Patent Publication Number: US-2011065811-A1

Title: Ethanolamine Glyceryl Ethers

Description:
The invention relates to ethanolamine glyceryl ether condensation products and their use in dispersions. 
     Dispersions are substance systems consisting of two or more phases in which one substance (the dispersed or disperse phase) is distributed; i.e. dispersed, in very fine form in another (the dispersing agent or dispersant). Both the dispersing agent and also the substances of the disperse phase may be solid, liquid or gaseous. According to the degree of distribution, a distinction is made between molecularly disperse systems, colloidally disperse systems, finely disperse systems and coarsely disperse systems. Examples of dispersions are suspensions, emulsions, foams, aerosols and smoke. Many industrial products are used in the form of dispersions. 
     In order to obtain stable dispersions, in particular suspensions or emulsions, interface-active substances (dispersants or emulsifiers) often have to be added which facilitate distribution of the phases, or make it possible in the first place, and counteract gel formation, phase separation, crystallization or sedimentation of the individual components. 
     The object was therefore to provide novel efficient dispersants and/or emulsifiers which are readily accessible industrially, can be used for a variety of substance systems, but are also toxicologically safe and ecologically compatible. 
     Surprisingly, it has been found that this object is achieved by special ethanolamine glyceryl ether condensation products. These exhibit in particular excellent interface-active properties, can be readily used in aqueous dispersions, suspension concentrates and suspoemulsions, but also in emulsions and emulsion concentrates, effect high compatibility of the components, for example adjuvants, dispersants, electrolytes etc. with one another and a high suspensibility (suspension power) of the components, and also a stabilization of the phases. 
     The invention provides ethanolamine glyceryl ether condensation products of the formula (I) 
     
       
         
         
             
             
         
       
     
     in which
 
R 1 , R 2  and R 3 , in each case independently of one another, may be identical or different and
 
are hydrogen,
 
are a linear or branched, saturated alkyl chain having 1 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms,
 
are a linear or branched unsaturated alkenyl group having 2 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms, are —CH 2 —CH 2 —OH or
 
are a radical of the formula (II)
 
     
       
         
         
             
             
         
       
     
     in which
     (O-A) is an alkyleneoxy group selected from ethyleneoxy group (EO), propyleneoxy group (PO), butyleneoxy group and/or phenyloxirane group,   a is a number from 0 to 50, preferably 0 to 20, particularly preferably 0 to 10,   b is a number from 0 to 50, preferably 0 to 20, particularly preferably 0 to 10,
 
R 5  is hydrogen and/or
       is (O-A) a H, in which (O-A) is an alkyleneoxy group selected from ethyleneoxy group (EO), propyleneoxy group (PO), butyleneoxy group and/or phenyloxirane group and a is a number from 1 to 30, and/or   is —(CR 6 R 7 ) a -phenyl, where R 6  and R 7 , which may be identical or different, are —H, are an OH group, are a linear or branched (C 1 -C 10 )-alkyl or are a linear or branched (C 2 -C 30 )-alkenyl and a is a number from 1 to 10, and/or   is —(CR 6 R 7 ) a -naphthyl, where R 6  and R 7 , which may be identical or different, are —H, are an OH group, are a linear or branched (C 1 -C 10 )-alkyl or are a linear or branched (C 2 -C 30 )-alkenyl and a is a number from 1 to 10, and/or   is a group of the formula (III)   
       

     
       
         
         
             
             
         
       
     
     and/or
         is R 8 R 9 N—(CH 2 ) b —, where R 8  and R 9 , which may be identical or different, are —H, linear or branched (C 1 -C 10 )-alkyl or linear or branched (C 2 -C 30 )-alkenyl and b is a number from 1 to 22, and/or   is HO—(CH 2 ) b —, where b is a number from 1 to 22, and/or   is —SO 3   − X + , —PO 3   2− X + X′ +  or —CH 2 COO − X + , where X +  and X′ +  are H + , Li + , Na + , K + , Ca 2+ /2, Mg 2+ /2 or N(R 8 ) 4   +  and the R 8  may be identical or different and are —H or (C 1 -C 10 )-alkyl, preferably (C 1 -C 4 )-alkyl, and/or   is a group of the formula (IV)       

