KR101149950B1 - Manufacturing method of polyether - Google Patents

Abstract

The present invention relates to a method for preparing a polyether, comprising: a raw material addition step of adding a raw material consisting of 95 to 135 parts by weight of a starting material having at least one active hydrogen and 2.0 to 3.5 parts by weight of a catalyst to a nitrogen-substituted reactor, The first stirring step of stirring with a stirrer provided in the reactor, the water removal step of removing the water in a vacuum pump in the reactor generated through the first stirring step described above, the alkyl stirred in a high shear in-line mixer in the reactor from which water is removed A ring-opening reaction step of starting the ring-opening reaction of the reactants by adding 475 to 670 parts by weight of ethylene oxide, a second stirring step of stirring the reactants in the reactor to which the alkylene oxide is added, and removing the monomers contained in the reactants after the second stirring step. It comprises a monomer removal step and a filtration step of filtering the reactants from which the monomer is removed.

Polyether, Catalyst, Ring Opening Reaction, Alkylene Oxide, Reactor, Magnesol, Filter Aid, Heat Exchanger

Description

Manufacturing Method of Polyether {MANUFACTURING METHOD OF POLYETHER}

The present invention relates to a method for producing a polyether, comprising a raw material addition step, a first stirring step, a water removal step, a ring-opening reaction step, a second stirring step, a monomer removal step and a filtration step.

The present invention relates to a method for producing a polyether, comprising a raw material addition step, a first stirring step, a water removal step, a ring-opening reaction step, a second stirring step, a monomer removal step and a filtration step.

Polyethers are polyoxypropylene glycols, polyoxyethylene glycols, polyoxybutylenes, polyepoxys and polytetras prepared from ring-opening reactions of starting materials under catalysts having ring-structured monomers such as cyclooxirane and epoxy. Hydrofuran and the like.

The above-mentioned components are used in various fields such as automobile materials such as automobile seats, heat insulating materials, thermal insulation materials and flooring materials, and building materials.

However, the polyether polyol prepared by the method of preparing a polyether used in the prior art has an unsatisfactory problem in that an unsaturated polyol is produced during epoxide polymerization, and a polyol having a molecular weight of 6000 or more is inadequate.

In addition, the basic catalyst based on the amine component has a problem that odor occurs due to the remaining catalyst component after the reaction, and polyol prepared by using a metal catalyst has a problem that a large amount of the metal catalyst is used because of low reactivity between the metal catalyst and propylene oxide. there was.

An object of the present invention is to provide a polyether having a high reaction efficiency and a high yield of polyether by using a reactor equipped with a heat exchanger for converting a gaseous monomer into a liquid phase in a reactor during polyether polymerization and a high shear in-line mixer having high agitation efficiency. It is to provide a manufacturing method.

An object of the present invention is to add a raw material consisting of 95 to 135 parts by weight of a starting material having at least one active hydrogen and 2.0 to 3.5 parts by weight of a catalyst to a nitrogen-substituted reactor, stirring the raw material in the reactor with a stirrer provided in the reactor In the first stirring step, the water removal step of removing the water in the reactor generated by the first stirring step with a vacuum pump, 475 to 670 parts by weight of the alkylene oxide stirred with a high shear in-line mixer in the reactor is removed The ring-opening reaction step of starting the ring-opening reaction of the reactant, the second stirring step of stirring the reactant in the reactor, the alkylene oxide is added, the monomer removal step of removing the monomer contained in the reactant after the second stirring step and the monomer is removed Preparation of a polyether characterized in that it comprises a filtration step of filtering the reactants By providing a method.

According to a preferred feature of the invention, the starting material consists of propylene glycol, ethylene glycol, glycerin, methyl glucoside, trimethylolpropane, pentaerythritol, butylene glycol, pentylene glycol, ethylenediamine, toluenediamine, glucose and sorbitol It is assumed to include one selected from the group.

According to a more preferred feature of the invention, the alkylene oxide is epibromohydrin, ethylene oxide, propylene oxide, butylene oxide, hexane oxide, alkylene oxide, 3,3-dimethyloxetane, tetrahydrofuran and glycy It is assumed to include one selected from the group consisting of diethers.

According to a further preferred feature of the invention, the catalyst comprises a basic catalyst or a metallic catalyst.

