Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof

Abstract

The invention relates to a method for producing siloxanes selectively carrying primary amino groups by reacting them with ammonia, and to compounds produced in this way.

1 . A compound comprising an amino-functional siloxane of general formula 1 or a quaternary ammonium derivative thereof, wherein
   M a M′ a1 M″ a2 M′″ a3 D b D′ b1 D″ b2 D′″ b3 T c Q d   (formula 1)
   where   M=(R 1   3 SiO 1/2 )   M′=(R 2 R 1   2 SiO 1/2 )   M″=(R 3 R 1   2 SiO 1/2 )   M′″=(R 4 R 1   2 SiO 1/2 )   D=(R 1   2 SiO 2/2 )   D′=(R 2 R 1 SiO 2/2 )   D″=(R 3 R 1 SiO 2/2 )   D′″=(R 4 R 1 SiO 2/2 )   T=(R 5 SiO 3/2 )   Q=(SiO 4/2 )   a is in the range of from 0 to 32;   a1 is in the range of from 0 to 10;   a2 is in the range of from 0 to 32;   a3 is in the range of from 0 to 10;   b is in the range of from 0 to 600;   b1 is in the range of from 0 to 50;   b2 is in the range of from 0 to 50;   b3 is in the range of from 0 to 50;   c is in the range of from 0 to 20; and   d is in the range of from 0 to 20;   wherein:   if a1=2, at least one of b1, b2, b3, a2 and a3 is not 0;   R 1  is each independently a linear or branched hydrocarbon radical having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms;   R 2  is each independently an organic radical comprising a primary amino function;   R 3  is each independently a radical selected from the group consisting of
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″, 
 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH 2 —CH(R′)O—) y —R″, 
 —CH 2 —CH 2 —(O) x′ —R IV , 
 —CH 2 —CH 2 —CH 2 —O—CH 2 —CH(OH)—CH 2 OH, and 
 —CH 2 —CH 2 —CH 2 —O—CH 2 —C(CH 2 OH) 2 —CH 2 —CH 3 , wherein 
   x is in a range of from 0 to 100,   x′ is in a range of from 0 to 1,   y is in a range of from 0 to 100,   R′ is each independently a linear or substituted alkyl or aryl group having 1 to 12 carbon atoms, where, within at least one of a radical R 4  and a molecule of the formula 1, mutually different substituents R′ are optionally present, and   R″ is each independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, or a group —C(O)—R′″ where R′″=an alkyl radical, a group —CH 2 —O—R′, or an alkylaryl group,   R IV  is an optionally substituted hydrocarbon radical having 1 to 50 carbon atoms,   R 4  is each independently a linear, cyclic or branched, saturated or unsaturated or aromatic hydrocarbon radical having 1 to 30 carbon atoms which is optionally substituted with a group comprising heteroatoms O, N, S, P or halogen atoms and which optionally contains no primary or secondary amine functions, and   R 5  is each independently a radical of R 1 , R 2 , R 3  or R 4 .   
     
     
         2 . The compound according to  claim 1 , wherein R 2  is a radical which, in addition to the amino function, comprises a hydroxyl group selected from the group consisting of 
       
         
           
           
               
               
           
         
         where 
         R 6  is each independently a radical selected from the group consisting of hydrogen and alkyl having 1 to 6 carbon atoms, 
         R 7  is each independently a divalent hydrocarbon radical which optionally comprises an ether function and which is optionally a polyoxyalkylene radical, and 
         m is an integer from 2 to 18. 
       
     
     
         3 . An ionic adduct comprising the compound according to  claim 1  wherein the amino-functional siloxane of the formula 1 is reacted with protic reactants H + A −  to obtain the ionic adduct comprising —NH 3   + A − , where A −  corresponds to an inorganic or organic anion. 
     