     
       
         
         
             
             
         
       
         
         
           
             where 
             X +  and X′ +  are H + , Li + , Na + , K + , Ca 2+ /2, Mg 2+ /2 or N(R 8 ) 4   + , and the R 8  may be identical or different and are —H or (C 1 -C 10 )-alkyl, preferably (C 1 -C 4 )-alkyl, and/or 
             is —C(R 11 ) 2 —COO − X + , —CO—R 12 —COO − X +  or —C(R 11 ) 2 C(R 11 ) 2 C(R 11 ) 2 —N(R 13 ) 2 , where the R 11  may be identical or different and are —H and/or CH 3 , R 12  is (C 1 -C 10 )-alkylene or (C 2 -C 30 )-alkenylene, the R 13  may be identical or different and are (C 1 -C 10 )-alkyl or (C 2 -C 30 )-alkenyl, X +  is H + , Li + , Na + , K + , Ca 2+ /2, Mg 2+ /2 or N(R 8 ) 4   + , and the R 8  may be identical or different and are —H or (C 1 -C 10 )-alkyl, preferably (C 1 -C 4 )-alkyl, and/or 
             is —C(R 14 ) 2 C(R 14 ) 2 C(R 14 ) 2 —N((GO) z H) 2 , where the R 14  may be identical or different and are —H and/or —CH 3 , G is —C 2 H 4 —, —C 3 H 6 — or —C 4 H 8 — and z is a number from 1 to 22, and/or 
             is a group of the formula (V) 
           
         
       
    
     
       
         
         
             
             
         
       
         
         c is a number from 1 to 25, preferably a number from 1 to 20, 
         (O-D) is an alkyleneoxy group selected from ethyleneoxy group (EO), propyleneoxy group (PO), butyleneoxy group and/or phenyloxirane group, 
         d is a number from 0 to 50, preferably 0 to 20, particularly preferably 0 to 10, 
         e is a number from 0 to 50, preferably 0 to 20, particularly preferably 0 to 10, and 
         R 4  can have the meaning of R 5 ,
 
with the proviso that at least one of the radicals R 1 , R 2  and R 3  is a radical of the formula (II) and at least one of the other radicals R 1 , R 2  and R 3  is selected from —CH 2 —CH 2 —OH and radicals of the formula (II).
 
       
    
     Within the context of the present invention, the alkenyl groups can be mono- or polyunsaturated. 
     In a preferred embodiment of the invention, at least two of the radicals R 1 , R 2  and R 3  are radicals of the formula (II). 
     In a further preferred embodiment of the invention two of the radicals R 1 , R 2  and R 3  are selected from —CH 2 —CH 2 —OH and radicals of the formula (II). In these compounds, accordingly, one of the radicals R 1 , R 2  and R 3  is a radical of the formula (II) and one of the other radicals R 1 , R 2  and R 3  is selected from —CH 2 —CH 2 —OH and radicals of the formula (II). Among these compounds, preference is in turn given to those in which two of the radicals R 1 , R 2  and R 3  are radicals of the formula (II). The third of the radicals R 1 , R 2  and R 3  is hydrogen or a linear or branched, saturated alkyl chain having 1 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms or is a linear or branched unsaturated alkenyl group having 2 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms, preferably a linear or branched, saturated alkyl chain having 1 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms or is a linear or branched unsaturated alkenyl group having 2 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms, and particularly preferably is a linear or branched, saturated alkyl chain having 1 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms. 
     In a further preferred embodiment of the invention all three radicals R 1 , R 2  and R 3  are selected from —CH 2 —CH 2 —OH and radicals of the formula (II). In these compounds, accordingly, at least one of the radicals R 1 , R 2  and R 3  is a radical of the formula (II) and the two other radicals R 1 , R 2  and R 3  are selected from —CH 2 —CH 2 —OH and radicals of the formula (II). In a particularly preferred embodiment of the invention, one of the radicals R 1 , R 2  and R 3  is a radical of the formula (II) and the two other radicals R 1 , R 2  and R 3  are radicals of the formula —CH 2 —CH 2 —OH. In a further especially preferred embodiment of the invention, two of the radicals R 1 , R 2  and R 3  are radicals of the formula (II) and the third of the radicals R 1 , R 2  and R 3  is a radical of the formula —CH 2 —CH 2 —OH. In a further especially preferred embodiment of the invention, all three radicals R 1 , R 2  and R 3  are radicals of the formula (II). 
     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein (O-A) and (O-D) are in each case a uniform alkyleneoxy group, (a+b) is a number from 0 to 20 and (d+e) is a number from 0 to 20. 
     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein (O-A) (a+b)  and (O-D) (d+e)  are mixed alkyleneoxy groups of the formula —(O-A 1 ) a -(O-A 2 ) b - or —(O-D 1 ) d -(O-D 2 ) e -, which can be arranged randomly or blockwise, and in which a and b are in each case a number from 1 to 30, and d and e are in each case a number from 1 to 20, (O-A 1 ) and (O-D 1 ) are an ethyleneoxy unit, and (O-A 2 ) and (O-D 2 ) are a propyleneoxy unit, a butyleneoxy unit, a phenyloxirane unit, or mixtures of these. 
     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein 
     the radicals R 1 , R 2  and R 3  are identical and are a group of the formula (IIa), 
     
