RU2275393C1 - Liquid polysulfide polymer production process (options) - Google Patents

Abstract

FIELD: optionally production.

SUBSTANCE: invention relates to liquid polysulfide polymer production process via mixing chlorine-containing monomers: di(β-chloroethyl)formal and 1,2,2-trichloropropane taken at molar ratio between 0.99:0.01 and 0.96:0.04 with sodium hydrosulfide and sulfur at temperature 70-75°C and vigorous stirring for 1.0-1.5 h. Subsequent interaction of reaction mixture components is effected at 85-97°C. Sodium hydrosulfide and sulfur are used at molar ratio 3.2:0.5 to 3.5:1.5 per 1 mole chlorine-containing monomers. Interaction of reaction mixture components is conducted for 3-4 h in presence of a quaternary ammonium halide or mixture thereof in amount 0.5-1.0% of the mass of monomers.

EFFECT: decreased process time, improved environmental safety, and reduced labor consumption.

2 cl, 4 ex

Description

The invention relates to a method for producing liquid polysulfide polymers, which can be used as a polymer base for sealing materials widely used in construction, aircraft and shipbuilding, and the electronics industry.

One of the urgent technical and environmental problems of the chemical industry is the production of sulfur-containing oligomers and polymers in a closed cycle without the discharge of harmful substances into wastewater and the atmosphere. Among these industries is the production of liquid polysulfide polymers such as thiocols, see Polymers Encyclopedia. T.3. M .: Soviet Encyclopedia, 1977, p. 45.

The closest in technical essence to the present invention is a method for producing liquid polysulfide polymers by mixing chlorine-containing monomers - di (β-chloroethyl) formal and 1,2,3-trichloropropane taken in a molar ratio of 0.99: 0.01-0.98 : 0.02, with a sulfide compound, which is used as sulfur or sodium disulfide or a mixture of an arbitrary composition of sulfur and sodium disulfide in an amount of 0.56-1.0 mol per 1 mol of a mixture of chlorine-containing monomers, performing its full or fractional supply, and for 1.5 hours at a temperature of 75-80 ° C and vigorous stirring is introduced an aqueous solution of sodium hydrosulfide in an amount of 1.92-3.15 mol per alkali metal hydrosulfide per 1 mol of a mixture of chlorine-containing monomers, and the reaction components are reacted at a temperature of (97 ± 2) ° С for 6.5 -7.5 hours.

An organic solvent, toluene, is used to isolate and purify the target product.

The essence of the prototype method is shown in accordance with specific examples given in the description of the invention, see Patent RU No. 2220158, IPC 7 C 08 G 75/16, 2003 and the Appendix to the application.

The disadvantages of this method are:

- the use of toxic, as well as fire and explosive substances - toluene for the purification and separation of the target product from an aqueous solution;

- the need for additional equipment and additional operations - distillation of toluene;

- the complexity of the complete removal of the organic solvent by conventional methods, which significantly degrades the consumer properties of polysulfide polymers, especially when used in construction;

- the duration of obtaining the target product.

The objective of the invention is to simplify the method of producing polysulfide polymers.

The technical problem is solved by the method of producing liquid polysulfide polymers by mixing chlorine-containing monomers -di (β-chloroethyl) formal and 1,2,3-trichloropropane taken in a molar ratio of 0.99: 0.01-0.96: 0.04, s sodium hydrosulfide and sulfur at a temperature of 70-75 ° C and vigorous stirring for 1.0-1.5 hours and subsequent interaction of the components of the reaction mass at a temperature of 85-97 ° C, in which sodium hydrosulfide with sulfur is taken in a molar ratio of 3, 2: 0.5-3.5: 1.5 per 1 mol of chlorine-containing monomers, and the interaction of the components is reactive th weight lead in the presence of a quaternary ammonium halide or a mixture of quaternary ammonium halides in an amount of 0.5-1.0% by weight of the monomers for 3-4 hours.

The technical problem is also solved by the method of producing liquid polysulfide polymers by mixing chlorine-containing monomers -di (β-chloroethyl) formal and 1,2,3-trichloropropane taken in a molar ratio of 0.99: 0.01-0.96: 0.04, with sodium hydrosulfide and a sulfide compound at a temperature of 70-75 ° C and vigorous stirring for 1.0-1.5 hours and subsequent interaction of the components of the reaction mass at a temperature of 85-97 ° C, in which sodium polysulfide is used as a sulfide compound the degree of polysulfide n = 2,7-4,2, while hydros sulphide with sodium polysulfide is taken in a molar ratio of 3.1: 0.6-3.5: 0.2 per 1 mol of chlorine-containing monomers, and the reaction components are reacted in the presence of quaternary ammonium halide or a mixture of quaternary ammonium halides in an amount of 0.5 -1.0% by weight of monomers within 3-4 hours.

