RU2458941C1 - Method of producing oligo-3,3-bis(azidomethyl)oxetane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing oligo-3,3-bis(azidomethyl)oxetane which is used as a hydroxyl-containing compound for producing energy-intensive polyurethane thermoplastic elastomers. The method involves cationic polymerisation of 3,3-bis(chloromethyl)oxetane in methylene chloride at 20-35°C in the presence of 1-10 wt % boron trifluoride etherate and a diatomic alcohol in molar ratio of 1:(5-15) to 3,3-bis(chloromethyl)oxetane. Further, the intermediate oligo-3,3-bis(chloromethyl)oxetane is separated in finely dispersed form, for which at the end of polymerisation, an organic solvent is added to the reaction mass, methylene chloride is evaporated and oligo-3,3-bis(chloromethyl)oxetane is precipitated with water. Sodium azide is then added to the obtained finely dispersed oligo-3,3-bis(chloromethyl)oxetane in a medium of an organic solvent at 90-130°C in the presence of 0.5-3 wt % tetrabutylammonium bromide.

EFFECT: highly efficient method of producing oligo-3,3-bis(azidomethyl)oxetane and high output of the end product.

5 cl, 1 tbl, 7 ex

Description

The invention relates to the field of production of azide-containing oligooxetanediols with a molecular weight of 1000-5000, which are used as hydroxyl-containing compounds to produce energy-intensive polyurethane thermoplastic elastomers.

A known method of producing poly-3,3-bis (azidomethyl) oxetane, comprising the interaction of poly-3,3-bis (chloromethyl) oxetane with sodium azide in a medium of dimethylformamide. To isolate poly-3,3-bis (azidomethyl) oxetane from the reaction mass in a finely divided form, the mixture is exposed to low temperatures from minus 5 ° C to minus 20 ° C for 1.5-2.0 hours, mixed with water at a ratio a solution of the polymer in dimethylformamide and water equal to 1.0: (1.0-2.0) vol. (RU Patent No. 2393175 C2, IPC C08G 65/325, C08G 73/00, C08G 65/1, 2010).

Poly-3,3-bis (azidomethyl) oxetane according to the known method is a high molecular weight product with a molecular weight of more than 50,000 and is not suitable for the production of polyurethane thermoplastic elastomers. To isolate the polymer in finely dispersed form, the use of temperature from minus 5 ° C to minus 20 ° C is required, which increases the energy load of the process. The amount of dimethylformamide taken into the azidation reaction is 5-7 times more than poly-3,3-bis (chloromethyl) oxetane, which leads to an increase in the volume of equipment used and a decrease in the coefficient of useful use.

A known method of producing polymers of 3,3-bis (chloromethyl) oxetane by cationic polymerization in a mixture of liquid sulfur dioxide with hexane or kerosene in the presence of surface-active additives at temperatures from minus 35 ° C to minus 50 ° C (from minus 15 ° C to minus 30 ° C) in the presence of 0.2-7.5 wt.% Catalyst of boron trifluoride. The selection of the polymer in fine form is carried out by adding methanol in an amount of from 5: 1 to 1:20 wt.h. (from 1: 1 to 1: 6 parts by weight) to a solution of 3,3-bis (chloromethyl) oxetane (USA Patent No. 2909492, 1959).

A known method of producing polymers of 3,3-bis (chloromethyl) oxetane by cationic polymerization in liquid sulfur dioxide at a temperature of from 0 ° C to minus 50 ° C (from minus 20 ° C to minus 25 ° C) in the presence of 1-7.5 wt .% catalyst of boron trifluoride. The selection of the polymer in fine form is carried out by adding methanol in an amount of 1.56: 1 wt.h. to 3,3-bis (chloromethyl) oxetane (see USA Patent No. 2722520, 1955).

A disadvantage of the known methods is the use of liquid sulfur dioxide with a boiling point of minus 10.1 ° C as a reaction medium, which requires the use of low temperatures or high pressure for the polymerization of 3,3-bis (chloromethyl) oxetane. This greatly complicates the hardware design during the implementation of the process in production. The use of large quantities of toxic methanol for the precipitation of polymers of 3,3-bis (chloromethyl) oxetane makes the process environmentally hazardous.