According to a further preferred feature of the invention, the basic catalyst comprises one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium oxide, trimethylamine and triethylamine, the metallic catalyst AlCl ₃ , ZnCl ₂ And FeCl ₃ , BF ₃ , BCl ₃ , BeCl ₂ , FeBr ₃ and SnCl ₄ .

According to a further preferred feature of the invention, the upper side in the reactor is to be provided with a heat exchanger for phase conversion of the reactant vaporized in the gas phase to the liquid phase.

According to a further preferred feature of the invention, the monomer removal step is to remove the unreacted monomer in the reactor by using a vacuum pump provided in the reactor.

According to a further preferred feature of the present invention, the filtration step is to filter the filter after stirring and adding 0.05 to 0.1 parts by weight of magnesol and 0.05 to 0.1 parts by weight of the filter aid to the reaction product from which the monomer is removed.

Polyether production method according to the present invention using a reactor equipped with a heat exchanger for converting the monomer of the gas phase into a liquid phase in the reactor during the polyether polymerization and a high shear in-line mixer with high agitation efficiency and yield of polyether Exhibits an excellent effect of improving.

In the following, preferred embodiments of the present invention and the physical properties of each component will be described in detail, which is intended to explain in detail enough to be able to easily carry out the invention by one of ordinary skill in the art, This does not mean that the technical spirit and scope of the present invention is limited.

Method for producing a polyether according to the present invention is a raw material addition step (S101) for adding a raw material consisting of 95 to 135 parts by weight of the starting material having at least one active hydrogen and 2.0 to 3.5 parts by weight of the catalyst to the nitrogen-substituted reactor (10), Vacuuming the water in the reactor 10 generated through the first stirring step (S103), the first stirring step (S103) described above to agitate the raw material in the reactor 10 with the stirrer 11 provided in the reactor (10) A ring opening reaction for starting the ring-opening reaction of the reactant by adding 475 to 670 parts by weight of the alkylene oxide stirred by the high shear inline mixer 30 into the reactor 10 in which the water is removed by the pump (S105) and the water is removed. Step (S107), the monomer stirring step of removing the monomer contained in the reactant after the second stirring step (S109), the above-mentioned second stirring step (S109) stirring the reactant in the reactor 10, the alkylene oxide is added (S111) ) And half of monomer removed It comprises a filtering step (S113) for filtering the water.

The above-described raw material addition step (S101) is a step of adding a raw material consisting of 95 to 135 parts by weight of a starting material having at least one active hydrogen and 2.0 to 3.5 parts by weight of a catalyst to the nitrogen-substituted reactor 10, starting with active hydrogen The material comprises one selected from the group consisting of propylene glycol, ethylene glycol, glycerin, methylglucoside, trimethylolpropane, pentaerythritol, butylene glycol, pentylene glycol, ethylenediamine, toluenediamine, glucose and sorbitol.

The aforementioned catalyst is used as a basic catalyst or a metallic catalyst, the basic catalyst comprising one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium oxide, trimethylamine and triethylamine, the metallic catalyst is AlCl ₃ , ZnCl ₂ , FeCl ₃ , BF ₃ , BCl ₃ , BeCl ₂ , FeBr ₃ and SnCl _{4 It} comprises one selected from the group consisting of.

When nitrogen is substituted for the reactor 10 described above, oxygen is removed in the reactor 10, thereby improving reaction efficiency.

The first stirring step (S103) is a step of stirring the raw material with the stirrer 11 provided in the reactor 10, the step of improving the reaction efficiency of the starting material and the catalyst having one or more active hydrogen.

The above-described water removal step (S105) is a step of removing the water in the reactor 10 generated by the above-described first stirring step (S103) with a vacuum pump, the reactant from which the water is removed in the reactor 10 is a reactor ( It is circulated to the outside through the external circulation pump 20 provided in 10) to maintain a constant temperature through the process to be put back into the reactor.

The ring-opening reaction step (S107) described above is a step of initiating the ring-opening reaction by adding 475 to 670 parts by weight of the stirred alkylene oxide to the high shear in-line mixer 30 in the reactor 10 in which water is removed. After adding the alkylene oxide so that the pressure is 0.1 to 1.0kg / cm ^{2 in} the reactor 10 by using the 30, and the temperature rises in the reactor 10 through the ring-opening reaction of the alkylene oxide, high shear inline The amount of alkylene oxide is further added to the reactor 10 using the blender 30 within a range in which the pressure is not more than 5 kg / cm ² .

