CN105061139A - Synthetic method for methallyl alcohol - Google Patents
Synthetic method for methallyl alcohol Download PDFInfo
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- CN105061139A CN105061139A CN201510427295.5A CN201510427295A CN105061139A CN 105061139 A CN105061139 A CN 105061139A CN 201510427295 A CN201510427295 A CN 201510427295A CN 105061139 A CN105061139 A CN 105061139A
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- China
- Prior art keywords
- synthetic method
- methallyl alcohol
- reaction
- amine salt
- methylacrylaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthetic method for methallyl alcohol and belongs to the technical field of organic synthesis. The synthetic method comprises the following two steps: (1), acrolein and formaldehyde or paraformaldehyde are taken as the raw materials to prepare methylacrolein in presence of a catalyst organic acid organic amine salt; (2), isopropanol and methylacrolein prepared in the step (1) are subjected to transfer reduction through negative hydrogen ions, and methallyl alcohol is prepared. The synthetic method has the advantages of environmental protection, feasibility, low cost, high yield and the like.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of synthetic method of methallyl alcohol.
Background technology
Methallyl alcohol, owing to can be used to synthesis of carboxylic acid class water reducer, obtained in recent years and developed on a large scale very much.But also few about methallyl alcohol synthetic method patent, principal synthetic routes has:
1, methacrylic chlorine water solution
See: JP61000033, JP2012232903, JP2009107949, JP2002371023, JP2002105015
This method advantage is that operational path is simple, and shortcoming has inorganic salt to produce.
2, Methylacrylaldehyde reduction method
See: CN102167657, JP2000154157, US4731488
This method adopts Methylacrylaldehyde Virahol or other alcohol hydride transfer to reduce, simpler than catalytic hydrogenating reduction technique, and be easy to produce, shortcoming to produce a small amount of metallic oxyhydroxide, needs harmless treatment formaldehyde.Wherein, Methylacrylaldehyde conveniently can be obtained by propionic aldehyde and formaldehyde condensation, sees: DE3213681, US4433174, US4283564, DE2855504.
3, oxygenizement of butene
This method only minority developed country adopts, and require to keep under strict control content lower than limits of explosion, technology difficulty is larger.
In sum, adopt propionic aldehyde and formaldehyde condensation, then be applicable to suitability for industrialized production with the Measures compare of Virahol reduction, critical technological point is the problems such as the environmental pollution of solution formaldehyde generation.
Summary of the invention
The object of this invention is to provide a kind of clean synthesis method of methallyl alcohol, environmental protection is easy, cost is low, specifically comprises the following steps:
1, Methylacrylaldehyde preparation
Catalyzer adopts organic acid organic amine salt, as formic acid dimethylamine salt, formic acid front three amine salt, formic acid diethylamine salt, triethylammonium formate, formic acid dipropyl amine salt, formic acid isopropyl amine salt, formic acid butylamine salt, in like manner corresponding acetic acid organic amine salt, propionic acid organic amine salt also can be used as catalyzer, preferred acetic acid dimethylamine salt, catalyst levels is the 1wt% of propionic aldehyde.Reaction is carried out at ambient pressure, temperature 40 ~ 100 DEG C, preferably 40 ~ 85 DEG C; The mol ratio of propionic aldehyde and formaldehyde is 1:1 ~ 3:1, preferred 1.5:1.
Wherein, step (1) concrete technology comprises: formaldehyde or paraformaldehyde are added on DL in the reaction unit containing Virahol, add organic amine, stirs and heats up; Adding organic acid after being down to room temperature makes its pH reach 5.6-6.5, adds propionic aldehyde, again adds organic acid and adjusts pH to be 5.6-6.5, carry out temperature rising reflux reaction; Reclaim excessive propionic aldehyde and Methylacrylaldehyde isopropanol mixture finally by fractionation, described mixture through sieving, after drying for next step.
2, the preparation of methallyl alcohol
Catalyzer is selected
m is Na, Zn, Al, preferably
the mole dosage of catalyzer is 0.05 ~ 0.1 times of Methylacrylaldehyde, preferably 0.07; 4 ~ 20 hours reaction times, preferably 8 hours; Temperature of reaction 50 ~ 100 DEG C, preferably 80 DEG C.
The present invention compared with prior art, has the advantages such as production cost is low, output is high, environmental protection, is suitable for suitability for industrialized production.
Embodiment
Following content is described further the present invention in conjunction with example.
Example 1:
In 500L reaction flask, paraformaldehyde (2mol formaldehyde) is added on DL in 100g Virahol, adds dimethylamine 1g, stir and be warming up to 60 DEG C of maintenances 4 hours, make paraformaldehyde depolymerization.Cool to 25 DEG C, then add acetic acid and make its pH reach 5.6, add 3mol propionic aldehyde, again add acetic acid and adjust pH to be 5.6, temperature rising reflux reacts.Temperature rises gradually, when temperature reach 65 DEG C no longer rise time, insulation reaction 2 hours, excessive propionic aldehyde 57g is reclaimed in straight-forward fractional distillation, then fractionates out Methylacrylaldehyde isopropanol mixture 220g, for next step after 4A ° of molecular sieve drying.