     
         4 . The compound according to  claim 1 , wherein the amino-functional siloxane of the formula 1 is converted by alkylation to a quaternary ammonium compound of the formula 2
   M a M″″ a1 M″ a2 M′″ a3 D b D″″ b1 D″ b2 D′″ b3 T c Q d   (formula 2)
   where   M=(R 1   3 SiO 1/2 )   M″″=(R 8 R 1   2 SiO 1/2 )   M″=(R 3 R 1   2 SiO 1/2 )   M′″=(R 4 R 1   2 SiO 1/2 )   D=(R 1   2 SiO 2/2 )   D″″=(R 8 R 1 SiO 2/2 )   D″=(R 3 R 1 SiO 2/2 )   D′″=(R 4 R 1 SiO 2/2 )   T=(R 5 SiO 3/2 )   Q=(SiO 4/2 )   a, a1, a2, a3, b, b1, b2, b3, c and d and the radicals R 1 , R 3 , R 4  and R 5  have the meaning given in  claim 1 , and   R 8  is each independently an organic radical comprising an ammonium function.   
     
     
         5 . The compound according to  claim 4 , wherein:
 R 8  is each independently a radical selected from the group consisting of   
       
         
           
           
               
               
           
         
       
       ; and
 R 9  is each independently a linear or branched hydrocarbon radical having 1 to 30 carbon atoms or an aromatic hydrocarbon radical having 6 to 30 carbon atoms. 
 
     
     
         6 . A method for producing selectively primary amino group-carrying siloxanes, comprising reacting an epoxy-functional compound with gaseous, dissolved or in situ generated ammonia. 
     
     
         7 . The method according to  claim 6  for producing the amino-functional siloxanes comprising
 reacting the epoxy-functional compound with ammonia optionally dissolved in a solvent or optionally with an ammonium compound which is capable of producing ammonia, optionally in the presence of a ring-opening catalyst, and optionally under pressure at a minimum temperature of 50° C. to 150° C., 
 wherein 
 the epoxy-functional compound is an epoxy-functional compound of formula 3
   M a M′″″ a1 M″ a2 M′″ a3 D b D′″″ b1 D″ b2 D′ b3 T c Q d   (formula 3)
 
 
 where 
 M=(R 1   3 SiO 1/2 ); 
 M′″″=(R 10 R 1   2 SiO 1/2 ); 
 M″=(R 3 R 1   2 SiO 1/2 ); 
 M′″=(R 4 R 1   2 SiO 1/2 ); 
 D=(R 1   2 SiO 2/2 ); 
 D′″″=(R 10 R 1 SiO 2/2 ); 
 D″=(R 3 R 1 SiO 2/2 ); 
 D′″=(R 4 R 1 SiO 2/2 ); 
 T=(R 5 SiO 3/2 ); and 
 Q=(SiO 4/2 ), 
 where 
 a is in a range of from 0 to 32; 
 a1 is in a range of from 0 to 10; 
 a2 is in a range of from 0 to 32; 
 a3 is in a range of from 0 to 10; 
 b is in a range of from 0 to 600; 
 b1 is in a range of from 0 to 50; 
 b2 is in a range of from 0 to 50; 
 b3 is in a range of from 0 to 50; 
 c is in a range of from 0 to 20; and 
 d is in a range of from 0 to 20; 
 wherein: 
 if a1=2, at least one of b1, b2, b3, a2 and a3 is not 0; 
 R 1  is each independently—a linear or branched hydrocarbon radical having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms; 
 R 2  is each independently—an organic radical comprising a primary amino function; 
 R 3  is each independently a radical selected from the group consisting of
 —CH 2 —CH 2 —CH 2 —O—(CH 2 —CH 2 O—) x —(CH—CH(R′)O—) y —R″, 
 —CH 2 —CH 2 —O—(CH—CHO—), —(CH 2 —CH(R′)O—)—R″, 
 —CH 2 —CH 2 —(O) x′ —R IV , 
 —CH 2 —CH 2 —CH 2 —O—CH 2 —CH(OH)—CH 2 OH, and 
 —CH 2 —CH 2 —CH 2 —O—CH 2 —C(CH 2 OH) 2 —CH 2 —CH 3 , wherein 
 
