CN103012079B - The method of solid base catalyst catalytically synthesizing glycol propenyl ether - Google Patents
The method of solid base catalyst catalytically synthesizing glycol propenyl ether Download PDFInfo
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- CN103012079B CN103012079B CN201210544927.2A CN201210544927A CN103012079B CN 103012079 B CN103012079 B CN 103012079B CN 201210544927 A CN201210544927 A CN 201210544927A CN 103012079 B CN103012079 B CN 103012079B
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- oxyethane
- vinylcarbinol
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Abstract
The invention discloses the method for solid base catalyst catalytically synthesizing glycol propenyl ether, belong to technology of fine chemicals.With vinylcarbinol and oxyethane for raw material, at load type solid body base catalyst KF/Al
2o
3effect under, oxyethane ring-opening reaction synthesizing glycol propenyl ether, described loading type KF/Al
2o
3the mass percent consumption of catalyzer is 0.5% ~ 3.0% of reactant total mass; The reaction molar ratio of described preparation glycol propylene base ether is: vinylcarbinol: oxyethane=2.0 ~ 6.0:1; Temperature of reaction is 90 ~ 130 DEG C.Advantage of the present invention is: adopt loading type KF/Al
2o
3catalyzer synthesizing glycol propenyl ether, overcome conventional homogeneous catalyst product separation difficulty, the shortcoming of product easy coloring, this technique is corrosion-free to equipment, environmentally safe, and energy consumption, material consumption are low, and catalyzer can be reused.
Description
Technical field
The present invention relates to the synthesis of glycol propylene base ether, be vinylcarbinol and oxyethane is raw material, at load type solid body base catalyst KF/Al
2o
3effect under, oxyethane ring-opening reaction synthesizing glycol propenyl ether.Belong to technology of fine chemicals.
Background technology
Glycol propylene base ether (Ethyleneglycolmonoallylether), containing ehter bond and hydroxyl, is that one not only has wetting ability but also have oil loving fine chemicals.In addition, glycol propylene base ether is also containing polymerizable functional group, and demonstrating higher activity, is a kind of photocuring reactive monomer of good performance.
Along with the development of science and technology and society to the pay attention to day by day of environmental protection and, environmentally friendly photocuring technology is more and more concerned, has been widely used in the fields such as coating, microelectronics, tackiness agent, ink.Reactive monomer conventional in current photo-curing material is based on acrylate polyfunctional monomer, but the shortcomings such as its flash-point is low, viscosity is high, volatility is large, toxicity is large, irritant gas is hidden, and many acrylate polyfunctional monomers are carcinogenic substance, bring many problem of environmental pollutions.Therefore develop new reactive monomer and study corresponding catalytic reaction process highly significant.
Glycol propylene base ether obtains under alkaline catalysts effect primarily of vinylcarbinol and oxyethane.The alkaline catalysts generally used at present has potassium hydroxide, sodium hydroxide etc., there is the problems such as poor selectivity, product are not easily separated, product is painted.Need badly exploitation easily separated, corrode little, pollute few catalyzer and production technique, meet industrial demand.
Summary of the invention
The object of the invention is to develop a kind of catalyzed by solid base system, provide a kind of catalyzer and product separation is easy, little to equipment corrosion, the method for the synthesizing glycol propenyl ether of economical in reaction, cleanliness without any pollution.
The object of the present invention is achieved like this:
The method of solid base catalyst catalytically synthesizing glycol propenyl ether, with vinylcarbinol and oxyethane for raw material, loading type KF/Al
2o
3solid alkali is catalyzer, oxyethane ring-opening reaction synthesizing glycol propenyl ether.
Wherein said reaction molar ratio is: vinylcarbinol: oxyethane=2.0 ~ 6.0:1 (mol), and the optimum mol ratio that feeds intake is 5:1(mol).
Wherein said catalyst quality per-cent consumption is 0.5 ~ 3.0% of reactant vinylcarbinol and oxyethane total mass, and optimum catalyst quality per-cent consumption is 1.5% of reactant vinylcarbinol and oxyethane quality.
