 column plates of enriching section) of 600g/h.Reflux ratio is adjusted to 2.After the distillation tower temperature begins to stablize, obtain having overhead stream and bottom stream as down-off and composition.
(1) overhead stream: 460g/hr
Form:
1,3-dioxolane 91.2wt%
Water 8.6wt%
(2) bottom stream: 140g/hr
Form:
1,3-dioxolane 0.0wt%
Water 97.7wt%
Formaldehyde 2.3wt%
98.0g above-mentioned obtain contain 1 of 8.6wt% water, 3-dioxolane azeotropic mixture and 81.6g add as the toluene of extraction agent and have in the 500ml glass flask of agitator, violent stirring is 1 minute in 30 ℃ water-bath.Subsequently, mixture was left standstill 20 minutes, measure the weight and the composition of isolating organic layer (extract) and water layer (raffinate).Table 1 demonstrates the result.
The above-mentioned organic layer that obtains (toluene 47.9wt%, 1,3-dioxolane 50.8wt%, water 0.9wt%) is transfused to glass orifice plate continuous still battery tower (internal diameter 50mm, 10 column plates of stripping stage, 20 column plates of enriching section) with the flow of 600g/h.Reflux ratio is adjusted to 8.After the distillation tower temperature begins to stablize, obtain having overhead stream and bottom stream as down-off and composition.
(1) overhead stream: 71g/hr
Form:
1,3-dioxolane 92.3wt%
Water 7.6wt%
Toluene 0.1wt%
(2) bottom stream: 529g/hr
Form:
1,3-dioxolane 45.4wt%
Water 20ppm
Toluene 54.4wt%
The above-mentioned bottom stream (2) that obtains is transfused to glass orifice plate continuous still battery tower (internal diameter 50mm, 5 column plates of stripping stage, 40 column plates of enriching section) with the flow of 529g/h.Reflux ratio is adjusted to 10.After the distillation tower temperature begins to stablize, obtain having as 1 of down-off and composition the 3-dioxolane.
(1) overhead stream: 237g/hr
Form:
1,3-dioxolane 99.9wt%
Toluene 0.01wt%
Water 45ppm
(2) bottom stream: 292g/hr
Form:
1,3-dioxolane 1.0wt%
Toluene 98.8wt%
Embodiment 3
The above results shows, is extracting 1,3-dioxolane efficient aspect, and method of the present invention is better than ordinary method.
Table 1
Ex.=embodiment, CEx=comparing embodiment * 1, the loss of 3-dioxolane is the ratio that remains in the dioxolane of water layer dioxolane and adding
| Weight (g) | Form (wt%) | 1, the loss of 3-dioxolane (wt%) | ||||
| | 1, the 3-dioxolane | Water | ||||
| Ex.1 | Organic layer | 189.9 | 53.7 | 45.6 | 0.7 | 3.3 |
| Water layer | 10.1 | 0.0 | 29.5 | 70.5 | ||
| Ex.2 | Organic layer | 170.1 | 47.9 | 50.8 | 0.9 | 2.9 |
| Water layer | 9.5 | 0.0 | 27.2 | 72.8 | ||
| Ex.3 | Organic layer | 189.7 | 53.8 | 45.5 | 0.7 | 3.6 |
| Water layer | 10.3 | 0.0 | 31.4 | 68.9 | ||
| CEx. 1 | Organic layer | 186.7 | 54.6 | 44.8 | 0.6 | 6.6 |
| Water layer | 13.3 | 0.0 | 44.6 | 55.4 | ||
| CEx. 2 | Organic layer | 183.8 | 55.7 | 43.8 | 0.6 | 11.5 |
| Water layer | 17.8 | 0.0 | 58.6 | 41.4 | ||
| CEx. 3 | Organic layer | 187.9 | 54.3 | 44.9 | 0.8 | 6.1 |
| Water layer | 12.4 | 0.0 | 44.2 | 55.8 | ||
The benzene that replaces when alkyl of the present invention is during as extraction agent, by the combination simple operation, for example extracts and distills, can obtain effectively substantially anhydrous 1, the 3-dioxolane, method of the present invention industrial be important.In addition, the method according to this invention obtain 1, the 3-dioxolane be suitable as the preparation polyacetal resin monomer.
