CN102775296A - Preparation method of 2,2-dimethylolbutanoicacid - Google Patents
Preparation method of 2,2-dimethylolbutanoicacid Download PDFInfo
- Publication number
- CN102775296A CN102775296A CN2012102489009A CN201210248900A CN102775296A CN 102775296 A CN102775296 A CN 102775296A CN 2012102489009 A CN2012102489009 A CN 2012102489009A CN 201210248900 A CN201210248900 A CN 201210248900A CN 102775296 A CN102775296 A CN 102775296A
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- China
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- preparation
- paraformaldehyde
- dimethylolpropionic acid
- hours
- mass ratio
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 title abstract 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000005575 aldol reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- YYKMQUOJKCKTSD-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanal Chemical compound CCC(CO)(CO)C=O YYKMQUOJKCKTSD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 methylols Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 2,2-dimethylolbutanoicacid. Paraformaldehyde and water are subjected to aldol reaction in the existence of a basic catalyst, hydrogen peroxide serves as an oxidizing agent, and 2,2-dimethylolbutanoicacid white crystals are obtained through oxidation and crystallization. The preparation method has the advantages that the prepared 2,2-dimethylolbutanoicacid is high in yield, the total yield of the 2,2-dimethylolbutanoicacid reaches 41%, the waste water discharge quantity is small, and operation is simple.
Description
Technical field
The present invention relates to a kind of chemical industry preparation method, specifically is a kind of 2, the preparation method of 2-dimethylolpropionic acid.
Background technology
2; The 2-dimethylolpropionic acid is the polyfunctional group organic cpds that contains two methylols, a carboxyl and an ethyl in a kind of molecular structure; Have lower fusing point and good solubility ability, can be widely used in aspects such as water-soluble poly propylhomoserin, water-soluble polyester, epoxy resin, sizing agent.At present, be raw material mainly in the industry, under the basic catalyst effect with formaldehyde and butyraldehyde-n; Through aldol reaction and oxidizing reaction Synthetic 2,2-dimethylolpropionic acid, used formaldehyde are 36% formaldehyde solution; Can cause water consumption more, and the dehydration cost is high, reacts wayward; Simultaneously, existing 2,2-dihydroxymethyl butyraldehyde preparation technology also exists the difficult crystallization of product, low, the processing cost high-technology difficult point of yield.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of 2, the preparation method of 2-dimethylolpropionic acid.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following:
A kind of 2, the preparation method of 2-dimethylolpropionic acid, this method may further comprise the steps:
1) in four-hole boiling flask, adds Paraformaldehyde 96 and water mixing stirring, reacted 2 hours down at 45-55 ℃, and add liquid caustic soda regulator solution pH between 9-10;
2) insulation was warming up to 80 ℃ and steams unreacted butyraldehyde-n and a spot of formaldehyde completely after 4 hours;
3) after distillation finishes, be cooled to 50 ℃, drip a certain amount of ydrogen peroxide 50 in 2 hours, and be incubated 6 hours, add vitriol oil acidifying, be decompressed to 12kPa and remove moisture;
4) behind the evaporate to dryness, add a certain amount of MIBK and be warming up to 100 ℃ of reflux water-dividings, after branch water was intact, cooling removed solid salt while hot, and crystallisation by cooling obtains bullion;
5) bullion is added solvent recrystallization again, obtain white crystal.
Further, the mass ratio of the water of input and Paraformaldehyde 96 is 1:1.
Further, the mass ratio of liquid caustic soda and Paraformaldehyde 96 is 5:6, and the concentration of liquid caustic soda is 5 %.
Further, the ydrogen peroxide 50 of input and the mass ratio of Paraformaldehyde 96 are 55:24, and the concentration of ydrogen peroxide 50 is 27 %.
Further, the mass ratio of the mibk of input and Paraformaldehyde 96 is 25:12.
The invention has the advantages that: 1) this prepared 2, the yield of 2-dimethylolpropionic acid is high, and its total recovery reaches 41 %.2) wastewater discharge is low, reduces the waste water reclamation cost, replaces 36% formaldehyde solution can reduce water consumption like Paraformaldehyde 96; Simultaneously, after hydrogen peroxide oxidation concentrates, add vitriol oil acidifying; Moisture is removed in decompression, and adds MIBK temperature rising reflux moisture, all can reduce wastewater discharge.
