CN103012079B - The method of solid base catalyst catalytically synthesizing glycol propenyl ether - Google Patents

Abstract

The invention discloses a method for catalyzing and synthesizing ethylene glycol propenyl ether with a solid base catalyst, and belongs to the technical field of fine chemicals. Propyl alcohol and ethylene oxide are used as raw materials, and under the action of the supported solid base catalyst KF/Al ₂ O ₃ , ethylene oxide is ring-opened to synthesize ethylene glycol propenyl ether. The supported KF/Al ₂ O _The mass percentage consumption of the catalyst is 0.5%～3.0% of the total mass of the reactant; the reaction molar ratio of the preparation of ethylene glycol propenyl ether is: propenyl alcohol: ethylene oxide=2.0～6.0:1; The temperature is 90~130°C. The advantages of the present invention are: using the supported KF/Al ₂ O ₃ catalyst to synthesize ethylene glycol propenyl ether, which overcomes the shortcomings of traditional homogeneous catalyst product separation difficulties and easy coloring of the product, and the process has no corrosion to equipment and is environmentally friendly. Pollution, low energy and material consumption, catalyst can be reused.

Description

The method for catalyzed synthesis of ethylene glycol propenyl ether by solid base catalyst

technical field

The invention relates to the synthesis of ethylene glycol propenyl ether, which uses propylene alcohol and ethylene oxide as raw materials, and under the action of the loaded solid base catalyst KF/ _Al2O3 , ethylene _oxide ring-opening reaction synthesizes ethylene glycol propylene base ether. It belongs to the technical field of fine chemicals.

Background technique

Ethylene glycol propenyl ether (Ethyleneglycolmonoallylether) contains ether linkages and hydroxyl groups, and is a fine chemical with both hydrophilic and lipophilic properties. In addition, ethylene glycol propenyl ether also contains polymerizable functional groups, showing high activity, and is a photocurable active monomer with good performance.

With the continuous development of science and technology and the increasing emphasis on environmental protection in society, more and more attention has been paid to environmentally friendly photocuring technology, which has been widely used in coatings, microelectronics, adhesives, inks and other fields. At present, active monomers commonly used in photocurable materials are mainly acrylate polyfunctional monomers, but they have disadvantages such as low flash point, high viscosity, high volatility, high toxicity, and irritating odor, and many acrylate polyfunctional The monomers are all carcinogens, which bring many environmental pollution problems. Therefore, it is meaningful to develop new active monomers and study the corresponding catalytic reaction process.

Ethylene glycol propenyl ether is mainly prepared from propenyl alcohol and ethylene oxide under the action of alkali catalyst. The alkali catalysts commonly used at present include potassium hydroxide, sodium hydroxide, etc., which have problems such as poor selectivity, difficult separation of products, and coloring of products. There is an urgent need to develop catalysts and production processes that are easy to separate, less corrosive, and less polluting to meet the needs of industrial production.

Contents of the invention

The purpose of the present invention is to develop a solid base catalytic system, and provide a method for synthesizing ethylene glycol propenyl ether which is easy to separate the catalyst from the product, less corrosive to equipment, economical in reaction, clean and pollution-free.

The purpose of the present invention is achieved like this:

A method for the synthesis of ethylene glycol propenyl ether catalyzed by a solid base catalyst, using propenyl alcohol and ethylene oxide as raw materials, supported KF/Al ₂ O ₃ solid base as a catalyst, and ethylene oxide ring-opening reaction to synthesize ethylene glycol propenyl ether ether.

The molar ratio of the reaction feed is: propylene alcohol: ethylene oxide = 2.0~6.0:1 (mol), and the most suitable feed molar ratio is 5:1 (mol).

Wherein, the mass percentage dosage of the catalyst is 0.5-3.0% of the total mass of the reactant propenyl alcohol and ethylene oxide, and the most suitable catalyst mass percentage dosage is 1.5% of the mass of the reactant propenyl alcohol and ethylene oxide.

Wherein the reaction temperature is 90-130°C, and the suitable reaction temperature is 100°C.

The catalyst used in the present invention is a supported KF/Al ₂ O ₃ solid base catalyst, which is prepared according to the following method: activate the carrier Al ₂ O ₃ in a muffle furnace at 200°C for 3 hours, dissolve KF in absolute ethanol, and add the activated After the Al ₂ O ₃ carrier, wherein the mass ratio of KF and Al ₂ O ₃ is 3:7, add polyethylene glycol-400, wherein polyethylene glycol-400 accounts for 5% of the total mass of KF and Al ₂ O ₃ , stirred at 60°C for 4h, heated to 105°C to evaporate ethanol and water, dried in vacuum at 105°C for 12h, placed in a muffle furnace and calcined at a certain temperature for 6h to obtain a supported KF/Al ₂ O ₃ solid catalyst.

After the reaction, the solid base catalyst can be separated from the product by filtration, realizes recycling, is less corrosive to equipment, and has no pollution to the environment.

The present invention has the advantages that: the loaded KF/Al ₂ O ₃ solid base catalyst is used, it does not dissolve during the reaction, and can be separated by filtration after the reaction is completed, thereby reducing energy consumption. The conversion rate of ethylene oxide is high, which can be as high as 98.64%. The catalyst has high activity and can be reused.

detailed description

The present invention is further illustrated by the following examples, but the present invention is not limited thereto.

