CN110947423B - Catalyst for synthesizing propylene glycol ether and preparation method thereof - Google Patents
Catalyst for synthesizing propylene glycol ether and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of chemical catalysis, and discloses a catalyst for synthesizing propylene glycol ether, wherein the catalyst is polyvinyl imidazole-divinylbenzene, and the preparation method comprises the following steps: adding azodiisobutyronitrile, N into an ethyl acetate solution of 1-vinylimidazole with the concentration of 0.5-1.2 mol/L2Or heating to 65-90 ℃ under inert gas, keeping the temperature for 0.5-2 h, adding an ethyl acetate solution of divinylbenzene, keeping the temperature for 12-24 h at 65-90 ℃, cooling, and drying a product to obtain the catalyst for synthesizing the propylene glycol ether, wherein the addition amount of the azobisisobutyronitrile is 0.01-5 wt% of 1-vinyl imidazole, and the molar ratio of the 1-vinyl imidazole to the divinylbenzene is 1: 0.01 to 20. The obtained catalyst for synthesizing propylene glycol ether has the advantages of high activity, high selectivity, low energy consumption, easy separation and the like, and is low in production cost and suitable for industrial production.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a catalyst for synthesizing propylene glycol ether and a preparation method thereof.
Background
Propylene glycol ether, especially Propylene Glycol Methyl Ether (PGME), has two functional groups with strong dissolving capacity in its chemical structure, ether bond and hydroxyl group, and is hydrophobic and hydrophilic, so that propylene glycol methyl ether may be used as universal solvent with excellent performance. The propylene glycol ether has lower toxicity to human body than glycol ether products, and belongs to low toxicity ethers. Has weak ether smell but no strong pungent smell, is used as an environment-friendly organic solvent, has wider and safer application, and can be used in various fields. Such as styrene-acrylic emulsion, acrylic emulsion and emulsion paint body thereof, viscosity regulator in brake fluid formula, raw material for organic synthesis and the like.
Due to the steric effect of the propylene oxide, the ring opening positions of the propylene oxide are different under the conditions of acid and alkali, and then the propylene oxide and alcohols undergo addition reaction, so that the alkali generates 1-methoxy-2-propanol, and the acid generates 2-methoxy-1-propanol. Meanwhile, the toxicity of the product I is higher than that of the product II, so that people pay more and more attention to the synthesis of propylene glycol ether by alkali catalysis.
At present, the traditional strong alkaline catalysts sodium (potassium) alkoxide and sodium hydroxide are mostly adopted for synthesizing propylene glycol ether industrially, but the catalysts have the defects of strong corrosivity, large generation amount of three wastes, difficult recovery of the catalysts and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a catalyst for synthesizing propylene glycol ether and a preparation method thereof.
The invention provides a catalyst for synthesizing propylene glycol ether, which is polyvinyl imidazole-divinylbenzene (PVIM-DVB) and has a structural formula
Wherein n is 10000-50000, and m is 10000-50000.
The invention also provides a preparation method of the catalyst for synthesizing the propylene glycol ether, which comprises the following steps:
adding azodiisobutyronitrile, N into an ethyl acetate solution of 1-vinylimidazole with the concentration of 0.5-1.2 mol/L2Or heating to 65-90 ℃ under inert gas, keeping the temperature for 0.5-2 h, adding an ethyl acetate solution of divinylbenzene, keeping the temperature for 12-24 h at 65-90 ℃, cooling, and drying a product to obtain the catalyst for synthesizing the propylene glycol ether, wherein the addition amount of the azobisisobutyronitrile is0.01 to 5 wt% of 1-vinylimidazole, wherein the molar ratio of the 1-vinylimidazole to divinylbenzene is 1: 0.01 to 20.
The invention provides a composite catalyst for synthesizing propylene glycol ether and a preparation method thereof, and the obtained catalyst PVIM-DVB for synthesizing propylene glycol ether has the advantages of high activity, high selectivity, low energy consumption, easy separation and the like. The addition of DVB allowed PVIM to evolve from linear polymers to crosslinked polymers that are insoluble in alcohol. Meanwhile, compared with the existing alkaline solid catalyst, the catalyst has high efficiency and few byproducts in catalyzing alcohol ether reaction. In addition, the catalyst has simple preparation process and low production cost, and is suitable for industrial production.
Drawings
FIG. 1 is a diagram showing a catalytic mechanism of a propylene glycol ether catalyst obtained in example 1 of the present invention;
FIG. 2 is an infrared characterization chart of the propylene glycol ether catalyst obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a catalyst for synthesizing propylene glycol ether, wherein the catalyst is polyvinyl imidazole-divinylbenzene (PVIM-DVB), and the structural formula of the catalyst is shown in the specification
Wherein n is 10000-50000, and m is 10000-50000.
Preferably, n is 20000 to 30000, and m is 20000 to 30000.