The solution to the technical problem allows to reduce the duration of the process of producing polysulfide polymers, improve its environmental friendliness and reduce the complexity.

The characteristic used in the method for producing the polysulfide polymer of quaternary ammonium halides:

1. Tetrabutylammonium iodide, formula

[CH ₃ (CH ₂ ) ₃ ] ₄ N ⁺ J ^- white crystalline substance, T _melt - 145-147 ° C

2. Tetrabutylammonium bromide, the formula

[CH ₃ (CH ₂ ) ₃ ] ₄ ] N ⁺ Br ^{is a} white crystalline substance, _Tmelt is 73-75 ° C, see "New reference chemist and technologist." The main properties of inorganic, organic and organoelement compounds, St. Petersburg: ANO NPO "Mir and family", 2002

3. alkyldimethylbenzylammonium chlorides fraction C ₁₀ -C ₁₆ -50% ethyl alcohol solution, a liquid of light yellow color, density at 20 ° C 0.85-0.90 g / cm ^3, manufactured under the trademark "Catapano C" of NIIPAV according to TU 2482-003-04706205-01.

4. Alkyltrimethylammonium chloride fraction C ₁₀ -C ₁₆ -50% alcohol solution, light yellow liquid, density at 20 ° C - 0.85-0.90 g / cm ³ , available under the trademark "ALKAPAV C" according to TU 2482-006-04706205-03. The producer of quaternary ammonium halides according to claims 3 and 4, Volgodonsk, Rostov Region, NIIPAV.

The invention is illustrated by the following examples of specific performance.

Example 1

In a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, put 484 ml of an aqueous solution with a concentration of 7.2 mol / L sodium hydrosulfide (3.5 mol), 48.1 g (1.5 mol) of sulfur powder with the content of the main substance is 99.5% and 0.85 g of tetrabutylammonium bromide (0.5% by weight of chlorine-containing monomers). The contents of the flask are heated with vigorous stirring to a temperature of 70-75 ° C, and then they are mixed for 16 hours with 167.4 g (0.96 mol) of di (β-chloroethyl) formal with a basic substance content of 99.2% and 6 , 1 g (0.04 mol) of 1,2,3-trichloropropane with a basic substance content of 97%. The interaction of the components of the reaction mass is carried out with vigorous stirring and a temperature of 85-90 ° C for 4 hours. Then the heating and stirring are stopped, the mother liquor of the salts is decanted. The resulting polymer is washed several times with water to remove salts and dried in vacuum at a temperature of 80-85 ° C and a residual pressure of 20 mm Hg within 2.5 hours. A yellow polysulfide polymer is obtained in an amount of 161.0 g (97.6%) with a viscosity of 10.2 Pa · s. Mass fraction of S, Cl, SH in%: 38.9; 0; 3.75. The number average molecular weight M _p = 1760.

Example 2

In a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 172.6 g (0.99 mol) of di (β-chloroethyl) formal with the basic substance content of 99.2% and 1.52 g (0.01) are placed mol) of 1,2,3-trichloropropane with a basic substance content of 97%. The contents of the flask are heated with vigorous stirring to a temperature of 70-75 ° C, and then for 1.5 hours they are mixed with 442 ml of an aqueous solution with a concentration of 7.2 mol / l sodium hydrosulfide (3.2 mol), and 3.4 g of a 50% alcohol solution of alkyltrimethylammonium chloride fraction C ₁₀ -C ₁₆ fraction (1% by weight of chlorine-containing monomers), followed by mixing with 16.1 g (0.5 mol) of sulfur powder with a basic substance content of 99.5%. The interaction of the components of the reaction mass is carried out with vigorous stirring and a temperature of 95-97 ° C for 3 hours. Then the heating and stirring are stopped, the mother liquor of the salts is decanted. The resulting polymer is washed several times with water for washing from salts and dried in vacuum at a temperature of 80-85 ° C and a residual pressure of 20 mm Hg within 2.5 hours. A polysulfide polymer of light yellow color is obtained in an amount of 161.4 g (97.5%) with a viscosity of 16.5 Pa · s. Mass fraction of S, Cl, SH in%: 39.1; 0; 2.9. The number average molecular weight M _p = 2275.

