CN109761949B - Industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane - Google Patents
Industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane Download PDFInfo
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- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 111
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000013067 intermediate product Substances 0.000 claims abstract description 32
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 28
- 239000003377 acid catalyst Substances 0.000 claims abstract description 25
- -1 triol ester Chemical class 0.000 claims abstract description 20
- 239000012670 alkaline solution Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 11
- 239000003054 catalyst Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 27
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 22
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 11
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 230000032050 esterification Effects 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 50
- 235000011187 glycerol Nutrition 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 5
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SFCPXHKCMRZQAC-UHFFFAOYSA-N 2,3-dihydroxypropyl benzoate Chemical compound OCC(O)COC(=O)C1=CC=CC=C1 SFCPXHKCMRZQAC-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- JEQLMQDIGPQFJR-UHFFFAOYSA-N methanesulfonic acid;sulfuric acid Chemical group CS(O)(=O)=O.OS(O)(=O)=O JEQLMQDIGPQFJR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps: (1) and (3) preparing carboxylic acid monopropylene triol ester by esterification: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 0.5-4h at 90-150 ℃ under the condition of an acid catalyst to obtain carboxylic acid monopropanol ester; (2) and ketal cyclization reaction: carboxylic acid monopropylene triol ester and acetone are subjected to cyclization reaction for 0.5 to 3 hours at the temperature of between 20 and 50 ℃ under the condition of an acid catalyst to obtain a cyclization intermediate product; (3) and (3) hydrolysis reaction: and (3) adding the intermediate product obtained in the step (2) into an alkaline solution, and reacting for 0.5-1h at the temperature of 20-50 ℃ to obtain the product. The industrial preparation method of the 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane has the characteristics of green and environment-friendly process, high selectivity of chemical reaction and high conversion rate of raw materials.
Description
Technical Field
The invention relates to the technical field of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, in particular to an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane.
Background
2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane is a product derived from renewable resources having a low volatilization rate. Compared with alcohol ether solvents, the alcohol ether solvent has lower toxicity and is more friendly to human health and environment. Can replace alcohol ether solvents and be used as solvents, cosolvents or film-forming aids and the like in the fields of coatings, printing ink, leather treatment and the like; used as carrier and solubilizer in daily chemical and fragrance industry; used in industrial cleaning and electronic chemical industries.
Currently, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane is commercially available in two categories: direct and indirect processes. The direct method is that under the acidic condition, acetone and glycerol directly ketal react to obtain a product; the indirect method is a synthesis method of the indirect method. The direct process uses a strong acid as a catalyst and glycerol and acetone undergo a ketal reaction to produce a product and water. At present, no matter a laboratory synthesis reaction or an industrial process, the separation of byproduct water is the bottleneck of product production, and as the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane is mutually soluble with water, unreacted acetone and glycerol are mutually soluble with water and the product, and simultaneously the glycerol is easy to deteriorate at a high temperature. The key point of the reaction process is to remove the generated water out of the system in time, but the components in the reaction system are dissolved with each other, so that the separation is difficult, and the actual conversion per pass of the reaction is low. The reported methods for removing water generated by the reaction of acetone and glycerol only comprise in-situ dehydration and azeotropic dehydration, but the two methods have defects, such as in-situ dehydration, generally use dehydrating agents such as anhydrous sodium sulfate and the like, have insignificant dehydration effect, bring difficulty to post-treatment and improve unit consumption; on the other hand, the boiling point of the raw material acetone is low (56 ℃ C), and common water-carrying agents cannot be used, so that the effect is not good.
Disclosure of Invention
The invention aims to provide an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which has the characteristics of green and environment-friendly process, high selectivity of industrial reaction and high conversion rate of raw materials.
The invention can be realized by the following technical scheme:
the invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 0.5 to 4 hours at the temperature of between 90 and 150 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monopropyl ester;
(2) and ketal cyclization reaction: carboxylic acid monopropanetriol ester and acetone in acidControlling the cyclization reaction for 0.5-3h at 20-50 ℃ under the condition of a sexual catalyst to obtain a hydrophobic cyclization intermediate product
；
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding into alkaline solution, reacting at 20-50 deg.C for 0.5-1h to obtain 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane.
The specific reaction process is as follows:
wherein R is C (n) H (2n + 1), n is 1-16, or R is C6H5。
Further, in the step (1), the molar ratio of the glycerol to the carboxylic acid is 1:1, and the addition amount of the catalyst is 0.05-10% of that of the glycerol.