By operating the high shear in-line mixer 30 while maintaining the pressure in the reactor 10 not to be more than 5kg / cm ² Injecting the alkylene oxide, when the reaction temperature reaches 150 ℃, the external circulating pump 20 The reactant is externally circulated to prevent the temperature of the reactant in the reactor 10 from exceeding 150 ° C.

If the reaction temperature in the reactor 10 is less than 90 ℃, the reaction rate is low, the productivity is lowered, when the reaction temperature exceeds 150 ℃ reaction rate is increased, but the product is pyrolyzed or by-products generated by the side reaction.

The alkylene oxide described above comprises one selected from the group consisting of epibromohydrin, ethylene oxide, propylene oxide, butylene oxide, hexane oxide, 3,3-dimethyloxetane, tetrahydrofuran and glycidyl ether. .

At this time, the upper side in the reactor 10 is provided with a heat exchanger 12 to maintain the temperature in the reactor 10 to 90 to 150 ℃ in order to phase-change the reactant evaporated in the gas phase into a liquid phase to improve the reaction efficiency Do it.

The aforementioned second stirring step (S109) is a step of stirring the reactants in the reactor 10 into which the alkylene oxide is added, and agitating the above-mentioned reactants through the stirrer 11 provided in the reactor 10 to increase the reaction efficiency. Step.

The above-described monomer removal step (S111) is a step of removing the monomer contained in the reactants passed through the second stirring step (S109) described above, by using the vacuum pump provided in the reactor 10 to remove the unreacted monomer in the reactor. do.

When removing the unreacted monomer using a vacuum pump, while maintaining the inside of the reactor 10 in a vacuum state, the monomer is removed for 25 to 35 minutes at a temperature of 110 to 115 ℃.

The above-described filtration step (S113) is a step of filtering the reactant from which the monomer has been removed. After adding and stirring, the filter is filtered.

The addition of the above-mentioned magnesol and filter aid removes the catalyst remaining in the reactant, and the polyether is obtained by filtering the reactant mixed with the magnesol and filter aid with a filter.

Hereinafter, the production method, yield (yield) and reaction rate of the polyether according to the present invention will be described with reference to Examples.

≪ Example 1 >

953 g of glycerin and 23.7 g of water-soluble potassium hydroxide having a 48% concentration were added to an 8 L high-pressure reactor, to prepare a mixture, the mixture was heated to 112 DEG C while stirring the mixture, and the water was removed under a vacuum pump to remove moisture. Propylene oxide is added so that the pressure in the dissolution reactor is 0.5 kg / cm ² in the high shear inline mixer, and when the temperature starts to rise in the reactor, the pressure in the reactor is maintained at 2.0 kg / cm ² using the high shear inline mixer. Propylene oxide is added as much as possible, so that the total amount of propylene oxide added is 4747 g. The reaction temperature is maintained at 112 ° C. and the reactor pressure is 2.0 kg / cm ² , and the reactants are stirred. When the reaction is complete, a vacuum pump is used. By removing the unreacted monomer contained in the reactants for 30 minutes at a temperature of 112 ℃ in a vacuum state, the reaction is removed unreacted monomer 430 g of magnesol and 430 g of filter aid were added to water, stirred, and filtered with a filter to prepare a polyether.

<Example 2>

Proceed in the same manner as in Example 1, using an 8L high pressure reactor equipped with a heat exchanger on the upper side of the reactor, when the temperature starts to rise in the reactor using a high shear in-line mixer and heat exchanger pressure 2.0kg / cm ^{2 in} the reactor The polyether was prepared by maintaining it as.

<Example 3>

Proceed in the same manner as in Example 2, polyether was prepared by adding 1070 g of glycerin, 26.6 g of water-soluble potassium hydroxide having a concentration of 48%, and 5330 g of propylene oxide.

<Example 4>

Proceed in the same manner as in Example 2, 1204 g of glycerin, 30.0 g of water-soluble potassium hydroxide having a concentration of 48%, and 5996 g of propylene oxide were prepared to prepare a polyether.

