CN105152907A - Synthetic method of 2,2-dimethylolpropionic acid - Google Patents
Synthetic method of 2,2-dimethylolpropionic acid Download PDFInfo
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- CN105152907A CN105152907A CN201510506578.9A CN201510506578A CN105152907A CN 105152907 A CN105152907 A CN 105152907A CN 201510506578 A CN201510506578 A CN 201510506578A CN 105152907 A CN105152907 A CN 105152907A
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- formaldehyde
- synthetic method
- propionic aldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of 2,2-dimethylolpropionic acid. The synthetic method comprises steps as follows: 1), formaldehyde and a catalyst are added to a three-mouth flask, and the molar ratio of formaldehyde to the catalyst is (2:0.03)-(2:0.05); 2), propionaldehyde is added to a dropping funnel, and the molar ratio of formaldehyde to propionaldehyde is (3:2)-(2:1); 3), stirring is started, the pH (potential of hydrogen) is controlled in the range from 10 to 11, the temperature is 25 DEG C, propionaldehyde is slowly and dropwise added, and then, a reaction continues for 5h with pH kept in the range from 10 to 11; 4), after the reaction ends, the mixture is neutralized until the pH is 7, reduced pressure distillation is performed, and unreacted formaldehyde and propionaldehyde are removed; 5), water is added to a product obtained in the step 4), the mixture is heated to the temperature of 50 DEG C, and 30% hydrogen peroxide is added; 6), reduced pressure distillation is performed under the barometric pressure of 0.6, unreacted substances are removed, cooling, crystallization, filtration, drying and recrystallization are performed, and white crystals of 2,2-dimethylolpropionic acid are obtained.
Description
Technical field
The present invention relates to chemical technology field, more particularly, relate to a kind of synthetic method of 2,2-dimethylol propionic acid.
Background technology
2,2-dimethylol propionic acid has hydroxyl and carboxyl polyfunctional reactant, and in the manufacture of water-based polyurethane, it is chainextender, again because introducing hydrophilic radical carboxyl, and make urethane obtain emulsifying property, thus can the self-emulsifying aqueous polyurethane of excellent in stability processed.Also have the stability of the light and heat being similar to diamond lattic structure, be widely used in the production of the water-based polymers such as aqueous polyurethane, waterborne polyester, aqueous epoxy resins as crosslinked, solidification dispersion, emulsifying agent, its product has high-performance.Except such use, DMPA still can be used for polyester coating, photopolymerization constituent, New Liquid Crystal material, tackiness agent and magnetic pipe recording material etc., all can improve the stability of product, wetting ability, uniformity and weather resistance after adding DMPA as the coating prepared with it not only non-environmental-pollution, and there is incrust, shockproof, sound insulation, waterproof, fire prevention, resistant to hydrolysis, solvent resistant, shock resistance, the premium properties such as bright and clean.Prepare the method for 2,2-dimethylolalkanoic acids in prior art, reaction will be carried out at a higher temperature, and needs noble metal catalyst, and cost is higher.
Summary of the invention
The technical problem to be solved in the present invention is, for the above-mentioned defect of prior art, provides a kind of synthetic method of low cost 2,2-dimethylol propionic acid.
The technical solution adopted for the present invention to solve the technical problems is:
The synthetic method of a kind of 2,2-dimethylol propionic acid of structure, wherein, comprises the following steps:
1) in the four-hole bottle of 250ml that agitator, reflux condensing tube, dropping funnel and thermometer are housed, add formaldehyde and catalyzer, the ratio of formaldehyde and catalyzer is 2: 0.03 ~ 2: 0.05, mol ratio;
2) propionic aldehyde is added in dropping funnel, and the ratio of formaldehyde and propionic aldehyde is 3: 2 ~ 2: 1, mol ratio;
3) start stirring, control pH=10 ~ 11, temperature are 25 DEG C, slowly drip propionic aldehyde, dropwise, and keep pH to continue reaction 5h at 10-11;
4), after reaction terminates, add appropriate formic acid and be neutralized to pH=7, reaction mass is added in a round-bottomed flask, carry out underpressure distillation (0.5 normal atmosphere), remove unreacted formaldehyde, propionic aldehyde;
5) step 4) product add water, be heated to 50 DEG C, slowly drip 30% superoxol, hydrogen peroxide and propionic aldehyde mol ratio are 1: 1, react 8 hours;
6) underpressure distillation removing unreacted reactant under 0.6 normal atmosphere, through cooling, crystallization, filtration, drying, recrystallization, obtains 2,2-dimethylol propionic acid white crystal;
Described catalyzer is selected from: the mixture of Ca (OH) 2, Ba (OH) 2, triethylamine and Ca (OH) 2 or the mixture of triethylamine and Ba (OH) 2.
Synthetic method of the present invention, wherein, in described step 5), adding water is distilled water, and add-on is 120ml.
Synthetic method of the present invention, wherein, described step 4) in the unreacted formaldehyde of removing, after propionic aldehyde, extract three times by methyl iso-butyl ketone (MIBK), removing side reaction product Methylacrylaldehyde, the volume ratio of methyl iso-butyl ketone (MIBK) and mother liquor is 0.9: 1, extraction time is 10 minutes, divides two-layer, discard methyl iso-butyl ketone (MIBK) phase after leaving standstill, the aqueous phase of lower floor is released, as the next step thing.
Synthetic method of the present invention, wherein, described step 6) in, described recrystallization, uses 95% ethanol for recrystallization solvent.