Further, in the step (2), the molar ratio of the carboxylic acid monopropantriol ester to the acetone is 1:1 to 10 percent, and the adding amount of the catalyst is 0.05 to 10 percent of carboxylic acid monopropanol ester.
Further, the acid catalyst in the step (1) is one or a mixture of more than two of methanesulfonic acid, p-toluenesulfonic acid, methyldi-sulfonic acid, sulfuric acid and cationic resin;
further, the acid catalyst in the step (2) is one or two of methanesulfonic acid, p-toluenesulfonic acid, methyldi sulfonic acid, boron trifluoride diethyl etherate, cationic resin aluminum trichloride and sodium bisulfate.
Further, the alkaline solution in the step (3) is selected from one or more than two of 18-32wt% of NaOH, anion resin and 18-32wt% of KOH.
Further, a dehydrating agent is added in the step (1), and the dehydrating agent is toluene and/or cyclohexane.
As another embodiment of the present invention, in the above-mentioned production method, commercially available glycerol monostearate may be selected instead of the carboxylic acid monopropanetriol ester obtained in step (1), and the reaction conditions in step (2) are maintained, so that step (1) is omitted.
The industrial preparation method of the 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane has the following beneficial effects:
the preparation method is green and environment-friendly in process, a drying agent is not needed in the whole preparation process by preparing the hydrophobic intermediate product, solid waste cannot be generated due to the drying agent, the added long-chain fatty acid can be reused, the long-chain fatty acid and glycerol can be biomass source raw materials, and water and an oil phase are separated in the reaction steps 1 and 2 in a physical layering mode, so that energy consumption is saved;
secondly, the reaction selectivity is high, the esterification on the 1-position of the glycerol is basically formed in the first step of reaction, the reaction selectivity in the second step of ketal reaction is high, and only two adjacent hydroxyl groups of the glycerol react to form five-membered rings.
Thirdly, the conversion rate of the raw materials is high, and because the hydrophobic chain segment is introduced into the ketal reaction raw materials in advance, the water generated in the ketal reaction process can be automatically separated from the system, so that the one-way conversion rate of the ketal reaction can be greatly improved, and the one-way conversion rate of the ketal reaction reaches more than 90 percent, and has higher conversion rate.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following detailed description is provided for the product of the present invention with reference to the examples.
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 0.5 to 4 hours at the temperature of between 90 and 150 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monopropyl ester;
(2) and ketal cyclization reaction: carboxylic acid monopropanol ester and acetone under the condition of acid catalystControlling the temperature to be 20-50 ℃ for cyclization reaction for 0.5-3h to obtain a hydrophobic cyclization intermediate product
；
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding into alkaline solution, reacting at 20-50 deg.C for 0.5-1h to obtain 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane.
Further, in the step (1), the molar ratio of the glycerol to the carboxylic acid is 1:1, and the addition amount of the catalyst is 0.05-10% of that of the glycerol.
Further, in the step (2), the molar ratio of the carboxylic acid monopropantriol ester to the acetone is 1:1 to 10 percent, and the adding amount of the catalyst is 0.05 to 10 percent of carboxylic acid monopropanol ester.
Further, the acid catalyst in the step (1) is one or a mixture of more than two of methanesulfonic acid, p-toluenesulfonic acid, methyldi-sulfonic acid, sulfuric acid and cationic resin;
further, the acid catalyst in the step (2) is one or two of methanesulfonic acid, p-toluenesulfonic acid, methyldi sulfonic acid, boron trifluoride diethyl etherate, cationic resin aluminum trichloride and sodium bisulfate.
Further, the alkaline solution in the step (3) is selected from one or more than two of 18-32wt% of NaOH, anion resin and 18-32wt% of KOH.
Further, a dehydrating agent is added in the step (1), and the dehydrating agent is toluene and/or cyclohexane.
As another embodiment of the present invention, in the above-mentioned production method, commercially available glycerol monostearate may be selected instead of the carboxylic acid monopropanetriol ester obtained in step (1), and the reaction conditions in step (2) are maintained, so that step (1) is omitted.
Example 1
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 2.25h at 150 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid monopropanol ester; the molar ratio of glycerol to carboxylic acid was 1:1, and the amount of catalyst added was 0.05% of glycerol. The acid catalyst is methanesulfonic acid and p-toluenesulfonic acid.