Example 2:
In 500L reaction flask, add anhydrous isopropyl alcohol 298g, brand-new aluminum isopropylate 24g, add anhydrous methyl propenal isopropanol mixture prepared by example 1, back flow reaction 8 hours, fractionation obtains:
Collect less than 80 DEG C fraction 236g, containing Methylacrylaldehyde 1.67%, acetone 37.11%, Virahol 59.34%;
80 ~ 100 DEG C of fraction 163g, containing Virahol 94.38%, methallyl alcohol 3.27%;
Vacuum fractionation must reduce pressure fraction 105g, containing Virahol 7.09%, methallyl alcohol 92.2%; Residue high boiling material 38g, cover is used for next batch.
Example 3:
Add Virahol 298g, brand-new aluminum isopropylate 12g being equipped with in high boiling material reaction flask, add anhydrous methyl propenal isopropanol mixture 220g, carry out fractionation by example 2:
Less than 80 DEG C fraction 234g, containing Methylacrylaldehyde 0.52%, acetone 36.7%, Virahol 60.9%;
80 ~ 100 DEG C of fraction 164g, containing Virahol 96.5%, methallyl alcohol 2.83%;
Vacuum fractionation must reduce pressure fraction 105g, containing methallyl alcohol 97.6%, Virahol 1.85%, and residue high boiling material 27g.
Claims (8)
1. a synthetic method for methallyl alcohol, is characterized in that, comprises the following steps:
(1) with propenal and formaldehyde or paraformaldehyde for raw material prepares Methylacrylaldehyde under the existence of catalyzer organic acid organic amine salt;
(2) Methylacrylaldehyde Virahol and step (1) obtained is reduced by hydride transfer and obtains methallyl alcohol.
2. the synthetic method of methallyl alcohol according to claim 1, is characterized in that: the concrete technology of described step (1) comprising: formaldehyde or paraformaldehyde are added on DL in the reaction unit containing Virahol, add organic amine, stirs and heats up; Adding organic acid after being down to room temperature makes its pH reach 5.6-6.5, adds propionic aldehyde, again adds organic acid and adjusts pH to be 5.6-6.5, carry out temperature rising reflux reaction; Reclaim excessive propionic aldehyde and Methylacrylaldehyde isopropanol mixture finally by fractionation, described mixture through sieving, after drying for next step.
3. the synthetic method of methallyl alcohol according to claim 1, is characterized in that: described organic acid organic amine salt is selected from formic acid dimethylamine salt, formic acid front three amine salt, formic acid diethylamine salt, triethylammonium formate, formic acid dipropyl amine salt, formic acid isopropyl amine salt, formic acid butylamine salt and corresponding acetic acid organic amine salt, propionic acid organic amine salt.
4. the synthetic method of methallyl alcohol according to claim 1, is characterized in that: in described step (1), the consumption of catalyzer is the 1wt% of propionic aldehyde.
5. the synthetic method of methallyl alcohol according to claim 1, is characterized in that: described step (1) reaction is carried out at ambient pressure, and temperature is 40 ~ 100 DEG C, and the mol ratio of propionic aldehyde and formaldehyde is 1:1 ~ 3:1.
6. the synthetic method of methallyl alcohol according to claim 5, is characterized in that: described step (1) temperature of reaction is 40 ~ 85 DEG C, and the mol ratio of propionic aldehyde and formaldehyde is 1.5:1.
7. the synthetic method of methallyl alcohol according to claim 1, it is characterized in that: described step (2) catalyzer is sodium isopropylate, Virahol zinc or aluminum isopropylate, its consumption is 0.05 ~ 0.1mol of Methylacrylaldehyde, 4 ~ 20 hours reaction times, temperature of reaction 50 ~ 100 DEG C.
8. the synthetic method of methallyl alcohol according to claim 7, is characterized in that: described step (2) catalyst levels is the 0.07mol of Methylacrylaldehyde, and the reaction times is 8 hours, and temperature of reaction is 80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510427295.5A CN105061139A (en) | 2015-07-20 | 2015-07-20 | Synthetic method for methallyl alcohol |
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| CN201510427295.5A CN105061139A (en) | 2015-07-20 | 2015-07-20 | Synthetic method for methallyl alcohol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324974A (en) * | 2017-06-09 | 2017-11-07 | 浙江大学宁波理工学院 | The method for preparing methallyl alcohol and acid amides simultaneously |
| CN107365245A (en) * | 2017-07-10 | 2017-11-21 | 中国化学赛鼎宁波工程有限公司 | A kind of methallyl alcohol production system and method |
| CN110872252A (en) * | 2019-12-12 | 2020-03-10 | 北京成宇化工有限公司 | Preparation method of 3-methylquinoline-8-sulfonyl chloride |
| CN113248345A (en) * | 2021-06-11 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
-
2015
- 2015-07-20 CN CN201510427295.5A patent/CN105061139A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324974A (en) * | 2017-06-09 | 2017-11-07 | 浙江大学宁波理工学院 | The method for preparing methallyl alcohol and acid amides simultaneously |
| CN107324974B (en) * | 2017-06-09 | 2021-01-26 | 浙江大学宁波理工学院 | Method for the simultaneous production of methallyl alcohol and amides |
| CN107365245A (en) * | 2017-07-10 | 2017-11-21 | 中国化学赛鼎宁波工程有限公司 | A kind of methallyl alcohol production system and method |
| CN110872252A (en) * | 2019-12-12 | 2020-03-10 | 北京成宇化工有限公司 | Preparation method of 3-methylquinoline-8-sulfonyl chloride |
| CN113248345A (en) * | 2021-06-11 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
| CN113248345B (en) * | 2021-06-11 | 2021-10-26 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
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Application publication date: 20151118 |