CN102702166A - Method for preparing glycerin shrinkage benzaldehyde - Google Patents
Method for preparing glycerin shrinkage benzaldehyde Download PDFInfo
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- CN102702166A CN102702166A CN2012101511185A CN201210151118A CN102702166A CN 102702166 A CN102702166 A CN 102702166A CN 2012101511185 A CN2012101511185 A CN 2012101511185A CN 201210151118 A CN201210151118 A CN 201210151118A CN 102702166 A CN102702166 A CN 102702166A
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Abstract
The invention discloses a method for preparing glycerin shrinkage benzaldehyde. The method comprises adding glycerin and benzaldehyde into ionic liquid serving as reaction media and catalysts to perform nucleophilic addition reaction, wherein anode ions and cathode ions of the ionic liquid at least contain one acid group. The method has the advantages of being environment-friendly, low in corrosion to devices, capable of effectively improving yield of the glycerin shrinkage benzaldehyde and the like. In addition, the catalysts can be repeatedly used.
Description
Technical field
The present invention relates to glycerine acetal (ketone) technical field, specifically a kind of preparation glycerol acetonide method of benzaldehyde.
Background technology
Greatly develop biofuel to sustainable economic development, advance energy substitution, alleviate environmental stress, the control urban atmospheric pollution guarantees that national energy security has the important strategic meaning.Yet the production method of bio-diesel oil mainly is to carry out transesterification reaction with animal-plant oil and low-molecular-weight alcohol (like methyl alcohol, ethanol etc.) at present.Shown in 1, formula 1 is a preparation biofuel reaction equation in the prior art.The a large amount of inferior quality glycerine of this reaction process meeting coproduction, 10 tons of biofuel of every production produce 1 ton of glycerine approximately.
Along with petroleum resources shortage day by day; Countries in the world are considered from environment protection and resource recovery angle, can continue to widely popularize biofuel, so by-product glycerin will be excessive; Drug on the market in glycerine market, thereby cause the traditional glycerol production equipment to stop production in succession.See from the another one angle,, possibly become new source of pollution if these raw glycerine waste liquids can not utilize and handle timely and effectively.Therefore; Production of biodiesel process effective comprehensive utilization of raw glycerine at a middle or low price becomes sternness of biofuel industry and crucial problem; How rationally utilizing raw glycerine, seek and develop its new purposes, will be the crucial and guarantee of biofuel industry Sustainable development.
Formula 2 is the reaction formula of glycerine and five yuan of aldehyde (ketone) reaction generations or six-membered cyclic acetal (ketone) glycerine acetal (ketone)
Formula 2
Shown in 2, glycerine can generate five-ring or six-membered cyclic acetal or ketal with various aldehydes or ketones reactions.Five-ring that this reaction generates or six-membered cyclic acetal or ketal are one type of high-grade novel fragrances that is superior to the parent carbonyl compound, extensive use is arranged, and have extremely strong diffusibility and stable chemical properties; Glycerine acetal (ketone) is that important carbonyl keeps form, is usually used in the midbody or the raw material of synthetic and paint, food, tobacco, makeup and the pharmaceutical industry etc. of steroid, glucide.At present, glycerine acetal (ketone) one of the most attracting research field be the glyceryl additive that preparation improves biofuel character.This type of glycerine acetal (ketone) joins in the fuel oil with 10% volume ratio, can be used as internal-combustion engine ignition accelerator and knock-compound, not only can reduce ignition temperature, pour point (PP) and viscosity, also can reduce the particulate emission of diesel oil fuel.The more important thing is that it can directly be retained in the biofuel, will make yield of biodiesel increase by 16%.
Therefore, glycerine is processed into other high value added products as starting material, not only can solves the superfluous crisis of glycerine; Can also the extension industry chain, make the biofuel raising the output; Improve overall economic efficiency, kill two birds with one stone still not a kind of Sustainable development route that meets Economic Development, environment protection needs; Also be the complete recycle that realizes natural resource, be similar to the green cleaning technique of zero release.