Methods for producing low molecular weight oligo-3,3-bis (azidomethyl) oxetane, including the isolation of intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, are not described in the literature.

The objective of the invention is to develop a method for producing high-yield low molecular weight azide-containing oligooxetanediols for polyurethane thermoplastic elastomers, suitable for industrial implementation.

The technical problem is solved by the method of producing oligo-3,3-bis (azidomethyl) oxetane, including cationic polymerization of 3,3-bis (chloromethyl) oxetane in methylene chloride at 20-35 ° C in the presence of boron trifluoride etherate catalyst in an amount of 1-10 wt. % (4-7 wt.%) And 1,4-butanediol in a ratio of 1: (5-15) mol. (1: (6-13 mol.)) To 3,3-bis (chloromethyl) oxetane, isolation of the intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, for which N is added to the reaction mass after polymerization N-dimethylformamide, methylene chloride was evaporated and oligo-3,3-bis (chloromethyl) oxetane was precipitated with water, and the subsequent reaction of oligo-3,3-bis (chloromethyl) oxetane with sodium azide in the presence of N, N-dimethylformamide in the presence of tetrabutylammonium catalyst bromide in an amount of 0.5-3 wt.% (1-2%) at 90-130 ° C (110-125 ° C).

The technical problem is also solved by the method of producing oligo-3,3-bis (azidomethyl) oxetane, including cationic polymerization of 3,3-bis (chloromethyl) oxetane in methylene chloride at 20-35 ° C in the presence of boron trifluoride etherate catalyst in an amount of 1-10 wt.% (4-7 wt.%) and 1,4-butanediol in a ratio of 1: (5-15) mol. (1: (6-13 mol.)) To 3,3-bis (chloromethyl) oxetane, isolation of the intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, for which dimethyl sulfoxide is added to the reaction mass at the end of polymerization, evaporated methylene chloride and precipitated oligo-3,3-bis (chloromethyl) oxetane with water, and the subsequent interaction of oligo-3,3-bis (chloromethyl) oxetane with sodium azide in a medium of dimethyl sulfoxide in the presence of a tetrabutylammonium bromide catalyst in an amount of 0.5-3 wt.% (1-2%) at 90-130 ° C (110-125 ° C).

The technical problem is also solved by the method of producing oligo-3,3-bis (azidomethyl) oxetane, including cationic polymerization of 3,3-bis (chloromethyl) oxetane in methylene chloride at 20-35 ° C in the presence of boron trifluoride etherate catalyst in an amount of 1-10 wt.% (4-7 wt.%) and ethylene glycol in a ratio of 1: (5-15) mol. (1: (6-13 mol.)) To 3,3-bis (chloromethyl) oxetane, isolation of the intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, for which N is added to the reaction mass after polymerization N-dimethylformamide, methylene chloride was evaporated and oligo-3,3-bis (chloromethyl) oxetane was precipitated with water, and the subsequent reaction of oligo-3,3-bis (chloromethyl) oxetane with sodium azide in the presence of N, N-dimethylformamide in the presence of tetrabutylammonium catalyst bromide in an amount of 0.5-3 wt.% (1-2%) at 90-130 ° C (110-125 ° C).

The technical problem is also solved by the method of producing oligo-3,3-bis (azidomethyl) oxetane, including cationic polymerization of 3,3-bis (chloromethyl) oxetane in methylene chloride at 20-35 ° C in the presence of boron trifluoride etherate catalyst in an amount of 1-10 wt.% (4-7 wt.%) and ethylene glycol in a ratio of 1: (5-15) mol. (1: (6-13 mol.)) To 3,3-bis (chloromethyl) oxetane, isolation of the intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, for which dimethyl sulfoxide is added to the reaction mass at the end of polymerization, evaporated methylene chloride and precipitated oligo-3,3-bis (chloromethyl) oxetane with water, and the subsequent interaction of oligo-3,3-bis (chloromethyl) oxetane with sodium azide in a medium of dimethyl sulfoxide in the presence of a tetrabutylammonium bromide catalyst in an amount of 0.5-3 wt.% (1-2%) at 90-130 ° C (110-125 ° C).

