CN102746141A - Method for synthesizing beta-hydroxy propionic acid - Google Patents
Method for synthesizing beta-hydroxy propionic acid Download PDFInfo
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- CN102746141A CN102746141A CN2012102799151A CN201210279915A CN102746141A CN 102746141 A CN102746141 A CN 102746141A CN 2012102799151 A CN2012102799151 A CN 2012102799151A CN 201210279915 A CN201210279915 A CN 201210279915A CN 102746141 A CN102746141 A CN 102746141A
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- acid
- ethylene lactic
- lactic acid
- preparing ethylene
- molecular sieve
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Abstract
Disclosed is a method for synthesizing a beta-hydroxy propionic acid. The method includes preparing propenoic acid into a propenoic acid solution with a mass fraction of 10% to 60% with water, adding polymerization inhibitor hydroquinone accounting for 0.1% to 1.0% of the quality of the propenoic acid, adding a catalyst to regulate the pH to be 0.5 to 4.0, replacing air in a kettle with nitrogen gas, reacting the mixture at a temperature of 60 DEG C to 280 DEG C for 1h to 24h, and cooling the mixture to a room temperature to obtain the beta-hydroxy propionic acid. The method for synthesizing the beta-hydroxy propionic acid has the advantages that raw materials are cheap and easy to obtain, reaction conditions are mild, technological conditions are simple, resultants are easy to separate, the reaction is provided with high yield, and defects that other chemical method materials are difficult to obtain and the biological method yield is low are overcome.
Description
Technical field
The present invention relates to a kind of method of synthetic ethylene lactic acid, be specifically related to homogeneous phase and the acid of heterogeneous catalysis propene hydrate makes ethylene lactic acid.
Background technology
Ethylene lactic acid (β-HP) as the monomer that gathers ethylene lactic acid, be the important industrial chemicals of a kind of potential.This molecule has two functional group's hydroxyls and carboxyl, is the precursor of a lot of optically active substances.Turn into generating ester with alcohol ester, oxidation generates propanedioic acid, and dehydration generates vinylformic acid, also can generate 1 through reductive action, ammediol etc.; 1, ammediol is again the monomer of polyester (PTT), can be used for producing coating, sizing agent, Water Treatment Chemicals and personal-care supplies; β-HP can also be as the raw material of biological polyester in addition; Poly (hydroxyalkanoate) (PHA) is the biodegradable thermoplastic material; Has physical property widely; Since in many biological metabolism approach, all can find the existence of β-HP, obvious especially in spontaneous biopolymerization reaction, gather 3-hydroxybutyric acid ethylene lactic acid (poly (3-HB-co-3-HP) with 3-hydroxybutyric acid effect formation.Based on above these characteristics,, will become the focus of the competition of chemical field so have market outlook in the production of following ethylene lactic acid.One of Chemicals of 12 kinds of tool potentialities to be exploited are classified β-HP on the our times as in the report of the USDOE in August, 2004.
At present, biotransformation method is in the majority in the compound method of report ethylene lactic acid, and chemical synthesis has the hydrolysis of 3-hydroxypropionitrile, oxidation of 3-hydroxy propanal and Reformatsky reaction, but vinylformic acid hydration report is seldom; Only in patent CN1753858A, reported; With carbonic acid gas, sulfur oxide, nitrogen oxide and pKa>7 organic bases or mineral alkali be that catalyzer carries out hydration, what obtain after this method reaction is the salt of beta-hydroxycarboxylic acids, and the dimer of ethers; Product need carry out acidifying; To obtain ethylene lactic acid and acrylic acid oligopolymer with the dodecanol distillation then, extract with ETHYLE ACETATE at last and remove impurity, so the recovery of product and separate complex.
Summary of the invention
The purpose of this invention is to provide that a kind of processing condition are simple, production cost is low, product separates easily and the method for the synthetic ethylene lactic acid that productive rate is high.
