CN110746269A - Synthesis method of 1, 3-propylene glycol - Google Patents
Synthesis method of 1, 3-propylene glycol Download PDFInfo
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- CN110746269A CN110746269A CN201911074645.9A CN201911074645A CN110746269A CN 110746269 A CN110746269 A CN 110746269A CN 201911074645 A CN201911074645 A CN 201911074645A CN 110746269 A CN110746269 A CN 110746269A
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- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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Abstract
The invention discloses a method for synthesizing 1, 3-propylene glycol, which comprises the following steps: using allyl alcohol, chloride and NaBH4Taking ethylene glycol dimethyl ether as a solvent as a raw material, and reacting at the temperature of 0-50 DEG CoAnd C, reacting for 4-12 h under normal pressure. The invention does not need to add a catalyst, and the synthesis method is simple and easy to implement, low in cost and mild in reaction condition.
Description
Technical Field
The invention relates to a synthesis method of 1, 3-propylene glycol, belonging to the technical field of organic synthesis.
Background
1, 3-propanediol (1, 3-PDO) with molecular formula C3H8O2It is an important organic chemical raw material, and can be widely used in the industries of cosmetics, coatings, pharmacy, antifreezing agents and the like. The most important application is as a high polymer material with excellent monomer synthesis performance, and the 1, 3-propanediol and terephthalic acid are copolymerized to prepare polytrimethylene terephthalate polyester fiber (PTT), which is a polymerThe polyester material with excellent performance has the high performance of polyethylene terephthalate (PET) and the easy processability of polybutylene terephthalate (PBT), has good rebound resilience and pollution resistance of nylon, is easy to dye and wear-resistant, has important application in the fields of carpets, engineering plastics, garment materials and the like, is a hotspot for the international development of synthetic fibers at present, is predicted by experts to be one of the most main new fiber varieties in the new century, and can meet the requirements of millions of tons of annual products and large 1,3-PDO in the coming years. However, the 1,3-PDO monomer is expensive and mainly depends on import at present, so that the application aspect is limited. Therefore, a way for producing 1, 3-propanediol with high efficiency and low cost needs to be found.
At present, the preparation methods of 1, 3-propylene glycol at home and abroad mainly comprise the following steps: (1) ethylene oxide process: 1, 3-propanediol is prepared from ethylene oxide by a hydroformylation reduction reaction at elevated pressure (130%oC, 10 MPa), has higher requirements on equipment, high energy consumption and high production cost. (2) Acrolein hydration method: the production line adopts acrolein as a raw material, and acrolein liquid has malodor, steam has irritation and lacrimation, can damage a respiratory system, and is harmful to the environment. (3) And (3) a microbial fermentation method: the 1,3-PDO is prepared by taking carbohydrate such as monosaccharide or polysaccharide as a raw material and fermenting the carbohydrate by dehydratase under proper conditions, and has the advantages that: the method has mild conditions and simple and convenient operation, is a renewable raw material, and meets the requirement of sustainable development of the current society. In the fermentation process, the glycerol with higher concentration and the fermentation product can inhibit the activities of dehydratase and engineering gene bacteria, in order to keep the activity of microorganisms in the fermentation liquor, the initial concentration of the glycerol is required to be lower than 17%, the concentration of the fermentation product 1,3-PDO is caused to be 60-80 g/L, a large amount of water needs to be evaporated in subsequent separation and purification, the energy consumption is increased, meanwhile, various inorganic salts need to be added in the fermentation process to provide nutrient substances for the microorganisms, the microorganism metabolites contain various organic acid impurities, the substrate residues are more, and the later separation is more difficult.
At present, the literature reports that the catalysts for synthesizing 1, 3-propylene glycol by hydrogenation of glycerol by a chemical method mainly comprise: pt-based catalysts, rhodium and iridium-based catalysts, and the like. The main problems of the preparation of 1, 3-propylene glycol by the catalytic hydrogenation of glycerol are as follows: (1) the conversion rate of glycerol and the selectivity of 1,3-PDO are low. The glycerol is subjected to catalytic hydrogenation to obtain products such as 1, 3-propylene glycol, 1, 2-propylene glycol, n-propanol, isopropanol, ethylene glycol, methanol, ethanol and the like, and the propylene glycol is easy to be deeply hydrogenated and cracked into small molecular substances under the action of a catalyst. (2) Most of the catalysts are noble metal catalysts, and the cost is relatively high. Therefore, it is highly desirable to find a way to produce 1, 3-propanediol with high efficiency and low cost.
Disclosure of Invention
The invention aims to provide a method for synthesizing 1, 3-propylene glycol by using allyl alcohol, chloride and NaBH4The reaction provides a new path for synthesizing the 1, 3-propanediol.