The solution to the technical problem allows to obtain the intermediate product oligo-3,3-bis (chloromethyl) oxetane in the form of a fine powder, which makes the process of its unloading from the reactor, washing, loading at the stage of interaction with sodium azide technologically advanced and significantly reduces material losses. The amount of methylene chloride used as a reaction medium decreases 1.7-2.2 times. The yield of the desired oligo-3,3-bis (azidomethyl) oxetane in this case increases from 55-61 to 80-83%.

As a regulator of the molecular weight of the oligomers, 1,4-butanediol and ethylene glycol are used.

As a catalyst for the cationic polymerization of 3,3-bis (chloromethyl) oxetane, boron trifluoride etherate is used. Tetrabutylammonium bromide is used as a catalyst for the azidation reaction.

The invention is illustrated by examples of specific performance.

Example 1

66.3 g of 3,3-bis (chloromethyl) oxetane and 15.4 g of 1,4-butanediol are charged into a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer at 25 ° C with stirring. 198.7 g of 3,3-bis (chloromethyl) oxetane are dissolved in 265 g of methylene chloride and dosed from a dropping funnel into the reaction mass for 2 hours. 38 g of boron trifluoride etherate is fed into the reaction mass by fractional dosing, without allowing heating above 35 ° C. After adding the total amount of catalyst and a solution of 3,3-bis (chloromethyl) oxetane, the reaction mixture was kept at 30-35 ° C for 2 hours. Then, 1060 g of methylene chloride are added to the reaction mass. The resulting solution of oligo-3,3-bis (chloromethyl) oxetane is washed from the catalyst with water, dried from water with calcined magnesium sulfate, methylene chloride is evaporated and a solid waxy substance is obtained, which is discharged from the flask with great losses. The yield of oligo-3,3-bis (chloromethyl) oxetane is 190.7 g (68%).

The oligo-3,3-bis (chloromethyl) oxetane is azidated in a reactor equipped with a stirrer, a jacket, a reflux condenser, a thermometer, in argon at a temperature of 125 ° C. 763 g of dimethylformamide, 190.7 g of oligo-3,3-bis (chloromethyl) oxetane, 208 g of sodium azide, 1.9 g of tetrabutylammonium bromide are charged and loaded at 125 ° C. for 25-30 hours. At the end of the azidation, 381 g of methylene chloride are added to the reaction mass, followed by 763 g of water to dissolve the salts. The reaction mass is divided into two layers. The organic layer was washed with water from the residues of dimethylformamide and salts, methylene chloride was evaporated. Oligo-3,3-bis (azidomethyl) oxetane is evacuated at 5-10 mm Hg. and 80 ° C for 2-3 hours. As a result, the product obtained is a viscous liquid from dark yellow to brown in color, which, when cooled, is structured into an ointment-like substance. The content of hydroxyl groups of 1.3 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 186.5 g (61%).

Example 2

66.3 g of 3,3-bis (chloromethyl) oxetane and 15.4 g of 1,4-butanediol are charged into a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer at 25 ° C with stirring. 198.7 g of 3,3-bis (chloromethyl) oxetane are dissolved in 265 g of methylene chloride and dosed from a dropping funnel into the reaction mass for 2 hours. 38 g of boron trifluoride etherate is fed into the reaction mass by fractional dosing, without allowing heating above 35 ° C. After adding the total amount of catalyst and a solution of 3,3-bis (chloromethyl) oxetane, the reaction mixture was kept at 30-35 ° C for 2 hours. Then, 265 g of dimethylformamide is added to the reaction mass with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 30-35 ° С and 795 g of water are added. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. A suspension of oligo-3,3-bis (chloromethyl) oxetane is squeezed from the water-dimethylformamide mixture and washed with water in a filter centrifuge. The resulting oligomer is a fine powder from white to cream color. After drying to a residual moisture of 0.1-0.2%, the yield of oligo-3,3-bis (chloromethyl) oxetane is 252 g (90%).