A kind of method for preparing ethylene lactic acid provided by the invention; This method is the acrylic acid aqueous solution that the vinylformic acid water is mixed with massfraction 10%～60%, adds the hydroquinone of polymerization retarder that accounts for vinylformic acid quality 0.1%～1.0%, and then adds catalyzer adjusting pH=0.5～4.0; With air in the nitrogen replacement still; Reacted 1～24 hour down at 60～280 ℃, be cooled to room temperature, promptly get ethylene lactic acid;
This catalyzer is selected from hydrogen salt, buffered soln, zeolite molecular sieve, loading type mineral acid, acidic cationic resin or the Lewis acid of protonic acid, protonic acid.
In the present invention, protonic acid is sulfuric acid, the acid of phosphoric acid inorganic proton, acetate, propionic acid or oxalic acid, corresponding, the hydrogen salt of protonic acid is the hydrogen salt of sulfuric acid, the acid of phosphoric acid inorganic proton, acetate, propionic acid or oxalic acid.
In the present invention, buffered soln is phosphoric acid-triethylamine buffered soln or phosphoric acid-potassium dihydrogen phosphate buffer solution.
In the present invention, zeolite molecular sieve is micropore AI zeolite molecular sieve or H-beta-zeolite molecular sieve.
In the present invention, the loading type mineral acid is H
3PO
4/ TiO
2, KH
2PO
4/ TiO
2Or Ni/SO
4 2--SnO
2
In the present invention, Lewis acid is ZnCl
2, CuCl
2, CoCl
2, FeCl
3Or SnCl
4
In the present invention, acidic cationic resin is strong acidic ion resin 001*7, strong acidic ion resin D072, acidulous cation resin D113 or acidulous cation resin 116.
In the present invention, preferably, reacted 3～18 hours down at 90～250 ℃.
Advantage of the present invention is: low in raw material cost is easy to get, and reaction conditions is gentle, and processing condition are simple, and product separates easily, and reaction has higher productive rate, has overcome the rare shortcoming of raw material and the low drawback of biological process productive rate of other chemical methods.
Vinylformic acid is not only as reagent in reaction, and is the donor as formed carbonium ion midbody in the reaction.Reaction is to be undertaken by the electrophilic addition course that generates the carbonium ion midbody.Add protonic acid and buffering solution, direct ionization goes out H in the reaction
+Improve H
+Concentration, help the formation of carbonium ion, promote reaction to move, thereby improved the yield of reaction to positive dirction.Mechanism is following:
And solid acid catalyst is extracted a negative hydrogen ion out through accepting a pair of electronics, promptly promotes vinylformic acid to form carbonium ion, and L represents the solid acid catalyst acid site, and mechanism is following:
Its reaction product is anti-Markovnikov rule; Reason is: because the sucting electronic effect of carbonyl makes uncle's carbonium ion
of generation more stable than secondary carbonium ion midbody
.
Advantage of the present invention is: low in raw material cost is easy to get, and reaction conditions is gentle, and processing condition are simple, and product separates easily, and reaction has higher productive rate, has overcome the rare shortcoming of raw material and the low drawback of biological process productive rate of other chemical methods.
Concrete embodiment
Below will do further description to the present invention through embodiment, in an embodiment:
Testing method detects the product characteristics that the present invention makes below adopting:
Performance liquid chromatography (HPLC)
The product that the present invention makes adopts day binary HPLC pump of island proper Tianjin company to detect, and this device is furnished with C18 post and UV-detector, and moving phase is the KH of 0.5 mol/L
2PO
4Buffered soln, flow velocity are 1 ml/min, and column temperature is 30 ℃.
Gc (GC)
Model and the testing conditions of GC are following: GC-2010, the OV-17 capillary chromatographic column (0.5 μ m * 30m)
From 80 ℃ of 180 ℃ of Zhongdao of rising, the vaporizer temperature is 200 ℃ to column temperature with 20 ℃/min heat-up rate, and detector temperature is 240 ℃.
Embodiment 1
200g vinylformic acid water is mixed with the acrylic acid aqueous solution of massfraction 10%, adds the hydroquinone of polymerization retarder of 0.2 g, regulate pH=1.00 with phosphoric acid then; Sealed reactor with nitrogen purging 4 times, is heated to 200 ℃ under stirring; Reaction 5h, cool to room temperature uses HPLC and GC-MS to analyze then; The reaction after product has ethylene lactic acid, alpha-hydroxypropionic acid (lactic acid), 3,3-oxo dipropionic acid, and unreacted vinylformic acid.Acrylic acid transformation efficiency is 86.67%, and the selectivity of ethylene lactic acid is 80.45%.