Beneficial effect of the present invention is: 2,2-dimethylol propionic acid synthetic method by products of the present invention are few, productive rate is high.
Embodiment
In order to make the object of the embodiment of the present invention, technical scheme and advantage clearly, clear, complete description is carried out below in conjunction with the technical scheme in the embodiment of the present invention, obviously, described embodiment is section Example of the present invention, instead of whole embodiment.Based on embodiments of the invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not paying creative work, all belongs to protection scope of the present invention.
The synthetic method of 2,2-dimethylol propionic acids of present pre-ferred embodiments, wherein, comprises the following steps:
1) in the four-hole bottle of 250ml that agitator, reflux condensing tube, dropping funnel and thermometer are housed, add formaldehyde and catalyzer, the ratio of formaldehyde and catalyzer is 2: 0.03 ~ 2: 0.05, mol ratio;
2) propionic aldehyde is added in dropping funnel, and the ratio of formaldehyde and propionic aldehyde is 3: 2 ~ 2: 1, mol ratio;
3) start stirring, control pH=10 ~ 11, temperature are 25 DEG C, slowly drip propionic aldehyde, dropwise, and keep pH to continue reaction 5h at 10-11;
4), after reaction terminates, add appropriate formic acid and be neutralized to pH=7, reaction mass is added in a round-bottomed flask, carry out underpressure distillation (0.5 normal atmosphere), remove unreacted formaldehyde, propionic aldehyde;
5) step 4) product add water, be heated to 50 DEG C, slowly drip 30% superoxol, hydrogen peroxide and propionic aldehyde mol ratio are 1: 1, react 8 hours;
6) underpressure distillation removing unreacted reactant under 0.6 normal atmosphere, through cooling, crystallization, filtration, drying, recrystallization, obtains 2,2-dimethylol propionic acid white crystal; Catalyzer is selected from: the mixture of Ca (OH) 2, Ba (OH) 2, triethylamine and Ca (OH) 2 or the mixture of triethylamine and Ba (OH) 2.2,2-dimethylol propionic acid synthetic method by products of the present invention are few, productive rate is high.
Above-mentioned steps 5) in, adding water is distilled water, and add-on is 120ml.
Above-mentioned steps 4) in the unreacted formaldehyde of removing, after propionic aldehyde, three times are extracted by methyl iso-butyl ketone (MIBK), removing side reaction product Methylacrylaldehyde, the volume ratio of methyl iso-butyl ketone (MIBK) and mother liquor is 0.9: 1, extraction time is 10 minutes, divides two-layer, discard methyl iso-butyl ketone (MIBK) phase after leaving standstill, the aqueous phase of lower floor is released, as the next step thing.
Above-mentioned steps 6) in, described recrystallization, uses 95% ethanol for recrystallization solvent.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (4)
1. the synthetic method of a dimethylol propionic acid, is characterized in that, comprises the following steps:
1) in the four-hole bottle of 250ml that agitator, reflux condensing tube, dropping funnel and thermometer are housed, add formaldehyde and catalyzer, the ratio of formaldehyde and catalyzer is 2: 0.03 ~ 2: 0.05, mol ratio;
2) propionic aldehyde is added in dropping funnel, and the ratio of formaldehyde and propionic aldehyde is 3: 2 ~ 2: 1, mol ratio;
3) start stirring, control pH=10 ~ 11, temperature are 25 DEG C, slowly drip propionic aldehyde, dropwise, and keep pH to continue reaction 5h at 10-11;
4), after reaction terminates, add appropriate formic acid and be neutralized to pH=7, reaction mass is added in a round-bottomed flask, carry out underpressure distillation (0.5 normal atmosphere), remove unreacted formaldehyde, propionic aldehyde;
5) step 4) product add water, be heated to 50 DEG C, slowly drip 30% superoxol, hydrogen peroxide and propionic aldehyde mol ratio are 1: 1, react 8 hours;
6) underpressure distillation removing unreacted reactant under 0.6 normal atmosphere, through cooling, crystallization, filtration, drying, recrystallization, obtains 2,2-dimethylol propionic acid white crystal;
Described catalyzer is selected from: the mixture of Ca (OH) 2, Ba (OH) 2, triethylamine and Ca (OH) 2 or the mixture of triethylamine and Ba (OH) 2.
2. synthetic method according to claim 1, is characterized in that, in described step 5), adding water is distilled water, and add-on is 120ml.
3. synthetic method according to claim 1, it is characterized in that, described step 4) in the unreacted formaldehyde of removing, after propionic aldehyde, extract three times by methyl iso-butyl ketone (MIBK), removing side reaction product Methylacrylaldehyde, the volume ratio of methyl iso-butyl ketone (MIBK) and mother liquor is 0.9: 1, extraction time is 10 minutes, divides two-layer, discard methyl iso-butyl ketone (MIBK) phase after leaving standstill, the aqueous phase of lower floor is released, as the next step thing.
4. synthetic method according to claim 1, is characterized in that, described step 6) in, described recrystallization, uses 95% ethanol for recrystallization solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510506578.9A CN105152907A (en) | 2015-08-18 | 2015-08-18 | Synthetic method of 2,2-dimethylolpropionic acid |
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| CN201510506578.9A CN105152907A (en) | 2015-08-18 | 2015-08-18 | Synthetic method of 2,2-dimethylolpropionic acid |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381300A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)propinonic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381300A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)propinonic acid |
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Application publication date: 20151216 |