The oligo-3,3-bis (chloromethyl) oxetane is azidated in a reactor equipped with a stirrer, a jacket, a reflux condenser, a thermometer, in argon at a temperature of 125 ° C. Download 1000 g of dimethylformamide, 252 g of oligo-3,3-bis (chloromethyl) oxetane, 274.7 g of sodium azide, 2.5 g of tetrabutylammonium bromide and stirred at 125 ° C for 25-30 hours. At the end of the azidation, 500 g of methylene chloride are added to the reaction mass, followed by 1000 g of water to dissolve the salts. The reaction mass is divided into two layers. The organic layer was washed with water from the residues of dimethylformamide and salts, methylene chloride was evaporated. Oligo-3,3-bis (azidomethyl) oxetane is evacuated at 5-10 mm Hg. and 80 ° C for 2-3 hours. As a result, the product obtained is a viscous liquid from dark yellow to brown in color, which, when cooled, is structured into an ointment-like substance. The content of hydroxyl groups of 1.46 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 253.8 g (83%).

Example 3

The method is carried out analogously to example 2 with the only difference that after the completion of the polymerization of 3,3-bis (chloromethyl) oxetane, 265 g of dimethyl sulfoxide are added to the reaction mass with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 30-35 ° C and 795 is added g of water. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. The oligonization of oligo-3,3-bis (chloromethyl) oxetane is carried out analogously to example 2 with the only difference that 1000 g of dimethyl sulfoxide is used as the reaction medium. The content of hydroxyl groups of 1.35 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 249 g (81.5%).

Example 4

In a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 28 g of 3,3-bis (chloromethyl) oxetane and 7.5 g of ethylene glycol are loaded at 25 ° C with stirring. 84 g of 3,3-bis (chloromethyl) oxetane are dissolved in 224 g of methylene chloride and dosed from a dropping funnel into the reaction mass for 2 hours. 16.1 g of boron trifluoride etherate are fed into the reaction mass by fractional dosing, preventing heating above 35 ° C. After adding the total amount of catalyst and a solution of 3,3-bis (chloromethyl) oxetane, the reaction mixture was kept at 30-35 ° C for 2 hours. Then, 112 g of dimethylformamide is added to the reaction mass with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 5-10 ° C and 336 g of water are added. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. A suspension of oligo-3,3-bis (chloromethyl) oxetane is squeezed from the water-dimethylformamide mixture and washed with water in a filter centrifuge. The resulting oligomer is a fine powder from white to cream color. After drying to a residual moisture of 0.1-0.2%, the yield of oligo-3,3-bis (chloromethyl) oxetane is 102.8 g (86%).

The oligomerization of oligo-3,3-bis (chloromethyl) oxetane is carried out in a reactor equipped with a stirrer, a jacket, a reflux condenser, a thermometer, in argon at a temperature of 115 ° C. 411 g of dimethylformamide, 102.8 g of oligo-3,3-bis (chloromethyl) oxetane, 112 g of sodium azide, 1 g of tetrabutylammonium bromide are charged and loaded at 125 ° C. for 25-30 hours. At the end of the azidation, 205.5 g of methylene chloride are added to the reaction mass, followed by 411 g of water to dissolve the salts. The reaction mass is divided into two layers. The organic layer was washed with water from the residues of dimethylformamide and salts, methylene chloride was evaporated. Oligo-3,3-bis (azidomethyl) oxetane is evacuated at 5-10 mm Hg. and 80 ° C for 2-3 hours. As a result, the resulting product is a viscous liquid from dark yellow to brown. The content of hydroxyl groups of 2.4 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 104 g (80%).

Example 5

The method is carried out analogously to example 4 with the only difference that after the polymerization of 3,3-bis (chloromethyl) oxetane is added to the reaction mass, 112 g of dimethyl sulfoxide are added with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 5-10 ° C and 336 are added g of water. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. The oligomerization of oligo-3,3-bis (chloromethyl) oxetane is carried out analogously to example 2 with the only difference that 411 g of dimethyl sulfoxide is used as the reaction medium. The content of hydroxyl groups of 2.6 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 106 g (82%).

Example 6

In a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 75 g of 3,3-bis (chloromethyl) oxetane and 13.4 g of 1,4-butanediol are charged with stirring. 225 g of 3,3-bis (chloromethyl) oxetane are dissolved in 450 g of methylene chloride and dosed from a dropping funnel into the reaction mass for 3 hours. 43 g of boron trifluoride etherate is fed into the reaction mass by fractional dosing, without allowing heating above 35 ° C. After adding the total amount of catalyst and a solution of 3,3-bis (chloromethyl) oxetane, the reaction mixture was kept at 30-35 ° C for 2 hours. Then, 300 g of dimethylformamide are added to the reaction mass with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 30-35 ° С and 900 g of water are added. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. A suspension of oligo-3,3-bis (chloromethyl) oxetane is squeezed from the water-dimethylformamide mixture and washed with water in a filter centrifuge. The resulting oligomer is a fine powder from white to cream color. After drying to a residual moisture of 0.1-0.2%, the yield of oligo-3,3-bis (chloromethyl) oxetane is 268 g (85.5%).