Example 3

In a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 429 ml of an aqueous solution with a concentration of 7.2 mol / L sodium hydrosulfide (3.1 mol), 240 ml of an aqueous solution with a concentration of 2.5 mol / L are placed and the degree of polysulfide n = 2.7 sodium polysulfide (0.6 mol) and 1.7 g of tetrabutylammonium iodide (1.0% by weight of chlorine-containing monomers). The contents of the flask are heated with vigorous stirring to a temperature of 70-75 ° C, and then for 1 h are mixed with 172.6 g (0.99 mol) of di (β-chloroethyl) formal with a basic substance content of 99.2% and 1 52 g (0.01 mol) of 1,2,3-trichloropropane with a basic substance content of 97%. The interaction of the components of the reaction mass is carried out with vigorous stirring and a temperature of 85-90 ° C for 4 hours. Then the heating and stirring are stopped, the mother liquor of the salts is decanted. The resulting polymer is washed several times with water to remove salts and dried in vacuum at a temperature of 80-85 ° C and a residual pressure of 20 mm Hg within 2.5 hours. A yellow polysulfide polymer is obtained in an amount of 162.8 g (98.1%) with a viscosity of 42.6 Pa · s. Mass fraction of S, Cl, SH in%: 39.2; 0; 2.12. The number average molecular weight M _p = 3110.

Example 4

In a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 167.4 g (0.96 mol) of di (β-chloroethyl) formal with the basic substance content of 99.2% and 6.1 g (0.04) are placed mol) of 1,2,3-trichloropropane with a basic substance content of 97%. The contents of the flask are heated with vigorous stirring to a temperature of 70-75 ° C, and then for 1.5 hours they are mixed with 484 ml of an aqueous solution with a concentration of 7.2 mol / L sodium hydrosulfide (3.5 mol), 91 ml of an aqueous solution with a concentration of 2.2 mol / l and a degree of polysulfide n = 4.2 of sodium polysulfide (0.2 mol) and 1.7 g of a 50% alcohol solution of alkyl dimethylbenzylammonium chlorides of fraction C ₁₀ -C ₁₆ (0.5% by weight chlorine-containing monomers). The interaction of the components of the reaction mass is carried out with vigorous stirring and a temperature of 95-97 ° C for 3 hours. Then the heating and stirring are stopped, the mother liquor of the salts is decanted. The resulting polymer is washed several times with water for washing from salts and dried in vacuum at a temperature of 80-85 ° C and a residual pressure of 20 mm Hg within 2.5 hours. A light yellow polysulfide polymer is obtained in an amount of 159.8 g (96.5%) with a viscosity of 2.8 Pa · s. Mass fraction of S, Cl, SH in%: 39.6; 0; 10.8. The number average molecular weight M _p = 610.

Thus, the inventive method for producing liquid polysulfide polymers can reduce the duration of the process, improve its environmental friendliness and reduce the complexity.

Claims (2)

1. The method of producing liquid polysulfide polymers by mixing chlorine-containing monomers - di (β-chloroethyl) formal and 1,2,3-trichloropropane, taken in a molar ratio of 0.99: 0.01-0.96: 0.04, with hydrosulfide sodium and sulfur at a temperature of 70-75 ° C and vigorous stirring for 1.0-1.5 hours and subsequent interaction of the components of the reaction mass at a temperature of 85-97 ° C, characterized in that the sodium hydrosulfide with sulfur is taken in a molar ratio of 3 , 2: 0.5-3.5: 1.5 per 1 mol of chlorine-containing monomers, and the interaction of the components of the reaction mass is carried out in addition the use of a quaternary ammonium halide or a mixture of quaternary ammonium halides in an amount of 0.5-1.0% by weight of the monomers for 3-4 hours 2. A method of producing liquid polysulfide oligomers by mixing chlorine-containing monomers - di (β-chloroethyl) formal and 1,2,3-trichloropropane, taken in a molar ratio of 0.99: 0.01-0.96: 0.04, with hydrosulfide sodium and a sulfide compound at a temperature of 70-75 ° C and vigorous stirring for 1.0-1.5 hours and subsequent interaction of the components of the reaction mass at a temperature of 85-97 ° C, characterized in that sodium polysulfide is used as a sulfide compound the degree of polysulfide n = 2,7-4,2, while hydrosulfide and sodium polysulfide they are taken in a molar ratio of 3.1: 0.63.5: 0.2 per 1 mol of chlorine-containing monomers, and the reaction components are reacted in the presence of a quaternary ammonium halide or a mixture of quaternary ammonium halides in an amount of 0.5-1.0% by weight of monomers for 3-4 hours