Embodiment
In the four-hole boiling flask of 1000ml, add 96 gram Paraformaldehyde 96s, 96 gram water start and stir, and heat up, and about 50 degree, drip 80 gram content, 5 % liquid caustic soda; In 2 hours, be added dropwise to complete between the control pH value 9-10, continued insulation reaction 4 hours, be warming up to 80 ℃ and reclaim unreacted butyraldehyde-n completely, and a spot of formaldehyde solution, interior temperature is steamed to 100 degree; Stop distillation, cooling is controlled at about 50 degree, slowly drips the ydrogen peroxide 50 of 220 gram content, 27 %; Be controlled in 2 hours and be added dropwise to complete, be added dropwise to complete back insulation reaction 6 hours, add vitriol oil acidifying after, be decompressed to 12kPa and steam and remove moisture; Behind the evaporate to dryness, add MIBK 200 grams and be warming up to 100 ℃ of reflux water-dividings again, has divided water after, lower the temperature; The filtering solid salt is filtrated and is further lowered the temperature while hot, separates out crystal, gets bullion; Bullion added carries out recrystallization again in the solvent, white crystal, record 2,2-dimethylolpropionic acid total recovery 41%.
Claims (5)
1. one kind 2, the preparation method of 2-dimethylolpropionic acid, this method may further comprise the steps:
1) in four-hole boiling flask, adds Paraformaldehyde 96 and water mixing stirring, reacted 2 hours down at 45-55 ℃, and add liquid caustic soda regulator solution pH between 9-10;
2) insulation was warming up to 80 ℃ and steams unreacted butyraldehyde-n and a spot of formaldehyde completely after 4 hours;
3) after distillation finishes, be cooled to 50 ℃, drip ydrogen peroxide 50 in 2 hours, and be incubated 6 hours, add vitriol oil acidifying, be decompressed to 12kPa and remove moisture;
4) behind the evaporate to dryness, add MIBK and be warming up to 100 ℃ of reflux water-dividings, after branch water is intact, be cooled to room temperature, remove solid salt while hot, crystallisation by cooling obtains bullion;
5) bullion is added solvent recrystallization again, obtain white crystal.
2. according to claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that: the water of said input and the mass ratio of Paraformaldehyde 96 are 1:1.
3. according to claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that: the mass ratio of said liquid caustic soda and Paraformaldehyde 96 is 5:6, and the concentration of liquid caustic soda is 5 %.
4. according to claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that: the ydrogen peroxide 50 of said input and the mass ratio of Paraformaldehyde 96 are 55:24, and the concentration of ydrogen peroxide 50 is 27 %.
5. according to claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that: the mibk of said input and the mass ratio of Paraformaldehyde 96 are 25:12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102489009A CN102775296A (en) | 2012-07-18 | 2012-07-18 | Preparation method of 2,2-dimethylolbutanoicacid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102489009A CN102775296A (en) | 2012-07-18 | 2012-07-18 | Preparation method of 2,2-dimethylolbutanoicacid |
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| Publication Number | Publication Date |
|---|---|
| CN102775296A true CN102775296A (en) | 2012-11-14 |
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| CN2012102489009A Pending CN102775296A (en) | 2012-07-18 | 2012-07-18 | Preparation method of 2,2-dimethylolbutanoicacid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812730A (en) * | 2013-07-26 | 2015-07-29 | Lg化学株式会社 | Method for preparing methylol alkanal |
| CN110294670A (en) * | 2019-07-18 | 2019-10-01 | 昆山复希工程技术有限公司 | A kind of process using microreactor continuous production 2,2- dimethylolpropionic acid |
| CN112374975A (en) * | 2020-11-24 | 2021-02-19 | 上海万香日化有限公司 | Preparation method of 3-isopropyl-3-butene-2-ketone |
-
2012
- 2012-07-18 CN CN2012102489009A patent/CN102775296A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 李彩云 等: "2, 2-二羟甲基丁酸的合成", 《化学世界》 * |
| 杨旭石 等: "三甲胺催化多聚甲醛与正丁醛制备2，2－二羟甲基丁醛", 《上海师范大学学报(自然科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812730A (en) * | 2013-07-26 | 2015-07-29 | Lg化学株式会社 | Method for preparing methylol alkanal |
| CN110294670A (en) * | 2019-07-18 | 2019-10-01 | 昆山复希工程技术有限公司 | A kind of process using microreactor continuous production 2,2- dimethylolpropionic acid |
| CN112374975A (en) * | 2020-11-24 | 2021-02-19 | 上海万香日化有限公司 | Preparation method of 3-isopropyl-3-butene-2-ketone |
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Application publication date: 20121114 |