The oligo-3,3-bis (chloromethyl) oxetane is azidated in a reactor equipped with a stirrer, a jacket, a reflux condenser, a thermometer, in argon at a temperature of 125 ° C. 1072 g of dimethylformamide, 268 g of oligo-3,3-bis (chloromethyl) oxetane, 292 g of sodium azide, 4 g of tetrabutylammonium bromide are charged and stirred at 125 ° C. for 25-30 hours. At the end of the azidation, 536 g of methylene chloride are added to the reaction mass, followed by 1072 g of water to dissolve the salts. The reaction mass is divided into two layers. The organic layer was washed with water from the residues of dimethylformamide and salts, methylene chloride was evaporated. Oligo-3,3-bis (azidomethyl) oxetane is evacuated at 5-10 mm Hg. and 80 ° C for 2-3 hours. As a result, the resulting product is a dark yellow to brown viscous liquid, which, upon cooling, is structured into a solid paraffin-like substance. The content of hydroxyl groups of 1.0 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 282.6 g (82.7%).

Example 7

The method is carried out analogously to example 6 with the only difference that after the polymerization is completed, 300 g of dimethyl sulfoxide are added to the reaction mass with stirring, methylene chloride is evaporated, the reaction mass is cooled to a temperature of 30-35 ° C and 900 g of water are added. The release of oligo-3,3-bis (chloromethyl) oxetane occurs in the form of a fine powder. The oligation of oligo-3,3-bis (chloromethyl) oxetane is carried out analogously to example 2 with the only difference that 1072 g of dimethyl sulfoxide are used as the reaction medium. The content of hydroxyl groups of 1.1 wt.%. The total yield of oligo-3,3-bis (azidomethyl) oxetane is 273 g (80%).

The examples are summarized in table.

As can be seen from examples of specific performance, the inventive method can significantly reduce material losses and increase the yield of the desired oligo-3,3-bis (azidomethyl) oxetane from 55-61 to 80-83%. The amount of methylene chloride used as a reaction medium decreases 1.7-2.2 times.

The proposed method was tested on a pilot installation of FKP "GosNIIHP" and confirmed the indicated positive effect.

Claims (5)

1. A method of producing oligo-3,3-bis (azidomethyl) oxetane, comprising the cationic polymerization of 3,3-bis (chloromethyl) oxetane in methylene chloride at 20-35 ° C in the presence of boron trifluoride etherate catalyst in an amount of 1-10 wt. % (4-7 wt.%) And dihydric alcohol in a ratio of 1: (5-15) mol. (1: (6-13 mol.)) To 3,3-bis (chloromethyl) oxetane, isolation of the intermediate oligo-3,3-bis (chloromethyl) oxetane in finely divided form, for which, upon completion of polymerization, an organic solvent is added to the reaction mass evaporated methylene chloride and precipitated oligo-3,3-bis (chloromethyl) oxetane with water, and the subsequent interaction of oligo-3,3-bis (chloromethyl) oxetane with sodium azide in an organic solvent in the presence of a tetrabutylammonium bromide catalyst in an amount of 0.5 -3 wt.% (1-2%) at 90-130 ° C (110-125 ° C). 2. The method according to claim 1, where 1,4-butanediol is used as the dihydric alcohol, and N, N-dimethylformamide is used as the organic solvent. 3. The method according to claim 1, where 1,4-butanediol is used as the dihydric alcohol, and dimethyl sulfoxide is used as the organic solvent. 4. The method according to claim 1, where ethylene glycol is used as the dihydric alcohol, and N, N-dimethylformamide is used as the organic solvent. 5. The method according to claim 1, where ethylene glycol is used as the dihydric alcohol, and dimethyl sulfoxide is used as the organic solvent.