Obtaining chloride and NaBH according to the reverse Ma's hydration mechanism of allyl alcohol4The following reactions occur:
formation of intermediate "TiH4, SnCl2, CoCl2”, “BH3". Conjecture of propenol and chloride-NaBH4The mechanism of the reaction is shown in the formula, chloride and NaBH4Reaction to form "BH3”, “BH3"complex with ethylene glycol dimethyl ether, complex with allyl alcohol inverse mahalanobis addition, because the electrophilic center of boron is boron atom, which has empty outer orbital, boron atom adds to the carbon atom of the more hydrogen-containing double bond with negative charge, and hydrogen atom adds a pair of electrons to the carbon atom of the less hydrogen-containing double bond with partial positive charge, then hydrolyzes, and then achieves inverse mahalanobis hydration to 1, 3-propanediol. Chloride hydrolysis ionization of H+Ionically, catalyze the mah-jong hydration of propenol to 1, 2-propanediol. Chloride will enhance NaBH4The reducing ability to carbon-carbon double bonds reduces allyl alcohol to n-propanol.
Mechanism for preparing 1, 3-propylene glycol by propylene alcohol reverse Ma's hydration
The invention provides a method for synthesizing 1, 3-propylene glycol, which uses allyl alcohol, chloride and NaBH4Taking ethylene glycol dimethyl ether as a solvent as a raw material, and reacting at the temperature of 0-50 DEG CoAnd C, reacting for 4-12 h under normal pressure.
The synthesis method of the 1, 3-propylene glycol specifically comprises the following steps:
(1) mixing chloride and NaBH4And ethylene glycol dimethyl ether are added into a 10 mL brown bottle and react for 1h at normal temperature;
the chloride and NaBH4The amount of the substance is 1:1 to 1:4, and the chloride is TICl4、SnCl2、CoCl2One of (1); the reaction temperature is 0-50%oC, reacting for 0.5-1 h under normal pressure; the dosage of 1 mmol of chloride ethylene glycol dimethyl ether is 3-6 mL;
(2) allyl alcohol was added to the above brown vial to react:
the mass ratio of the chloride to the allyl alcohol is 1:1 to 1:4, and the reaction temperature is 0 to 50oC, reacting for 4-14 h under normal pressure;
(3) water was added to the above brown vial to effect a reaction:
the allyl alcohol and H2The amount ratio of O substance is 1:1 to 1:5, the reaction temperature is 0 to 50oAnd C, reacting for 0.5-1 h under normal pressure.
The invention provides a synthesis method of preferable 1, 3-propylene glycol, which comprises the following steps: mixing TiCl4(1 mmol,1 equiv), NaBH4(2 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 14H, and then 1 mmol H was added2O reaction is carried out for 1 h; to obtain the 1, 3-propylene glycol.
The invention has the beneficial effects that:
(1) the method has the advantages of no catalyst in the reaction process, simple reaction, cheap raw materials and easy operation control;
(2) the by-products of the invention are mainly 1, 2-propylene glycol and n-propanol. The added value of the product is relatively high.
(3) The synthesis method of the invention has the advantages of simple required equipment, low cost and mild reaction conditions.
Drawings
FIG. 1 is a mass spectrum of 1, 3-propanediol, the product obtained in example 1.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
mixing TiCl4(1 mmol, 1 equiv), NaBH4(2 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 14H, and then 1 mmol H was added2And O is reacted for 1 h. The equation for the reaction is as follows:
preparation of 1, 3-propylene glycol by anti-Ma's hydration of allyl alcohol
FIG. 1 shows the mass spectrum of 1, 3-propanediol, the product obtained in this example: m/z 58 is- (CH)2)3Fragment peak of-O, m/z 45 is- (CH)2)2Fragment peak of-OH, m/z 28 is- (CH)2)2The fragment peak of (a) is the highest relative abundance on the mass spectrum (100), and is detected to be more than 98% by comparison with the literature and similarity with a GC-MS standard library. From this, it was further confirmed that the synthesized substance was 1, 3-propanediol. GC-MS (EI, 70eV) m/z (%):58(86), 45(16), 28 (100).