Example 5

Proceed in the same manner as in Example 2, 1338 g of glycerin, 33.3 g of water-soluble potassium hydroxide having a concentration of 48%, and 6662 g of propylene oxide were prepared to prepare a polyether.

Comparative Example 1

A mixture was prepared by adding 953 g of glycerin and 23.7 of water-soluble potassium hydroxide having a concentration of 48% to an 8 L high-pressure reactor, heating the temperature of the mixture to 112 ° C. while stirring the mixture, removing water by vacuum pressure and removing water. However, propylene oxide is added so that the pressure in the reactor is 0.5kg / cm ² using an inline mixer, and when the temperature starts to rise in the reactor, propylene oxide is added to maintain the pressure in the reactor at 2.0kg / cm ^2, and the propylene is added. The total input amount of oxide is 4747g, the reaction temperature is maintained at 112 ℃, the reactor pressure is 2.0kg / cm ² while stirring the reactants, when the reaction is terminated using a vacuum pump to a temperature of 112 ℃ Remove the unreacted monomer contained in the reactant for 30 minutes, and 430 g of magnesol and filter aid in the reactant from which the unreacted monomer was removed. 430 g was added, stirred and filtered through a filter to prepare a polyether.

The obtained amounts of the polyethers prepared through Examples 1 to 5 and Comparative Example 1 and the reaction rates of propylene oxide were measured and shown in Table 1 below.

(However, the reaction rate of propylene oxide was measured using a Liqui-flo meter of bronkhorst.)

TABLE 1

As shown in Table 1 above, it can be seen that the method of preparing the polyether according to the present invention has a superior effect on the reaction rate and the obtained amount compared to the conventional production method.

1 is a flow chart showing a method for producing a polyether according to the present invention.

2 is a schematic diagram showing an apparatus for producing a polyether according to the present invention.

*** Description of the main parts of the drawings ***

10; Reactor

11; agitator

12; heat transmitter

20; Circulation pump

30; High shear inline blender

Claims (8)

Adding a raw material comprising 95 to 135 parts by weight of a starting material having at least one active hydrogen and 2.0 to 3.5 parts by weight of a catalyst to a nitrogen-substituted reactor; A first stirring step of stirring the raw materials in the reactor with a stirrer provided in the reactor; A water removal step of removing water with a vacuum pump in the reactor generated through the first stirring step; A ring-opening reaction step of starting the ring-opening reaction of the reactant by adding 475 to 670 parts by weight of the stirred alkylene oxide with a high shear inline mixer in the reactor from which water is removed; A second stirring step of stirring the reactant in the reactor in which the alkylene oxide is added; A monomer removal step of removing the monomer contained in the reactant after the second stirring step; And It comprises a; filtration step of filtering the reactant from which the monomer is removed; The starting material comprises one selected from the group consisting of glycerin, methylglucoside, trimethylolpropane, pentaerythritol, glucose and sorbitol, The monomer removal step is made by removing the unreacted monomer in the reactor using a vacuum pump provided in the reactor, The filtration step is a method for producing a polyether, characterized in that by filtering with a filter after adding and stirring 0.05 to 0.1 parts by weight of the magnesol and 0.05 to 0.1 parts by weight of the filter aid to the monomer is removed. delete The method according to claim 1, The alkylene oxide comprises one selected from the group consisting of epibromohydrin, ethylene oxide, propylene oxide, butylene oxide, hexane oxide, 3,3-dimethyl oxetane, tetrahydrofuran and glycidyl ether Method for producing a polyether, characterized in that. The method according to claim 1, The catalyst is a method of producing a polyether, characterized in that it comprises a basic catalyst or a metallic catalyst. The method of claim 4, The basic catalyst comprises one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium oxide, trimethylamine and triethylamine, and the metallic catalyst is AlCl ₃ , ZnCl ₂ , FeCl ₃ , BF ₃ , BCl ₃ , Method for producing a polyether comprising one selected from the group consisting of BeCl ₂ , FeBr ₃ and SnCl ₄ . The method according to claim 1, The upper side of the reactor is a method for producing a polyether, characterized in that the heat exchanger is provided for the phase conversion of the reactant vaporized in the gas phase to the liquid phase. delete delete

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