Preparation method of glycidyl terminated allyl alcohol polyoxyethylene ether

Abstract

The invention discloses a preparation method of glycidyl terminated allyl alcohol polyoxyethylene ether. The method comprises the following technical steps: 1) adding solid sodium hydroxide, calcium chloride and water into a pressure reaction kettle, fully stirring and dissolving, and then decompressing and dehydrating till being dried; 2) controlling the temperature, inflating nitrogen to the pressure reaction kettle to constant pressure, then, putting a quaternary ammonium salt phase transfer catalyst and an allyl alcohol polyoxyethylene ether into the pressure reaction kettle, vacuumizing and replacing nitrogen, then dropwise adding epoxy chloropropane without air by vacuumization at a low temperature for synthetic reaction, and after dropwise addition, continuously carrying out reaction; and 3) after reaction, filtering to remove salt, neutralizing by phosphoric acid and degassing to recover excessive epoxy chloropropane to obtain a coarse product, and then, refining the coarse product. The product prepared by the method disclosed by the invention has the characteristics of light color and luster, high terminating rate, high double bond protective rate and simplicity in process.

Description

technical field

[0001] The invention belongs to the technical field of chemical industry, and in particular relates to a preparation method of glycidyl-terminated allyl alcohol polyoxyethylene ether. Background technique

[0002] Glycidyl-terminated allyl alcohol polyoxyethylene ether has two functional groups—terminated epoxy group and carbon-carbon double bond. It is an important organic synthesis intermediate in the chemical industry and can be used to modify organic compounds. Silicon, polyurethane and nano self-assembly systems, etc. At present, similar foreign products are not only close to colorless in color, but also have a sealing rate as high as 95%, while domestic products are difficult to match, their color is light yellow to yellow, and the sealing rate is within 90%. So far, there are very few published patents on glycidyl-terminated polyethers.

[0003] There are mainly two kinds of synthetic methods reported in the literature, two-step method and one-step m...

Examples

Embodiment 1

[0033] In this example, 300g H 2 O, 160g NaOH and 48g CaCl 2 Put it into a 2L pressure reactor, raise the temperature to 110°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 5g of P.T.C (tetra-n-butylammonium bromide) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 555g of ECH was passed into the dripping storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 35°C, and ECH was slowly added dropwise. After the dropwise addition, the reaction was continued for 5 hours and the material was discharged. Remove salt by filtration, neutralize with phosphoric acid, recover ECH (about 342.9g) by vacuuming, and add acid clay to refine. The resulting product has a color of 40, a capping rate of 93.2%, and ...

Embodiment 2

[0035] In this example, 300g H 2 O, 120g NaOH and 24g CaCl 2 Put it into a 2L pressure reactor, raise the temperature to 90°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 3g of P.T.C (trioctylmethylammonium chloride) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 740g of ECH was passed into the drip storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 45°C, ECH was slowly added dropwise, and after the end of the dropwise addition, the reaction was continued for 2 hours and the material was discharged. Filter to remove salt, phosphoric acid neutralize, vacuumize to recover ECH (about 530g), add magnesium silicate to refine. The resulting product has a color of 40, a capping rate of 92.8%, an...

Embodiment 3

[0037] In this example, 210g H 2 O, 140g NaOH and 70g CaCl 2Put it into a 2L pressure reactor, raise the temperature to 120°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 4g of P.T.C (tetraethylammonium chloride) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 279g of ECH was passed into the dripping storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 32°C, ECH was slowly added dropwise, and after the end of the dropwise addition, the reaction was continued for 7h and the material was discharged. Remove salt by filtration, neutralize phosphoric acid, recover ECH (about 530g) by vacuuming, and add activated carbon for refining. The resulting product has a color of 40, a capping rate of 92.4%...

technical field

[0001] The invention belongs to the technical field of chemical industry, and in particular relates to a preparation method of glycidyl-terminated allyl alcohol polyoxyethylene ether. Background technique

[0002] Glycidyl-terminated allyl alcohol polyoxyethylene ether has two functional groups—terminated epoxy group and carbon-carbon double bond. It is an important organic synthesis intermediate in the chemical industry and can be used to modify organic compounds. Silicon, polyurethane and nano self-assembly systems, etc. At present, similar foreign products are not only close to colorless in color, but also have a sealing rate as high as 95%, while domestic products are difficult to match, their color is light yellow to yellow, and the sealing rate is within 90%. So far, there are very few published patents on glycidyl-terminated polyethers.

[0003] There are mainly two kinds of synthetic methods reported in the literature, two-step method and one-step m...

Examples

Embodiment 1

[0033] In this example, 300g H 2 O, 160g NaOH and 48g CaCl 2 Put it into a 2L pressure reactor, raise the temperature to 110°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 5g of P.T.C (tetra-n-butylammonium bromide) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 555g of ECH was passed into the dripping storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 35°C, and ECH was slowly added dropwise. After the dropwise addition, the reaction was continued for 5 hours and the material was discharged. Remove salt by filtration, neutralize with phosphoric acid, recover ECH (about 342.9g) by vacuuming, and add acid clay to refine. The resulting product has a color of 40, a capping rate of 93.2%, and ...

Embodiment 2

[0035] In this example, 300g H 2 O, 120g NaOH and 24g CaCl 2 Put it into a 2L pressure reactor, raise the temperature to 90°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 3g of P.T.C (trioctylmethylammonium chloride) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 740g of ECH was passed into the drip storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 45°C, ECH was slowly added dropwise, and after the end of the dropwise addition, the reaction was continued for 2 hours and the material was discharged. Filter to remove salt, phosphoric acid neutralize, vacuumize to recover ECH (about 530g), add magnesium silicate to refine. The resulting product has a color of 40, a capping rate of 92.8%, an...

Embodiment 3

[0037] In this example, 210g H 2 O, 140g NaOH and 70g CaCl 2Put it into a 2L pressure reactor, raise the temperature to 120°C, stir for 0.5h, and then vacuumize and dehydrate to dryness. Fill the kettle with nitrogen to normal pressure, lower the temperature to 25°C, continue to add 4g of P.T.C (tetraethylammonium chloride) and 984g of APEG (average molecular weight: 492g / moL), and replace the nitrogen with vacuum. Then, 279g of ECH was passed into the dripping storage tank, and at the same time, the temperature was lowered to below 25°C, and the nitrogen was replaced by vacuuming. The temperature of the pressure reactor was raised to 32°C, ECH was slowly added dropwise, and after the end of the dropwise addition, the reaction was continued for 7h and the material was discharged. Remove salt by filtration, neutralize phosphoric acid, recover ECH (about 530g) by vacuuming, and add activated carbon for refining. The resulting product has a color of 40, a capping rate of 92.4%...

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