The embodiment of the invention also provides a preparation method of the catalyst for synthesizing the propylene glycol ether, which comprises the following steps:
adding azodiisobutyronitrile, N into an ethyl acetate solution of 1-vinylimidazole with the concentration of 0.5-1.2 mol/L2Or heating to 65-90 ℃ under inert gas, keeping for 0.5-2 h, and then adding divinylKeeping the ethyl acetate solution of benzene at 65-90 ℃ for 12-24 h, cooling, and drying the product to obtain the catalyst for synthesizing the propylene glycol ether, wherein the addition amount of the azobisisobutyronitrile is 0.01-5 wt% of 1-vinylimidazole, and the molar ratio of the 1-vinylimidazole to the divinylbenzene is 1: 0.01 to 20.
Preferably, the azodiisobutyronitrile is added in an amount of 0.2 to 0.6 wt% of 1-vinylimidazole, and the molar ratio of 1-vinylimidazole/divinylbenzene is 1: 0.2 to 3. More preferably, the azodiisobutyronitrile is added in an amount of 0.3 to 0.5 wt% of 1-vinylimidazole, and the molar ratio of 1-vinylimidazole/divinylbenzene is 1: 0.5 to 2.
The catalytic mechanism of the catalyst for synthesizing propylene glycol ether can be summarized into the following two key steps: (1) CH (CH)3Deprotonation of the OH group and (2) opening of the propylene oxide ring. In CH3In the process of OH dissociation into hydrogen protons and methoxy ions, methoxy attacks PO through an SN2 pathway, and opens a carbon-oxygen bond for ring opening before the proton is transferred to a negative ion. And the rate-determining step of the reaction consists in the ring opening of the PO. Therefore, the catalyst for synthesizing the propylene glycol ether has a synergistic effect on the ring opening of the epoxy resin.
The preparation method and the application of the catalyst for synthesizing propylene glycol ether are illustrated by the following specific examples.
Example 1:
synthesis of polyvinylimidazole-divinylbenzene (PVIM-DVB):
2.3g vinylimidazole, 0.02g azobisisobutyronitrile in 30mL ethyl acetate, N2Purging and replacing air for 30min, and heating to 90 ℃ for reaction for 1 h; then, an ethyl acetate solution containing 2.3g of divinylbenzene is added dropwise to react for 24 hours, the mixture is cooled to room temperature and moved to a vacuum drying oven to be dried for 24 hours at 60 ℃, and light yellow solid PVIM-DVB is obtained. The infrared characterization is shown in FIG. 2, which shows the characteristic absorption peaks, 1650cm, of VIM and DVB units-1The peak at (B) is the stretching vibration peak of imidazole unit C ═ N bond, 1500cm-1The peak is the stretching vibration peak of C ═ C bond between imidazole ring and benzene ring, 900cm-1、650cm-1The peak is the out-of-plane extension of the C-H bond on the benzene ringAnd (4) contracting the vibration peak. The appearance of these characteristic peaks is sufficient to indicate that the monomer VIM and DVB are cross-linked and copolymerized to form the copolymer PVIM-DVB.
Example 2:
synthesis of polyvinylimidazole-divinylbenzene (PVIM-DVB):
2.3g vinylimidazole, 0.02g azobisisobutyronitrile in 30mL ethyl acetate, N2Purging and replacing air for 30min, and heating to 90 ℃ for reaction for 1 h; then, an ethyl acetate solution containing 4.6g of divinylbenzene is dropwise added to react for 24 hours, the mixture is cooled to room temperature and moved to a vacuum drying oven to be dried for 24 hours at the temperature of 60 ℃, and light yellow solid PVIM-DVB is obtained.
Example 3:
synthesis of polyvinylimidazole-divinylbenzene (PVIM-DVB):
2.3g vinylimidazole, 0.02g azobisisobutyronitrile in 30mL ethyl acetate, N2Purging and replacing air for 30min, and heating to 90 ℃ for reaction for 1 h; then, an ethyl acetate solution containing 0.46g of divinylbenzene was added dropwise to react for 24 hours, cooled to room temperature, moved to a vacuum drying oven, and dried at 60 ℃ for 24 hours to obtain PVIM-DVB as a pale yellow solid. The catalyst is used in the alcoholysis ring-opening reaction of the propylene oxide, and the catalyst has a dissolving phenomenon and is not beneficial to recycling.
Example 4:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:6, the polyvinyl imidazole-divinylbenzene is 0.55 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 97.00% and the selectivity of propylene glycol monomethyl ether was calculated to be 97.85%.
Example 5:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 130 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:6, the polyvinyl imidazole-divinylbenzene is 0.55 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 99.40%, and the selectivity of propylene glycol monomethyl ether was calculated to be 95.41%.
Example 6:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:3, the polyvinyl imidazole-divinylbenzene is 0.55 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 97.69%, and the selectivity of propylene glycol monomethyl ether was calculated to be 97.85%.