Wherein said temperature of reaction is 90 ~ 130 DEG C, and suitable temperature of reaction is 100 DEG C.
The catalyzer that the present invention uses is loading type KF/Al
2o
3solid base catalyst, prepares: in accordance with the following methods by carrier A l
2o
3as for 200 DEG C of activation 3h in retort furnace, KF is dissolved in dehydrated alcohol, adds the Al after activation
2o
3carrier, wherein KF and Al
2o
3mass ratio be 3:7, add PEG-4000, wherein PEG-4000 accounts for KF and Al
2o
3stir 4h at 5%, 60 DEG C of total mass, be heated to 105 DEG C and boil off second alcohol and water, vacuum-drying 12h at 105 DEG C, be placed in retort furnace roasting 6h at a certain temperature, obtain loading type KF/Al
2o
3solid catalyst.
Getting final product and product separation through filtering after the reaction of this solid base catalyst, realizing recycling, little to equipment corrosion, environmentally safe.
Advantage of the present invention is: adopt loading type KF/Al
2o
3solid base catalyst, does not dissolve in reaction process, has reacted rear filtration and separable, reduces energy consumption.Oxyethane transformation efficiency is high, can up to 98.64%.Catalyst activity is high and can reuse.
Embodiment
By following instance, the invention will be further described, but not thereby limiting the invention.
In embodiment, after reaction, the concentration gas chromatograph of each material carries out quantitative analysis.Adopt GC9790 type gas chromatograph, split stream sampling, is furnished with temperature programming parts, flame ionization ditector.Capillary chromatograph is SE-54(methyl polysiloxane) type 30m × 0.32mm × 0.45 μm.
In embodiment, the transformation efficiency of oxyethane obtains by following formulae discovery:
The catalyzer used in embodiments all below the present invention is loading type KF/Al
2o
3catalyzed by solid base, its preparation method is: by carrier A l
2o
3as for 200 DEG C of activation 3h in retort furnace, 30gKF is dissolved in 200mL dehydrated alcohol, adds the Al after 70g activation
2o
3carrier, i.e. KF and Al
2o
3mass ratio be 3:7, add 5g PEG-4000, at 60 DEG C, stir 4h, be heated to 105 DEG C and boil off second alcohol and water, vacuum-drying 12h at 105 DEG C, be placed in retort furnace roasting 6h at a certain temperature, obtain loading type KF/Al
2o
3solid catalyst.
Embodiment 1
It is in the reactor of 2L that 191.4g vinylcarbinol and 3.96g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 72.6g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=2.0:1 (mol).Oxyethane transformation efficiency is 79.78%, and glycol propylene base ether productive rate is 63.44%.
Embodiment 2
It is in the reactor of 2L that 191.4g vinylcarbinol and 3.96g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=3.0:1 (mol).Oxyethane transformation efficiency is 87.83%, and glycol propylene base ether productive rate is 70.85%.
Embodiment 3
It is in the reactor of 2L that 255.2g vinylcarbinol and 4.55g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=4.0:1 (mol).Oxyethane transformation efficiency is 93.23%, and glycol propylene base ether productive rate is 75.83%.
Embodiment 4
It is in the reactor of 2L that 319g vinylcarbinol and 5.51g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=5.0:1 (mol), and catalyst levels is 1.5%.Oxyethane transformation efficiency is 97.35%, and glycol propylene base ether productive rate is 80.32%.
Embodiment 5
It is in the reactor of 2L that 382.8g vinylcarbinol and 6.47g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=6.0:1 (mol).Oxyethane transformation efficiency is 98.64%, and glycol propylene base ether productive rate is 81.55%.
Embodiment 6
It is in the reactor of 2L that 319g vinylcarbinol and 1.84g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said catalysts consumption is 0.5%.Oxyethane transformation efficiency is 84.89%, and glycol propylene base ether productive rate is 73.19%.
Embodiment 7
It is in the reactor of 2L that 319g vinylcarbinol and 3.67g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said catalysts consumption is 1.0%.Oxyethane transformation efficiency is 89.20%, and glycol propylene base ether productive rate is 75.97%.