Claims (5)
1. one kind by making formaldehyde or produce raw material and ethylene glycol prepared in reaction 1 in the presence of an acidic catalyst of formaldehyde, the method for 3-dioxolane, and it comprises the steps:
(1) in the presence of the benzene that the alkyl as the following general formula (1) of extraction agent replaces by from the reaction mixture that forms, extracting 1 in the isolating reaction distillation thing by distilling, the 3-dioxolane,
(2) by distillation make generation extract dehydration and
(3) separate 1 by distilling in the extract by dehydration, the 3-dioxolane,
Wherein, R
1Be alkyl with 1 to 4 carbon atom, each R
2To R
5Be hydrogen atom or alkyl independently with 1 to 4 carbon atom.
2. the process of claim 1 wherein the reaction distillation thing by distillation tower by separating in the reaction mixture.
3. claim 1 or 2 method, wherein the reaction distillation thing is transfused to upgrading tower earlier forming 1,3-dioxolane-water azeotropic mixture thick 1, the 3-dioxolane, to thick 1, the 3-dioxolane carries out the extraction step operation subsequently.
4. the process of claim 1 wherein benzene that alkyl replaces be at least a be selected from toluene, ortho-xylene ,-benzene that the alkyl of dimethylbenzene and right-dimethylbenzene replaces.
5. the process of claim 1 wherein in extraction step, use based on 1 part of (weight) 1, the amount of the benzene that the alkyl of 3-dioxolane replaces is 0.1 to 10 part (weight).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP198649/1995 | 1995-08-03 | ||
| JP7198649A JPH0948774A (en) | 1995-08-03 | 1995-08-03 | Production of 1,3-dioxolane |
| JP198649/95 | 1995-08-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149055A CN1149055A (en) | 1997-05-07 |
| CN1128796C true CN1128796C (en) | 2003-11-26 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96112618A Expired - Fee Related CN1128796C (en) | 1995-08-03 | 1996-08-03 | Process for production of 1,3-dioxolane |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0948774A (en) |
| KR (1) | KR100485226B1 (en) |
| CN (1) | CN1128796C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464645A (en) * | 2010-11-16 | 2012-05-23 | 天津赛普泰克科技有限公司 | Process for refining dioxolane through extractive distillation |
| CN102174033A (en) * | 2011-03-07 | 2011-09-07 | 天津游龙科技发展有限公司 | New method for preparing 1,3-dioxolane by catalytic condensation |
| CN102267972B (en) * | 2011-06-15 | 2013-03-13 | 四川之江化工新材料有限公司 | Method for producing 1,3-dioxolame based on reaction-separation coupling |
| CN102794185B (en) * | 2012-08-28 | 2014-07-23 | 四川之江高新材料股份有限公司 | Method, catalyst and device for prepareing 1,3-dioxolane |
| CN112292372A (en) * | 2018-05-18 | 2021-01-29 | 巴斯夫欧洲公司 | Process for preparing dioxolanes |
| EP3793985B1 (en) | 2018-05-18 | 2022-10-12 | Basf Se | Process for preparing dioxolane |
| CN111978284A (en) * | 2020-08-14 | 2020-11-24 | 中化学科学技术研究有限公司 | Preparation process and preparation system of dioxolane |
-
1995
- 1995-08-03 JP JP7198649A patent/JPH0948774A/en active Pending
-
1996
- 1996-08-02 KR KR1019960032355A patent/KR100485226B1/en not_active IP Right Cessation
- 1996-08-03 CN CN96112618A patent/CN1128796C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1149055A (en) | 1997-05-07 |
| JPH0948774A (en) | 1997-02-18 |
| KR100485226B1 (en) | 2005-12-26 |
| KR970010759A (en) | 1997-03-27 |
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