Process for the coupled preparation of trisilylamine and polysilazanes having a molar mass of up to 500 g/mol

Patent metadata

Field	Value
Publication number	US-9446954-B2
Application number	US-201314345587-A
Country	US
Kind code	B2
Filing date	Jun 5, 2013
Priority date	May 27, 2013
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

The invention relates to a process for preparing trisilylamine and polysilazanes in the liquid phase, in which ammonia is introduced in a superstoichiometric amount relative to 5 monochlorosilane which is present in an inert solvent. Here, a reaction in which trisilylamine and polysilazanes are formed proceeds. TSA is subsequently separated off in gaseous form from the product mixture. The TSA obtained is purified by filtration and distillation and obtained in high or very high purity. The bottom product mixture is conveyed from the reactor through a filter unit in which solid ammonium chloride is separated off to give a liquid mixture of polysilazanes and solvent. This is fed to a further distillation to recover solvent. As a result of the NH 3 being introduced in a superstoichiometric amount relative to monochlorosilane, monochlorosilane is completely reacted in the reactor. This completely prevents the reaction of monochlorosilane with additional disilylamine formed in small amounts to form solid ammonium chloride in the downstream plant parts for purification of the TSA. The solutions filtered downstream of the reactor are accordingly completely free of solids.

First claim

The invention claimed is:

1. A liquid phase process for preparing trisilylamine and polysilazanes, comprising
(a) charging monochlorosilane (MCS) as a solution in a solvent (L) to a reactor ( 1 )
(b) introducing ammonia (NH 3 ) in a stoichiometric excess relative to the monochlorosilane (MCS) into the reactor ( 1 ) to conduct reaction and obtain a product mixture comprising trisilylamine (TSA), L, NH 4 Cl, disilylamine (DSA), NH 3 and polysilazanes (PS);
(c) depressurizing the reactor and setting the reactor to a pressure of from 0.5 bar to 0.8 bar;
(d) conveying a mixture of TSA, L, NH 4 Cl, DSA, and NH 3 in gaseous form from the top of the reactor ( 1 ) through a distillation unit ( 2 ), wherein the NH 3 is separated off under reduced pressure provided by a vacuum unit ( 8 ) to obtain a gaseous product mixture of TSA, L, NH4Cl and DSA;
(e) condensing the gaseous product mixture comprising TSA, L, NH4Cl, and DSA in a heat exchanger ( 7 ) to obtain a condensed product mixture;
(f) collecting the condensed product mixture (TSA, L, NH 4 Cl, DSA) in a vessel ( 6 ),
(g) filtering the condensed product mixture through filter unit ( 3 ), wherein solid ammonium chloride (NH 4 Cl) is separated off from the filtrate comprising TSA, L and DSA;
(h) conveying the filtrate from the filter unit ( 3 ) into a distillation column ( 4 ) in which the DSA is separated off at the top and the TSA and L are conveyed into a distillation column ( 11 ) in which TSA is separated off at the top from the solvent (L);
(i) recovering the solvent (L);
(j) conveying a product mixture comprising PS, L and NH 4 Cl from the bottom of the reactor ( 1 ) through a filter unit ( 5 ) in which solid ammonium chloride (NH 4 Cl) is separated off, to obtain a mixture of polysilazanes (PS) and solvent (L) which is collected in a vessel 9 ; and
(k) conveying the mixture of polysilazanes (PS) and solvent (L) to a distillation column ( 10 ) in which the solvent is recovered at the top and a mixture of polysilazanes (PS) is obtained from the bottom of the distillation column;
wherein the solvent (L) is inert towards monochlorosilane, ammonia, trisilylamine (TSA), disilylamine (DSA) and polysilazanes (PS) and has a boiling point higher than that of TSA.

2. The process of claim 1 , wherein the stoichiometric excess of the ammonia (NH 3 ) introduced into the reactor ( 1 ) relative to the monochlorosilane is from 2 to 20%.

3. The process of claim 1 , wherein the solvent (L) is toluene.

4. The process of claim 1 , wherein the solvent (L) is in a volume excess over monochlorosilane (MCS).

5. The process of claim 1 , wherein a temperature of the reaction in the reactor ( 1 ) is from −60 to +40° C.

6. The process of claim 1 , wherein
a temperature of the filtration of the product mixture (PS, L, NH 4 Cl) from the bottom of the reactor is less than or equal to room temperature, and a clear filtrate is obtained, and/or
a pressure of the distillation of the mixture of polysilazanes (PS) and solvent (L) is 0.5 bar.

7. A plant to conduct the liquid phase process of claim 1 , comprising:
a reactor ( 1 ) having feed lines for ammonia, MCS and (L), an outlet for product mixture (TSA, L, NH 4 Cl, DSA, NH 3 ), which opens into a distillation unit ( 2 ) downstream of the reactor ( 1 ), and a discharge facility from the bottom of the reactor which opens into a downstream filter unit ( 5 );
a heat exchanger ( 7 ) having an attached vacuum pump ( 8 ) and a vessel ( 6 ) which is equipped with a line to a filter unit ( 3 ) which has at least one solids outlet for NH 4 Cl and a further line for transfer of a filtrate which opens into
a distillation column ( 4 ) which is equipped with an outlet at the top and a discharge facility from the bottom, which opens into
a distillation column ( 11 ) which is equipped with an outlet at the top and a discharge facility from the bottom,

wherein the downstream filter unit ( 5 ) has at least one solids outlet and a further line for transfer of the filtrate which opens into a vessel ( 9 ) and then a distillation column ( 10 ),
wherein distillation column ( 10 ) is equipped with an outlet at the top and a discharge facility from the bottom.

Assignees

• Hoppe Carl-Friedrich
• Goetz Christian
• Uehlenbruck Goswin
• Rauleder Hartwig
• Evonik Degussa Gmbh

Inventors

• Hoppe Carl-Friedrich
• Goetz Christian
• Uehlenbruck Goswin
• Rauleder Hartwig

Classifications

• B01D3/143

  by two or more of a fractionation, separation or rectification step · CPC title

• B01J2219/24

  Stationary reactors without moving elements inside · CPC title

• C08G77/62

  Nitrogen atoms · CPC title

• C01B21/087 Primary

  containing one or more hydrogen atoms · CPC title

• B01J19/24

  Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) · CPC title