 x is in a range of from 0 to 100, 
 x′ is in a range of from 0 to 1, 
 y is in a range of from 0 to 100, 
 R′ is each independently a linear or substituted alkyl or aryl group having 1 to 12 carbon atoms, where, within at least one of a radical R 4  and a molecule of the formula 1, mutually different substituents R′ are optionally present, and 
 R″ is each independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, or a group —C(O)—R′″ where R′″=an alkyl radical, a group —CH, —O—R′, or an alkylaryl group, 
 R IV  is an optionally substituted hydrocarbon radical having 1 to 50 carbon atoms, 
 R 4  is each independently a linear, cyclic or branched, saturated or unsaturated or aromatic hydrocarbon radical having 1 to 30 carbon atoms which is optionally substituted with a group comprising heteroatoms O, N, S, P or halogen atoms and which optionally contains no primary or secondary amine functions, and 
 R 5  is each independently a radical of R 1 , R 2 , R 3  or R 4 , and 
 R 10  is each independently an organic epoxy radical. 
 
     
     
         8 . The method according to  claim 7 , wherein the epoxy-functional compound of the formula 3 comprises R 10 , wherein R 10  is each independently an organic epoxy radical selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         9 . The method according to  claim 7 , wherein the ammonium compound used comprises one or more selected from the group consisting of gaseous ammonia, aqueous ammonia solutions, alcoholic ammonia solutions, ammonium halides, ammonium carbonate, hydrogencarbonate, ammonium sulfate, hydrogensulfate, ammonium sulfamate, ammonium phosphate, hydrogenphosphate, dihydrogenphosphate, ammonium cyanate, ammonium carboxylates, ammonium acetate, ammonium hydrogenoxalate, oxalate, ammonium hydrogencitrate, ammonium benzoate, ammonium formate, ammonium carbamate, ammonium lactate, ammonium tartrate, ammonium succinate, hydroxylamine, hydroxylamine-O-sulfonic acid, amidosulfonic acid and urotropin. 
     
     
         10 . The method according to  claim 7 , comprising passing gaseous ammonia in a pressureless manner through a mixture comprising the epoxy-functional compound. 
     
     
         11 . The method according to  claim 7 , comprising carrying out the reaction at a pressure above 1 bar. 
     
     
         12 . An emulsifier for a cosmetic preparation, a compatibilizer for plastic blends, a release agent, a hydrophobicizing agent, a dispersant for colored pigments and fillers, an additive for textile finishing, a conditioner for hair, a primer for surface coating/adhesion promoter, an additive for corrosion protection formulations, a PU foam stabilizer, an antifoam, or a wetting agent, comprising the amine functional siloxane of the formula 1 according to  claim 1 . 
     
     
         13 . A preparation in the form of a solution, emulsion, dispersion or a mixture, comprising the compound according to  claim 1 , comprising a further additive and one more accessory materials selected from the group consisting of fillers, emulsifiers, dyes, pigments. 
     
     
         14 . The compound according to  claim 1 , wherein at least one of b1, b2, b3, a2 and a3 is not 0. 
     
     
         15 . An ionic adduct comprising the compound according to  claim 2 . 
     
     
         16 . The method according to  claim 7 , comprising carrying out the reaction at a pressure in a range of from 2 to 50 bar. 
     
     
         17 . An emulsifier for a cosmetic preparation, a compatibilizer for plastic blends, a release agent, a hydrophobicizing agent, a dispersant for colored pigments and fillers, an additive for textile finishing, a conditioner for hair, a primer for surface coating/adhesion promoter, an additive for corrosion protection formulations, a PU foam stabilizer, an antifoam, or a wetting agent, comprising the amine functional siloxane of the formula 2 according to  claim 4 . 
     
     
         18 . A preparation in the form of a solution, emulsion, dispersion or a mixture, comprising the compound according to  claim 4 , comprising a further additive and one more accessory materials selected from the group consisting of fillers, emulsifiers, dyes, pigments.