Embodiment 2
200g vinylformic acid water is mixed with the acrylic acid aqueous solution of massfraction 30%, adds the hydroquinone of polymerization retarder of 0.6 g, regulate pH=0.60 with phosphoric acid then; Sealed reactor with nitrogen purging 4 times, is heated to 120 ℃ under stirring; Reaction 10h, cool to room temperature promptly gets ethylene lactic acid then.Sampling analysis, acrylic acid transformation efficiency are 90.27%, and the selectivity of ethylene lactic acid is 87.45%.
Embodiment 3
500g vinylformic acid water is mixed with the acrylic acid aqueous solution of massfraction 10%, adds the hydroquinone of polymerization retarder of 0.5 g, add loading type mineral acid Ni/SO then
4 2--SnO
2Regulate pH=2.70, sealed reactor with nitrogen purging 4 times, is heated to 120 ℃ under stirring, and reacts 12h, and cool to room temperature promptly gets ethylene lactic acid.Sampling analysis, acrylic acid transformation efficiency are 78.67%, and the selectivity of ethylene lactic acid is 68.45%.
Embodiment 4
200g vinylformic acid water is mixed with the acrylic acid aqueous solution of massfraction 10%, adds the hydroquinone of polymerization retarder of 0.2 g, add the strongly acidic cationic exchange resin D072 that anticipates then; Regulate pH=2.30, sealed reactor is with nitrogen purging 4 times; Be heated to 120 ℃ under stirring; Reaction 12h, cool to room temperature promptly gets ethylene lactic acid.Sampling analysis, acrylic acid transformation efficiency are 94.67%, and the selectivity of ethylene lactic acid is 75.45%.
Embodiment 5
200g vinylformic acid water is mixed with the acrylic acid aqueous solution of massfraction 25%, adds the hydroquinone of polymerization retarder of 0.5g, the Lewis acid ZnCl that adds then
2, regulate pH=2.00, sealed reactor with nitrogen purging 4 times, is heated to 150 ℃ under stirring, and reacts 10h, cool to room temperature; Sampling analysis, acrylic acid transformation efficiency are 90.67%, and the selectivity of ethylene lactic acid is 85.95%.
Embodiment 6
Step according to embodiment 1 is carried out, and just temperature of reaction is 120 ℃, and the reaction times is 12h.The acrylic acid transformation efficiency of gained is 91.85%, and the selectivity of ethylene lactic acid is 59.82%.
Embodiment 7
Step according to embodiment 1 is carried out, and regulates pH=2.00 with phosphoric acid-triethylamine buffered soln, reacts 3 hours down at 200 ℃.Sampling analysis, acrylic acid transformation efficiency are 95.56%, and the selectivity of ethylene lactic acid is 89.45%.
Embodiment 8
Step according to embodiment 2 is carried out, and just phosphoric acid is replaced regulating pH=0.60 with sulfuric acid.Acrylic acid transformation efficiency is 90.77%, and the selectivity of ethylene lactic acid is 79.85%.
Embodiment 9
Step according to embodiment 3 is carried out, and changes the loading type inorganic acid catalyst into the H-beta-zeolite molecular sieve.Reaction conditions is constant.Acrylic acid transformation efficiency is 92.57%, and the selectivity of ethylene lactic acid is 77.85%.
Claims (9)
1. a method for preparing ethylene lactic acid is characterized in that, this method is the acrylic acid aqueous solution that the vinylformic acid water is mixed with massfraction 10%～60%; Add the hydroquinone of polymerization retarder that accounts for vinylformic acid quality 0.1%～1.0%; And then add catalyzer adjusting pH=0.5～4.0, with air in the nitrogen replacement still, reacted 1～24 hour down at 60～280 ℃; Be cooled to room temperature, promptly get ethylene lactic acid;
This catalyzer is selected from hydrogen salt, buffered soln, zeolite molecular sieve, loading type mineral acid, acidic cationic resin or the Lewis acid of protonic acid, protonic acid.
2. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that, protonic acid is sulfuric acid, the acid of phosphoric acid inorganic proton, acetate, propionic acid or oxalic acid.
3. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that, the hydrogen salt of protonic acid is the hydrogen salt of sulfuric acid, the acid of phosphoric acid inorganic proton, acetate, propionic acid or oxalic acid.
4. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that, buffered soln is phosphoric acid-triethylamine buffered soln or phosphoric acid-potassium dihydrogen phosphate buffer solution.
5. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that, zeolite molecular sieve is micropore AI zeolite molecular sieve or H-beta-zeolite molecular sieve.
6. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that the loading type mineral acid is H
3PO
4/ TiO
2, KH
2PO
4/ TiO
2Or Ni/SO
4 2--SnO
2
7. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that Lewis acid is ZnCl
2, CuCl
2, CoCl
2, FeCl
3Or SnCl
4
8. a kind of method for preparing ethylene lactic acid according to claim 1; It is characterized in that acidic cationic resin is strong acidic ion resin 001*7, strong acidic ion resin D072, acidulous cation resin D113 or acidulous cation resin 116.
9. a kind of method for preparing ethylene lactic acid according to claim 1 is characterized in that, reacts 3～18 hours down at 90～250 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461512A (en) * | 2021-08-06 | 2021-10-01 | 上海交通大学 | Preparation method of 3-hydroxypropionic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114657B1 (en) * | 1983-01-20 | 1987-03-18 | Mitsubishi Gas Chemical Company, Inc. | Process for production of hydroxycarboxylic acids |
| US5284979A (en) * | 1991-11-27 | 1994-02-08 | Degussa Aktiengesellschaft | Process for the prepartion of 3-hydroxyalkanals |
| CN1572759A (en) * | 2003-05-28 | 2005-02-02 | 三井化学株式会社 | Process for producing hydroxyl group-containing compound |
| CN1670006A (en) * | 2004-03-15 | 2005-09-21 | 中国科学院大连化学物理研究所 | Process for producing lower alcohol by direct hydration of low carbon olefin |
| CN1753858A (en) * | 2003-02-24 | 2006-03-29 | 嘉吉有限公司 | Process for preparing 3-hydroxycarboxylic acids |
-
2012
- 2012-08-08 CN CN2012102799151A patent/CN102746141A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114657B1 (en) * | 1983-01-20 | 1987-03-18 | Mitsubishi Gas Chemical Company, Inc. | Process for production of hydroxycarboxylic acids |
| US5284979A (en) * | 1991-11-27 | 1994-02-08 | Degussa Aktiengesellschaft | Process for the prepartion of 3-hydroxyalkanals |
| CN1753858A (en) * | 2003-02-24 | 2006-03-29 | 嘉吉有限公司 | Process for preparing 3-hydroxycarboxylic acids |
| CN1572759A (en) * | 2003-05-28 | 2005-02-02 | 三井化学株式会社 | Process for producing hydroxyl group-containing compound |
| CN1670006A (en) * | 2004-03-15 | 2005-09-21 | 中国科学院大连化学物理研究所 | Process for producing lower alcohol by direct hydration of low carbon olefin |
Non-Patent Citations (3)
| Title |
|---|
| 方孝斌: "生物可降解高分子3-羟基丙酸聚酯的合成与表征", 《安徽大学硕士学位论文》, 1 April 2007 (2007-04-01) * |
| 沈长洲等: "丙烯酸及甲基丙烯酸高温水合反应的研究", 《化学试剂》, vol. 19, no. 2, 31 December 1997 (1997-12-31), pages 77 - 79 * |
| 陈亮等: "酸催化丙烯醛水合规律的研究", 《茂名学院学报》, vol. 17, no. 1, 28 February 2007 (2007-02-28), pages 9 - 12 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461512A (en) * | 2021-08-06 | 2021-10-01 | 上海交通大学 | Preparation method of 3-hydroxypropionic acid |
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