Mostly the condensation reaction of traditional aldehyde (ketone) is glycols acetal (ketone), less for the research of synthetic glycerine class acetal (ketone).The catalyzer of glycerine and aldehyde ketone condensation prepared glycerine acetal (ketone) is generally mineral acid (like H
2SO
4, HCl, H
3PO
4Deng).Because these system side reactions are many, strong to equipment corrosion, product purity is low, post-reaction treatment is complicated, produce a large amount of acid waste residues and waste liquid have brought havoc to environment, cause secondary pollution, its use is restricted greatly.Some solid acid catalysts that grew up afterwards; Though has overcome above-mentioned weak point like heteropolyacid, niobic acid, molecular sieve etc., and aftertreatment technology is simplified, yet the active site density of solid heterogeneous catalyst is low; Relative reactivity is lower; Inactivation generally needs long reaction times and higher temperature easily, is easy to generate more by product.Therefore; Exploitation cleaning, green glycerine acetal (ketone) generate technology, solve harsh processing condition, design a catalytic activity height; The product separate easily; Substitute the eco-friendly chemical conversion process of mineral acid and volatile, deleterious band water organic solvent, make the production greenization more of glycerine acetal (ketone), be green novel hardware and software platform compound glycerine higher value application, biofuel large-scale production, satisfy the inevitable choice that green bio materialization worker requires.
In view of the problem and the defective that exist in above-mentioned existing glycerine and aldehyde (ketone) reaction, the inventor relies on practical experience for many years and enriches a kind of preparation method who prepares the glycerol acetonide phenyl aldehyde of expertise research and development, to solve the problem that exists in the prior art.
Summary of the invention
In order to solve the problems referred to above that exist in the prior art, the invention provides a kind of glycerol acetonide method of benzaldehyde.Have environmental protection, equipment corrosion is low, and catalyzer can reuse, and effectively improves the characteristics such as productive rate of glycerol acetonide phenyl aldehyde.
In order to solve the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of preparation glycerol acetonide method of benzaldehyde joins glycerine and phenyl aldehyde as carrying out nucleophilic addition in the ionic liquid of reaction medium and catalyzer, contains an acidic-group in said ion liquid positively charged ion and the negatively charged ion at least.
Further; Said positively charged ion is selected from a kind of in the following positively charged ion: alkyl imidazole positively charged ion, sulfonic acid substituted alkyl glyoxaline cation, allyl imidazole positively charged ion, carboxyl substituted alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, sulfonic acid substituted alkyl pyridylium, carboxyl substituted alkyl pyridine positively charged ion, sulfonic acid substituted alkyl vulkacit H positively charged ion, sulfonic acid substituted alkyl triethylene diamine positively charged ion, carboxyl substituted alkylamine positively charged ion and sulfonic acid substituted alkylamine positively charged ion.
Further, said positively charged ion is preferably alkyl imidazole positively charged ion, sulfonic acid substituted alkyl glyoxaline cation or sulfonic acid substituted alkyl pyridylium.
Further, said negatively charged ion is selected from a kind of in the following negatively charged ion: sulfate anion (HSO
4 -), acetate negatively charged ion (CH
3COO
-), phosphate anion (H
2PO
4 -), fluoroboric acid negatively charged ion (BF
4 -), hexafluorophosphoric acid negatively charged ion (PF
6 -), trifluoromethanesulfonic acid negatively charged ion (CF
3SO
3 -), methylsulphonic acid negatively charged ion (CH
3SO
3 -), formic acid negatively charged ion (HCOO
-), salt acid anion (Cl
-), nitric acid negatively charged ion (NO
3 -), trifluoroacetic acid negatively charged ion (CF
3CO
2 -), sulfurous acid negatively charged ion (HSO
3 -), carbonate anion (HCO
3 -) and toluene sulfonic acide negatively charged ion (CH
3(C
6H
4) SO
3 -).
Further, said negatively charged ion is preferably sulfate anion, trifluoromethanesulfonic acid negatively charged ion or methylsulphonic acid negatively charged ion.
Further, said ionic liquid is preferably trifluoromethayl sulfonic acid root 1-methyl-3-fourth sulfonic group imidazoles ([BSmim] CF
3SO
3), bisulfate ion 1-methyl-3-fourth sulfonic group imidazoles ([BSmim] HSO
4) or bisulfate ion 1-ethyl-3-Methylimidazole ([Emim] HSO
4).
Further, the mol ratio of phenyl aldehyde and glycerine is 1:0.25～10 in the said nucleophilic addition.
Further, the temperature of reaction of said nucleophilic addition is 25～100 ℃, and the reaction times is 5～180 minutes.
Further, phenyl aldehyde and ion liquid mol ratio are 1:0.05～1 in the said nucleophilic addition.