(2) And ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 1.75h under the condition of an acid catalyst and at the temperature of 50 ℃ to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1:1, the adding amount of the catalyst is 0.05 percent of that of the carboxylic acid monopropylene triol ester. The acidic catalyst is sulfuric acid methanesulfonic acid.
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 0.75h at 50 ℃ to obtain the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution was 18wt% NaOH.
Example 2
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 0.5h at 120 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid monopropanol ester; the molar ratio of glycerol to carboxylic acid was 1:1, and the amount of catalyst added was 10% of glycerol. The acidic catalyst is sulfuric acid.
(2) And ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 0.5h under the condition of an acid catalyst and at the temperature of 35 ℃ to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1: 10, adding 5 percent of catalyst based on the carboxylic acid monopropylene triol ester; the acid catalyst is boron trifluoride diethyl etherate.
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 0.5h at 35 ℃ to obtain the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution is an anionic resin.
Example 3
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 4 hours at 90 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monostearate; the molar ratio of glycerol to carboxylic acid was 1:1 and the amount of catalyst added was 5% of glycerol. The acidic catalyst is p-toluenesulfonic acid.
(2) And ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 3 hours at 20 ℃ under the condition of an acid catalyst to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1: 5, the adding amount of the catalyst is 2 percent of that of the carboxylic acid monopropylene triol ester. The acidic catalyst is a cationic resin.
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 1h at the temperature of 20 ℃ to obtain the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution is one or two of 25wt% NaOH and 32wt% KOHThe above.
Example 4
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 3h at 100 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monostearate; the molar ratio of glycerol to carboxylic acid was 1:1, and the amount of catalyst added was 6% of glycerol. The acidic catalyst is a cationic resin.
(2) And ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 1h under the condition of an acid catalyst and at the temperature of 40 ℃ to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1: 7, the adding amount of the catalyst is 3 percent of that of the carboxylic acid monopropanol ester. The acid catalyst is methanesulfonic acid, p-toluenesulfonic acid and methyldi-sulfonic acid.
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 0.8h at 40 ℃ to obtain the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution is 23wt% NaOH and anion resin.
In the embodiment, a dehydrating agent is also added in the step (1), and the dehydrating agent is toluene and cyclohexane.
Example 5
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 3h at 100 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monostearate; the molar ratio of glycerol to carboxylic acid was 1:1, and the amount of catalyst added was 6% of glycerol. The acidic catalyst is sulfuric acid.
(2) And ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 1h under the condition of an acid catalyst and at the temperature of 40 ℃ to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1: 7, the adding amount of the catalyst is 3 percent of that of the carboxylic acid monopropanol ester. The acid catalyst is boron trifluoride diethyl etherate.
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 0.8h at 40 ℃ to obtain the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution is 23wt% NaOH and anion resin.
In the embodiment, a dehydrating agent is further added in the step (1), and the dehydrating agent is cyclohexane.
Example 6
The invention discloses an industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, which comprises the following steps:
(1) and ketal cyclization reaction: commercial glyceryl monostearate and acetone are subjected to cyclization reaction for 1h at 30 ℃ under the condition of an acid catalyst to obtain a hydrophobic cyclization intermediate product
(ii) a The molar ratio of the carboxylic acid monopropanol ester to the acetone is 1: 3, the adding amount of the catalyst is 4 percent of that of the carboxylic acid monopropylene triol ester. The acidic catalyst is methanesulfonic acid.
(2) And (3) hydrolysis reaction: the intermediate product obtained in the step (1) is treated
Adding into alkaline solution, and reacting at 30 deg.C for 0.6h to obtainTo the product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane. The alkaline solution is 28wt% NaOH and 34wt% KOH.
Application example 1
15.4 kg of glycerin monostearate and 10 kg of acetone are added into a reaction kettle, 0.06 kg of catalyst p-toluenesulfonic acid is added into the reaction kettle, and the reaction temperature is controlled to be 40 DEGoAnd C, finishing the reaction for 60min, extracting the catalyst by using water, recovering the excessive acetone by normal pressure distillation, and obtaining 16.8 kg of acetone glyceryl monostearate, wherein the yield is 98 percent, and the purity is as follows: 98.5 percent.
Adding 16.8 kg of the intermediate product into a reaction kettle, hydrolyzing ester group of the intermediate product through high-pressure steam of 4MPa, distilling the obtained oil phase under reduced pressure, recovering byproduct stearic acid at the bottom of the kettle, and keeping the temperature at the top of the kettle to be 120 DEGoC, the vacuum degree is 90 kpa, and the 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane with the purity of 98.5 percent can be obtained.