Example 2:
mixing TiCl4(1 mmol, 1 equiv), NaBH4(1 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 0.5H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 14H, and then 1 mmol H was added2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 3:
mixing TiCl4(1 mmol, 1 equiv), NaBH4(3 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 12H, and then 1 mmol H was added2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 4
SnCl2(1 mmol, 1 equiv), NaBH4(2 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 10H, and then 1 mmol H was added2O reacts for 0.5 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 5
SnCl2(1 mmol, 1 equiv), NaBH4(2 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (2 mmol, 1 equiv) propenol was added, reacted at room temperature for 12H, and then 2 mmol H was added2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 6
Adding CoCl2(1 mmol, 1 equiv), NaBH4(3 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 12H, then 3 mmol H was added2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 7
Adding CoCl4(1 mmol, 1 equiv), NaBH4(2 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were addedAdding into 10 mL brown bottle, reacting at room temperature for 1H, adding (3 mmol, 1 equiv) propenol, reacting at room temperature for 10H, and adding 4 mmol H2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 8
Adding CoCl2(1 mmol, 1 equiv), NaBH4(4 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 1H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 10H, and then 2 mmol H was added2And O is reacted for 1 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Example 9
Mixing TiCl4(1 mmol, 1 equiv), NaBH4(3 mmol, 1 equiv) and ethylene glycol dimethyl ether (3 mL) were added to a 10 mL brown vial, reacted at room temperature for 0.5H, then (1 mmol, 1 equiv) propenol was added, reacted at room temperature for 14H, and then 3 mmol H was added2O reacts for 0.5 h.
The product obtained in this example was 1, 3-propanediol by gas chromatography-mass spectrometer detection.
Claims (4)
1. A method for synthesizing 1, 3-propylene glycol is characterized in that: using allyl alcohol, chloride and NaBH4Taking ethylene glycol dimethyl ether as a solvent as a raw material, and reacting at the temperature of 0-50 DEG CoAnd C, reacting for 4-12 h under normal pressure.
2. The method for synthesizing 1, 3-propanediol according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) mixing chloride and NaBH4And ethylene glycol dimethyl ether were added to a brown vial to carry out a reaction;
the chloride is reacted with NaBH4The ratio of the amount of the substances is 1: 1-1: 4, the amount of 1 mmol of the chloride ethylene glycol dimethyl ether is 3-6 mL, and the reaction temperature is 0-50oC, reacting for 0.5-1 h under normal pressure;
(2) adding allyl alcohol into the brown bottle for reaction;
the mass ratio of the chloride to the allyl alcohol is 1:1 to 1:4, and the reaction temperature is 0 to 50oC, reacting for 4-14 h under normal pressure;
(3) adding water into the brown bottle for reaction;
the allyl alcohol and H2The amount ratio of O substance is 1:1 to 1:5, and the reaction temperature is 0 to 50oAnd C, reacting for 0.5-1 h under normal pressure.
3. The method for synthesizing 1, 3-propanediol according to claim 2, wherein: the chloride is TICl4、SnCl2、CoCl2One kind of (1).
4. The method for synthesizing 1, 3-propanediol according to claim 2, wherein: the method comprises the following steps:
1 mmol of TiCl4、2 mmol NaBH4Adding 3 mL of ethylene glycol dimethyl ether into a 10 mL brown bottle, reacting at normal temperature for 1H, adding 1 mmol of allyl alcohol, reacting at normal temperature for 14H, and adding 1 mmol of H2O reaction is carried out for 1 h; to obtain the 1, 3-propylene glycol.
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| WO2003006455A1 (en) * | 2001-07-11 | 2003-01-23 | Eli Lilly And Company | Pharmaceutical compounds with serotonin receptor activity |
| CN101407448A (en) * | 2008-11-07 | 2009-04-15 | 南京工业大学 | Method for continuously preparing 1, 3-propylene glycol by one-step conversion of glycerol |
| CN101696157A (en) * | 2009-10-29 | 2010-04-21 | 上海福尔福特种材料科技发展有限公司 | Method for preparing 1,2,4-butanetriol |
| CN109970511A (en) * | 2019-04-19 | 2019-07-05 | 江苏扬农化工集团有限公司 | A kind of method of HPPO by-product resource utilization synthesis 1,3- propylene glycol |
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2019
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| WO2003006455A1 (en) * | 2001-07-11 | 2003-01-23 | Eli Lilly And Company | Pharmaceutical compounds with serotonin receptor activity |
| CN101407448A (en) * | 2008-11-07 | 2009-04-15 | 南京工业大学 | Method for continuously preparing 1, 3-propylene glycol by one-step conversion of glycerol |
| CN101696157A (en) * | 2009-10-29 | 2010-04-21 | 上海福尔福特种材料科技发展有限公司 | Method for preparing 1,2,4-butanetriol |
| CN109970511A (en) * | 2019-04-19 | 2019-07-05 | 江苏扬农化工集团有限公司 | A kind of method of HPPO by-product resource utilization synthesis 1,3- propylene glycol |
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