Embodiment 8
It is in the reactor of 2L that 319g vinylcarbinol and 7.35g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said catalysts consumption is 2.0%.Oxyethane transformation efficiency is 95.69%, and glycol propylene base ether productive rate is 79.89%.
Embodiment 9
It is in the reactor of 2L that 319g vinylcarbinol and 11.02g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, temperature of reaction is constant in 100 DEG C, and wherein said catalysts consumption is 3.0%.Oxyethane transformation efficiency is 94.35%, and glycol propylene base ether productive rate is 79.10%.
Embodiment 10
It is in the reactor of 2L that 319g vinylcarbinol and 5.51g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 90 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, and wherein said temperature of reaction is constant in 90 DEG C.Oxyethane transformation efficiency is 73.92%, and glycol propylene base ether productive rate is 64.51%.
Embodiment 11
It is in the reactor of 2L that 319g vinylcarbinol and 5.51g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 110 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, and wherein said temperature of reaction is constant in 110 DEG C.Oxyethane transformation efficiency is 95.94%, and glycol propylene base ether productive rate is 79.08%.
Embodiment 12
It is in the reactor of 2L that 319g vinylcarbinol and 5.51g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 120 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, and wherein said temperature of reaction is constant in 120 DEG C.Oxyethane transformation efficiency is 94.37%, and glycol propylene base ether productive rate is 77.51%.
Embodiment 13
It is in the reactor of 2L that 319g vinylcarbinol and 5.51g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 130 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, and wherein said temperature of reaction is constant in 130 DEG C.Oxyethane transformation efficiency is 93.23%, and glycol propylene base ether productive rate is 76.03%.
Claims (1)
1. the method for solid base catalyst catalytically synthesizing glycol propenyl ether, it is characterized in that carrying out according to following step: it is in the reactor of 2L that 382.8g vinylcarbinol and 6.47g catalyzer are joined volume, airtight rear stirring, intensification, when temperature reaches 100 DEG C, continue in reactor, import oxyethane 48.4g, reacting kettle inner pressure is 0.2 ~ 0.4MPa, and temperature of reaction is constant in 100 DEG C, and wherein said reaction molar ratio is: vinylcarbinol: oxyethane=6.0:1 (mol); Oxyethane transformation efficiency is 98.64%, and glycol propylene base ether productive rate is 81.55%;
Wherein said alkaline catalysts, prepares: in accordance with the following methods by carrier A l
2o
3as for 200 DEG C of activation 3h in retort furnace, 30gKF is dissolved in 200mL dehydrated alcohol, adds the Al after 70g activation
2o
3carrier, i.e. KF and Al
2o
3mass ratio be 3:7, add 5g PEG-4000, at 60 DEG C, stir 4h, be heated to 105 DEG C and boil off second alcohol and water, vacuum-drying 12h at 105 DEG C, be placed in retort furnace roasting 6h at a certain temperature, obtain loading type KF/Al
2o
3solid catalyst.
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| CN103435455B (en) * | 2013-08-23 | 2015-04-29 | 扬州晨化新材料股份有限公司 | Preparation method of ethylene glycol allyl ether |
| CN103524343B (en) * | 2013-09-27 | 2015-04-08 | 常州大学 | Method for synthesizing hydroxy-propyl acrylate |
| CN112645831B (en) * | 2020-12-14 | 2022-12-13 | 浙江鑫甬生物化工股份有限公司 | Synthesis and crystallization method of high-purity N-hydroxymethyl acrylamide |
| CN113061243B (en) * | 2021-03-30 | 2022-07-05 | 浙江皇马科技股份有限公司 | Preparation method of allyl alcohol polyoxypropylene ether |
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| CN102795973A (en) * | 2012-08-16 | 2012-11-28 | 常州大学 | Synthetic method of ethylene glycol monoallyl ether |
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|---|
| 固体碱催化剂KF/Al2O3催化合成乙二醇丁醚;郭登峰等;《南京理工大学学报（自然科学版）》;20110228;第35卷(第1期);第122-126页 * |
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