Application example 2
10 kg of glycerol and 13.26 kg of benzoic acid are added into a reaction kettle, 0.05 kg of methanesulfonic acid catalyst and 2kg of toluene water-carrying agent are added, the reaction is finished at 120 ℃ for 150 min, the catalyst is extracted and recovered by water, and the raw materials are removed by reduced pressure distillation to obtain glycerol monobenzoate as an intermediate, wherein the yield is 97.5%, and the purity is 99%.
Adding 8.5 kg of glycerol monobenzoate and 10 kg of acetone and 0.025 kg of methanesulfonic acid serving as a catalyst into a reaction kettle, reacting for 60min at 35 ℃, extracting and recovering the catalyst by using water, and distilling and recovering excessive acetone at normal pressure to obtain 9.8 kg of acetone-glycidol benzoate, wherein the yield is 96%, and the purity is as follows: 98.5 percent.
Adding 9.8 kg of the intermediate product into a reaction kettle, adding 5 kg of 32wt% NaOH solution, keeping the temperature at 60 ℃, stirring and reacting for 30min, adding sulfuric acid to adjust the pH to 7, carrying out phase separation, carrying out reduced pressure distillation on an oil phase, recycling benzoic acid at the bottom of the kettle, and obtaining 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane with the purity of 98.5% at the top of the tower (the temperature at the top of the distillation tower is 120 ℃ and the vacuum degree is 90 kpa).
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be readily apparent to those skilled in the art from the disclosure herein, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (4)
1. An industrial preparation method of 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane is characterized by comprising the following steps:
(1) and preparing a hydrophobic intermediate carboxylic acid monopropylene triol ester by an esterification reaction: glycerol and carboxylic acid are taken as raw materials, and dehydration reaction is carried out for 0.5 to 4 hours at the temperature of between 90 and 150 ℃ under the condition of an acid catalyst to obtain a hydrophobic intermediate product carboxylic acid glycerol monopropyl ester;
(2) and ketal cyclization reaction: carboxylic acid monopropanol ester and acetone are subjected to cyclization reaction for 0.5-3h under the condition of an acid catalyst and at the temperature of 20-50 ℃ to obtain a hydrophobic cyclization intermediate product
；
(3) And (3) hydrolysis reaction: the intermediate product obtained in the step (2)
Adding the mixture into an alkaline solution, and reacting for 0.5-1h at the temperature of 20-50 ℃ to obtain a product 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane;
wherein R is C (n) H (2n + 1), n is 1-16, or R is C6H5；
In the step (1), the molar ratio of glycerol to carboxylic acid is 1:1, and the addition amount of the catalyst is 0.05-10% of that of glycerol; in the step (2), the molar ratio of the carboxylic acid monopropylene triol ester to the acetone is 1:1 to 10 percent, the adding amount of the catalyst is 0.05 to 10 percent of carboxylic acid monopropylene triol ester; the acidic catalyst in the step (1) is one or a mixture of more than two of methanesulfonic acid, p-toluenesulfonic acid, methyldi-sulfonic acid, sulfuric acid and cationic resin.
2. The process for industrially producing 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane according to claim 1, characterized in that: the acidic catalyst in the step (2) is one or two of methanesulfonic acid, p-toluenesulfonic acid, methyldi-sulfonic acid, boron trifluoride diethyl etherate and sodium bisulfate.
3. The process for industrially producing 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane according to claim 1, characterized in that: the alkaline solution in the step (3) is selected from one or more than two of 18-32wt% of NaOH and 18-32wt% of KOH.
4. The process for industrially producing 2, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane according to claim 2, characterized in that: and (2) adding a dehydrating agent into the step (1), wherein the dehydrating agent is toluene and/or cyclohexane.
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| CN104829584A (en) * | 2015-05-19 | 2015-08-12 | 江苏福瑞生物医药有限公司 | Synthesis method of (R)-glyceraldehyde acetonide compound |
| CN108373410A (en) * | 2018-04-11 | 2018-08-07 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of dimethyl hydrine acetate |
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| CN104829584A (en) * | 2015-05-19 | 2015-08-12 | 江苏福瑞生物医药有限公司 | Synthesis method of (R)-glyceraldehyde acetonide compound |
| CN108373410A (en) * | 2018-04-11 | 2018-08-07 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of dimethyl hydrine acetate |
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