Compared with prior art, beneficial effect of the present invention is:
1, ionic liquid of the present invention can be simultaneously as reaction medium and catalyzer in nucleophilic addition, and reaction conditions is gentle, and is environmentally friendly, low to equipment corrosion;
2, the present invention adopt simple technology promptly separable, reclaim ionic-liquid catalyst, the catalyzer of recovery can reuse, and catalytic performance is stable;
3, the use that has the water absorption character acidic ion liquid; Not only avoid the use of the poisonous organic band aqua of volatility; Stopped extra composition pollution products; And ionic liquid in time absorbs moisture, reached pulling condensation reaction balance and moved to product side, effectively improves productive rate, quality and the selectivity of glycerol acetonide phenyl aldehyde.
4, simple, the safety of preparing method's technology of the ionic liquid-catalyzed system of the present invention, easy to operate, the product subsequent disposal is simple, and glycerol conversion yield is high, and product glycerol acetonide phenyl aldehyde is had selectivity preferably.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but not as to qualification of the present invention.
Ionic liquid of the present invention is common commercially available or prepare according to ordinary method of the prior art.At least contain an acidic-group in ion liquid positively charged ion and the negatively charged ion and be meant that acidic-group can also can be in negatively charged ion in positively charged ion; When acidic-group is two or more; It can exist in the positively charged ion also simultaneously can be in negatively charged ion, and these two or more acidic-groups can be identical also can be different.
Following embodiment please refer to formula 2, wherein is raw material and glycerine reaction with the phenyl aldehyde.
Embodiment 1
In reaction kettle, add 2.33g (10mmol) bisulfate ion N-butyl-pyridinium ([BPy] HSO successively
4) ionic liquid and 27.6g (0.3mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 70 ℃, nucleophilic addition was carried out 120 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 3:1.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 93.58%, and the five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following, five-ring: six-ring=1:1.52; Trans (E) of five-ring product and the mol ratio of cis (Z) do; E: Z=1:1.15, the mol ratio of the trans and cis of six-ring product is E:Z=1:0.67.
Embodiment 2
In reaction kettle, add 6.32g (20mmol) bisulfate ion 1-methyl-3-butyl sulfonic acid base imidazoles ([BSMim] HSO successively
4) ionic liquid and 13.8g (0.15mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 25 ℃, nucleophilic addition was carried out 180 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 1.5:1.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 85.06%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:1.63 (mol ratio), five-ring product E:Z=1:1.14 (mol ratio), six-ring product E:Z=1:0.76 (mol ratio).
Embodiment 3
In reaction kettle, add 1.84g (5mmol) trifluoromethayl sulfonic acid root 1-methyl-3-butyl sulfonic acid base imidazoles ([BSMim] CF successively
3SO
3) ionic liquid and 46.045g (0.5mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 50 ℃, nucleophilic addition was carried out 5 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 5:1.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 98.58%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:1.59 (mol ratio), five-ring product E:Z=1:1.16 (mol ratio), six-ring product E:Z=1:0.63 (mol ratio).
Embodiment 4
In reaction kettle, add 15.65g (50mmol) bisulfate ion N-butyl sulfonic acid yl pyridines ([BSPy] HSO successively
4) ionic liquid and 9.21g (0.1mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 100 ℃, nucleophilic addition was carried out 30 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 1:1.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 75.36%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:0.87 (mol ratio), five-ring product E:Z=1:1.15 (mol ratio), six-ring product E:Z=1:0.77 (mol ratio).
Embodiment 5
In reaction kettle, add 9.0g (50mmol) bisulfate ion Methylimidazole ([HMim] HSO successively
4) ionic liquid and 46.03g (0.5mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 5.3g (0.05mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 70 ℃, nucleophilic addition was carried out 90 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 10:1.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 72.27%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:0.79 (mol ratio), five-ring product E:Z=1:1.135 (mol ratio), six-ring product E:Z=1:0.76 (mol ratio).
Embodiment 6
In reaction kettle, add 3.00g (15mmol) bisulfate ion choline ([Choline] HSO successively
4) ionic liquid and 4.60g (0.05mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 90 ℃, nucleophilic addition was carried out 60 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 1:2.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 76.12%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:0.91 (mol ratio), five-ring product E:Z=1:1.14 (mol ratio), six-ring product E:Z=1:0.78 (mol ratio).