Example 7:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:9, the polyvinyl imidazole-divinylbenzene is 0.55 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 94.15%, and the selectivity of propylene glycol monomethyl ether was calculated to be 95.40%.
Example 8:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:12, the polyvinyl imidazole-divinylbenzene is 0.55 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 90.96%, and the selectivity of propylene glycol monomethyl ether was calculated to be 98.28%.
Example 9:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:6, the polyvinyl imidazole-divinylbenzene is 0.33 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 91.95%, and the selectivity of propylene glycol monomethyl ether was calculated to be 95.44%.
Example 10:
uniformly mixing methanol and the polyvinyl imidazole-divinylbenzene obtained in example 1, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 120 ℃, and rapidly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:6, the weight of the polyvinyl imidazole-divinylbenzene is 0.77 wt%, and reacting the mixture for 45 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 97.66%, and the selectivity of propylene glycol monomethyl ether was calculated to be 90.63%.
Comparative example 1:
synthesis of homopolymer PDVB:
2.3g of divinylbenzene, 0.01g of azobisisobutyronitrile were dissolved in 30mL of ethyl acetate, N2Purging and replacing air for 30min, heating to 90 ℃, reacting for 24h, cooling to room temperature, moving to a vacuum drying oven, aging and drying at 60 ℃ for 24h to obtain a white solid.
Uniformly mixing methanol and PDVB, feeding the mixture into a high-pressure reaction kettle, stamping the mixture to 0.8-1.2 MPa, heating the mixture to 90 ℃, quickly adding propylene oxide by using a pump, wherein the molar ratio of the propylene oxide to the alcohol is 1:3, the PDVB is 0.33 wt%, and reacting for 50 min. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 2.83%, and the selectivity of propylene glycol monomethyl ether was calculated to be 99.99%.
As can be seen from the examples and comparative example 1, the imidazole unit in 1-vinylimidazole plays a decisive role in increasing the conversion and selectivity; the addition of the divinylbenzene also enables the PVIM to be converted from homogeneous phase to heterogeneous PVIM-DVB, so that the catalyst is easy to recover, and a foundation is laid for further industrialization.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The application of the catalyst for synthesizing the propylene glycol ether is characterized in that the catalyst is polyvinyl imidazole-divinylbenzene, and the structural formula of the catalyst is shown in the specification
Wherein n is 10000-50000, m is 10000-50000, and the catalyst is used for catalyzing the reaction of propylene oxide and alcohol to synthesize propylene glycol ether.
2. The use according to claim 1, wherein the catalyst is prepared by a process comprising the steps of: adding azodiisobutyronitrile, N into an ethyl acetate solution of 1-vinylimidazole with the concentration of 0.5-1.2 mol/L2Or heating to 65-90 ℃ under inert gas, keeping the temperature for 0.5-2 h, adding an ethyl acetate solution of divinylbenzene, keeping the temperature for 12-24 h at 65-90 ℃, cooling, and drying a product to obtain the catalyst for synthesizing the propylene glycol ether, wherein the addition amount of the azobisisobutyronitrile is 0.01-5 wt% of 1-vinyl imidazole, and the molar ratio of the 1-vinyl imidazole to the divinylbenzene is 1: 0.01 to 20.
3. Use according to claim 2, wherein azobisisobutyronitrile is added in an amount of 0.2 to 0.6 wt% of 1-vinylimidazole.
4. Use according to claim 2, wherein azobisisobutyronitrile is added in an amount of 0.3 to 0.5 wt% of 1-vinylimidazole.
5. Use according to claim 2, wherein the molar ratio of 1-vinylimidazole to divinylbenzene is from 1: 0.2 to 3.
6. Use according to claim 2, wherein the molar ratio of 1-vinylimidazole to divinylbenzene is from 1: 0.5 to 2.
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| US20060058413A1 (en) * | 2002-12-30 | 2006-03-16 | Aniela Leistner | Adsorbing material for blood and plasma cleaning method and for albumin purification |
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN103182324A (en) * | 2011-12-28 | 2013-07-03 | 中国石油天然气股份有限公司 | Method for preparing hydrophobic organic framework solid base catalyst |
| CN107400043A (en) * | 2016-05-20 | 2017-11-28 | 中国科学院过程工程研究所 | Application and propylene glycol synthetic method of the ionic liquid in propylene glycol synthesis |
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Patent Citations (4)
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| US20060058413A1 (en) * | 2002-12-30 | 2006-03-16 | Aniela Leistner | Adsorbing material for blood and plasma cleaning method and for albumin purification |
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN103182324A (en) * | 2011-12-28 | 2013-07-03 | 中国石油天然气股份有限公司 | Method for preparing hydrophobic organic framework solid base catalyst |
| CN107400043A (en) * | 2016-05-20 | 2017-11-28 | 中国科学院过程工程研究所 | Application and propylene glycol synthetic method of the ionic liquid in propylene glycol synthesis |
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