In the embodiments, the concentration of each substance after the reaction is quantitatively analyzed by gas chromatography. GC9790 type gas chromatograph is adopted, with split flow injection, equipped with a temperature-programmed component, and a hydrogen flame ionization detector. The capillary chromatographic column is SE-54 (methylpolysiloxane) type 30m×0.32mm×0.45μm.

In an embodiment, the conversion rate of oxyethane is calculated by the following formula:

The catalyst used in all the following examples of the present invention is supported KF/Al ₂ O ₃ solid base catalyst, and its preparation method is: activate the carrier Al ₂ O ₃ in a muffle furnace at 200°C for 3 hours, dissolve 30g of KF in 200mL In absolute ethanol, add 70g of activated Al ₂ O ₃ carrier, that is, the mass ratio of KF to Al ₂ O ₃ is 3:7, add 5g of polyethylene glycol-400, stir at 60°C for 4h, and heat to 105°C Ethanol and water were evaporated, vacuum-dried at 105°C for 12 hours, placed in a muffle furnace and calcined at a certain temperature for 6 hours to obtain a supported KF/Al ₂ O ₃ solid catalyst.

Example 1

Add 191.4g of propylene alcohol and 3.96g of catalyst into a reaction kettle with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 72.6g of ethylene oxide into the reaction kettle, and the pressure in the reaction kettle is 0.2 ~0.4MPa, the reaction temperature is constant at 100°C, and the molar ratio of the reaction feed is: propenyl alcohol: ethylene oxide = 2.0:1 (mol). The conversion rate of ethylene oxide was 79.78%, and the yield of ethylene glycol propenyl ether was 63.44%.

Example 2

Add 191.4g of propylene alcohol and 3.96g of catalyst into a reaction kettle with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reaction kettle, and the pressure in the reaction kettle is 0.2 ~0.4MPa, the reaction temperature is constant at 100°C, wherein the reaction feed molar ratio is: propenyl alcohol: ethylene oxide = 3.0:1 (mol). The conversion rate of ethylene oxide was 87.83%, and the yield of ethylene glycol propenyl ether was 70.85%.

Example 3

Add 255.2g of propylene alcohol and 4.55g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2 ~0.4MPa, the reaction temperature is constant at 100°C, wherein the reaction feed molar ratio is: propenyl alcohol: ethylene oxide = 4.0:1 (mol). The conversion rate of ethylene oxide was 93.23%, and the yield of ethylene glycol propenyl ether was 75.83%.

Example 4

Add 319g of propylene alcohol and 5.51g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, the reaction temperature is constant at 100°C, the molar ratio of the reaction feed is: propenol: ethylene oxide = 5.0:1 (mol), and the catalyst dosage is 1.5%. The conversion rate of ethylene oxide was 97.35%, and the yield of ethylene glycol propenyl ether was 80.32%.

Example 5

Add 382.8g of propylene alcohol and 6.47g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2 ~0.4MPa, the reaction temperature is constant at 100°C, and the molar ratio of the reaction feed is: propenyl alcohol: ethylene oxide = 6.0:1 (mol). The conversion rate of ethylene oxide was 98.64%, and the yield of ethylene glycol propenyl ether was 81.55%.

Example 6

Add 319g of propylene alcohol and 1.84g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, the reaction temperature is constant at 100°C, and the reaction catalyst dosage is 0.5%. The conversion rate of ethylene oxide was 84.89%, and the yield of ethylene glycol propenyl ether was 73.19%.

Example 7

Add 319g of propylene alcohol and 3.67g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, the reaction temperature is constant at 100°C, and the reaction catalyst dosage is 1.0%. The conversion rate of ethylene oxide was 89.20%, and the yield of ethylene glycol propenyl ether was 75.97%.

Example 8

Add 319g of propylene alcohol and 7.35g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, the reaction temperature is constant at 100°C, and the reaction catalyst dosage is 2.0%. The conversion rate of ethylene oxide was 95.69%, and the yield of ethylene glycol propenyl ether was 79.89%.

Example 9

Add 319g of propylene alcohol and 11.02g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 100°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, the reaction temperature is constant at 100°C, and the reaction catalyst dosage is 3.0%. The conversion of ethylene oxide was 94.35%, and the yield of ethylene glycol propenyl ether was 79.10%.

Example 10

Add 319g of propylene alcohol and 5.51g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 90°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, wherein the reaction temperature is kept constant at 90°C. The conversion rate of ethylene oxide was 73.92%, and the yield of ethylene glycol propenyl ether was 64.51%.

Example 11

Add 319g of propylene alcohol and 5.51g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 110°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, wherein the reaction temperature is kept constant at 110°C. The conversion rate of ethylene oxide was 95.94%, and the yield of ethylene glycol propenyl ether was 79.08%.

Example 12

Add 319g of propylene alcohol and 5.51g of catalyst into a reaction kettle with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 120°C, continue to introduce 48.4g of ethylene oxide into the reaction kettle, and the pressure in the reaction kettle is 0.2~ 0.4MPa, wherein the reaction temperature is kept constant at 120°C. The conversion rate of ethylene oxide was 94.37%, and the yield of ethylene glycol propenyl ether was 77.51%.

Example 13

Add 319g of propylene alcohol and 5.51g of catalyst into a reactor with a volume of 2L, seal it, stir, and raise the temperature. When the temperature reaches 130°C, continue to introduce 48.4g of ethylene oxide into the reactor, and the pressure inside the reactor is 0.2~ 0.4MPa, wherein the reaction temperature is kept constant at 130°C. The conversion rate of ethylene oxide was 93.23%, and the yield of ethylene glycol propenyl ether was 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.