Embodiment 7
In reaction kettle, add 4.13g (18.75mmol) bisulfate ion 1-methyl-3-allyl imidazole (AMimHSO successively
4) ionic liquid and 2.30g (0.025mol) glycerine, stirring and evenly mixing; And then in reaction kettle, add 10.6g (0.1mol) phenyl aldehyde successively, and stir down slowly heating, be warmed up to 100 ℃, nucleophilic addition was carried out 10 minutes; Wherein, the mol ratio of glycerine and phenyl aldehyde is 1:4.After reaction finishes, the standing and reacting still, system is divided into two-layer up and down automatically.The upper strata be reactant with mixture of products mutually, lower floor be ionic liquid with the intact glycerine of unreacted mutually.The direct separation upper oil phase is carried out nuclear-magnetism and is detected qualitative, quantitative, and lower floor uses CH
2Cl
2Extracting and separating glycerine and ionic liquid, ionic liquid is removed organic solvent through decompression and is able to recycle and reuse.Oil phase is quantitative with the 400MHz NMR; Phenyl aldehyde transforms 80.88%; The five-ring product of glycerol acetonide phenyl aldehyde and the mol ratio of six-ring product are following; Five-ring: six-ring=1:1.31 (mol ratio), five-ring product E:Z=1:1.12 (mol ratio), six-ring product E:Z=1:0.76 (mol ratio).
Preparation glycerol acetonide method of benzaldehyde of the present invention adopt ionic liquid in the alcohol aldehyde nucleophilic addition as catalyzer and reaction medium; Not only reaction conditions is gentle, and is environmentally friendly, low to equipment corrosion; The use that has the water absorption character acidic ion liquid simultaneously; Not only avoid the use of the poisonous organic band aqua of volatility, stopped extra composition pollution products, and ionic liquid in time absorbs moisture; Reached pulling condensation reaction balance and moved, effectively improved productive rate, quality and the selectivity of glycerine acetal (ketone) to product side.
(ionic liquids ILs) as a kind of environmentally friendly solvent and liquid acid catalyst, has other organic and inorganic solvents and the not available advantage of traditional catalyst to ionic liquid; As having the high-density reaction active site of liquid acid and the non-volatility of solid acid, system is uniformly dispersed, catalyzer and product separate easily; Liquid range is wide; Heat stability is good, of a great variety, reusable etc.The present inventor utilizes designability, high resolution and the special catalytic performance of ILs; Change rule according to its character and come the design function ionic liquid; The strong functionalized ion liquid of synthetic acidic on purpose; With as the clean catalysis agent and the reaction solvent that are high added value chemical glycerol acetonide phenyl aldehyde with green hardware and software platform compound transformation of glycerol, solve the corrodibility of traditional mineral acidolysis process, toxic problem.The more important thing is; Use with water absorption character acidic ion liquid; Not only avoid the use of the poisonous organic band aqua of volatility, stopped extra composition pollution products, and ionic liquid in time absorbs moisture; Reached pulling condensation reaction balance and moved, effectively improved productive rate, quality and the selectivity of glycerine acetal (ketone) to product side.
Above embodiment is merely exemplary embodiment of the present invention, is not used in restriction the present invention, and protection scope of the present invention is defined by the claims.Those skilled in the art can make various modifications or be equal to replacement the present invention in essence of the present invention and protection domain, this modification or be equal to replacement and also should be regarded as dropping in protection scope of the present invention.
Claims (9)
1. one kind prepares the glycerol acetonide method of benzaldehyde; It is characterized in that; Glycerine and phenyl aldehyde are joined as carrying out nucleophilic addition in the ionic liquid of reaction medium and catalyzer, contain an acidic-group in said ion liquid positively charged ion and the negatively charged ion at least.
2. preparation glycerol acetonide method of benzaldehyde according to claim 1; It is characterized in that; Said positively charged ion is selected from a kind of in the following positively charged ion: alkyl imidazole positively charged ion, sulfonic acid substituted alkyl glyoxaline cation, allyl imidazole positively charged ion, carboxyl substituted alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, sulfonic acid substituted alkyl pyridylium, carboxyl substituted alkyl pyridine positively charged ion, sulfonic acid substituted alkyl vulkacit H positively charged ion, sulfonic acid substituted alkyl triethylene diamine positively charged ion, carboxyl substituted alkylamine positively charged ion and sulfonic acid substituted alkylamine positively charged ion.
3. preparation glycerol acetonide method of benzaldehyde according to claim 2 is characterized in that, said positively charged ion is preferably alkyl imidazole positively charged ion, sulfonic acid substituted alkyl glyoxaline cation or sulfonic acid substituted alkyl pyridylium.
4. preparation glycerol acetonide method of benzaldehyde according to claim 1 is characterized in that, said negatively charged ion is selected from a kind of in the following negatively charged ion: sulfate anion (HSO
4 -), acetate negatively charged ion (CH
3COO
-), phosphate anion (H
2PO
4 -), fluoroboric acid negatively charged ion (BF
4 -), hexafluorophosphoric acid negatively charged ion (PF
6 -), trifluoromethanesulfonic acid negatively charged ion (CF
3SO
3 -), methylsulphonic acid negatively charged ion (CH
3SO
3 -), formic acid negatively charged ion (HCOO
-), salt acid anion (Cl
-), nitric acid negatively charged ion (NO
3 -), trifluoroacetic acid negatively charged ion (CF
3CO
2 -), sulfurous acid negatively charged ion (HSO
3 -), carbonate anion (HCO
3 -) and toluene sulfonic acide negatively charged ion (CH
3(C
6H
4) SO
3 -).
5. preparation glycerol acetonide method of benzaldehyde according to claim 4 is characterized in that said negatively charged ion is preferably sulfate anion, trifluoromethanesulfonic acid negatively charged ion or methylsulphonic acid negatively charged ion.
6. preparation glycerol acetonide method of benzaldehyde according to claim 1; It is characterized in that said ionic liquid is preferably trifluoromethayl sulfonic acid root 1-methyl-3-fourth sulfonic group imidazoles, bisulfate ion 1-methyl-3-fourth sulfonic group imidazoles or bisulfate ion 1-ethyl-3-Methylimidazole.
7. preparation glycerol acetonide method of benzaldehyde according to claim 1 is characterized in that the mol ratio of phenyl aldehyde and glycerine is 1:0.25～10 in the said nucleophilic addition.
8. preparation glycerol acetonide method of benzaldehyde according to claim 1 is characterized in that the temperature of reaction of said nucleophilic addition is 25～100 ℃, and the reaction times is 5～180 minutes.
9. preparation glycerol acetonide method of benzaldehyde according to claim 1 is characterized in that phenyl aldehyde and ion liquid mol ratio are 1:0.05～1 in the said nucleophilic addition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819447A (en) * | 2014-03-14 | 2014-05-28 | 管有云 | Method for preparing glycerinum ketal ester by using glycerinum |
| CN104311527A (en) * | 2014-09-19 | 2015-01-28 | 河南师范大学 | Acidic bifunctional ionic liquid catalysis method for synthesis of benzoxanthene derivative |
| CN109574981A (en) * | 2019-01-15 | 2019-04-05 | 浙江昊唐实业有限公司 | A method of preparing glycerin shrinkage benzaldehyde |
| CN111253362A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing ketal and/or acetal glycerol |
| CN112174927A (en) * | 2020-11-05 | 2021-01-05 | 金睿睿 | Preparation method of glycerol formal |
| CN114471084A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Aromatic hydrocarbon-containing organic waste gas absorbent and preparation method and application thereof |
-
2012
- 2012-05-15 CN CN2012101511185A patent/CN102702166A/en active Pending
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| Title |
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| 王桂敏等: "酸催化甘油与苯甲醛缩合制备六元环缩醛", 《应用化学》 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819447A (en) * | 2014-03-14 | 2014-05-28 | 管有云 | Method for preparing glycerinum ketal ester by using glycerinum |
| CN103819447B (en) * | 2014-03-14 | 2016-07-13 | 管有云 | A kind of method being prepared glycerol acetonide ketone ester by glycerol |
| CN104311527A (en) * | 2014-09-19 | 2015-01-28 | 河南师范大学 | Acidic bifunctional ionic liquid catalysis method for synthesis of benzoxanthene derivative |
| CN111253362A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing ketal and/or acetal glycerol |
| CN111253362B (en) * | 2018-11-30 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing ketal and/or acetal glycerol |
| CN109574981A (en) * | 2019-01-15 | 2019-04-05 | 浙江昊唐实业有限公司 | A method of preparing glycerin shrinkage benzaldehyde |
| CN109574981B (en) * | 2019-01-15 | 2020-06-23 | 上海芜玮环境科技有限公司 | Method for preparing glycerol benzaldehyde |
| CN114471084A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Aromatic hydrocarbon-containing organic waste gas absorbent and preparation method and application thereof |
| CN114471084B (en) * | 2020-10-28 | 2023-07-04 | 中国石油化工股份有限公司 | Aromatic hydrocarbon-containing organic waste gas absorbent and preparation method and application thereof |
| CN112174927A (en) * | 2020-11-05 | 2021-01-05 | 金睿睿 | Preparation method of glycerol formal |
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Application publication date: 20121003 |