       
         
         
             
             
         
       
     
     in which
     R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is hydrogen.   

     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein 
     the radicals R 1 , R 2  and R 3  are identical and are a group of the formula (IIa), 
     
       
         
         
             
             
         
       
     
     in which
     R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is a group of the formula (III)   

     
       
         
         
             
             
         
       
     
     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein 
     the radicals R 1 , R 2  and R 3  are identical and are a group of the formula (IIb) 
     
       
         
         
             
             
         
       
     
     in which
     (O-A) (a+b)  is a uniform alkyleneoxy group and (a+b) is a number from 1 to 50 and is a mixed alkyleneoxy group of the formula —(O-A 1 ) a -(O-A 2 ) b -, which can be arranged randomly or blockwise and in which (a+b) is a number from 1 to 50, (O-A 1 ) is an ethyleneoxy unit and (O-A 2 ) is a propyleneoxy unit, a butyleneoxy unit, a phenyloxirane unit or mixtures of these,   R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is hydrogen.   

     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein 
     the radicals R 1 , R 2  and R 3  are identical and are a group of the formula (IIc) 
     
       
         
         
             
             
         
       
     
     in which
     (O-A) is an alkyleneoxy group, preferably a propyleneoxy group,   a is a number from 1 to 50,   R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is hydrogen.   

     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein
     R 1  is an alkyl group having 1 to 20, preferably 3 to 20 and particularly preferably 4 to 18, carbon atoms, and   R 2  and R 3  are identical and are a group of the formula (IId)   

     
       
         
         
             
             
         
       
     
     in which
     R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is hydrogen.   

     A further preferred subject matter of the invention is ethanolamine glyceryl ether condensation products of the formula (I) wherein
     R 1  is an alkyl group having 1 to 10 carbon atoms, preferably an n-butyl group, and   R 2  and R 3  are identical and are a group of the formula (IId)   

     
       
         
         
             
             
         
       
     
     in which
     R 5  is hydrogen,   c is a number from 1 to 25, preferably 1 to 20, particularly preferably 2 to 15, especially preferably 4 to 12, extraordinarily preferably 6 to 10, and   R 4  is hydrogen.   

     The ethanolamine glyceryl ether condensation products according to the invention are suitable in an advantageous manner for producing dispersions. A further subject matter of the present invention is dispersions comprising one or more of the ethanolamine glyceryl ether condensation products according to the invention. 
     The ethanolamine glyceryl ether condensation products according to the invention are additionally suitable in an advantageous manner as interface-active substances. A further subject matter of the present invention is therefore also the use of one or more of the ethanolamine glyceryl ether condensation products according to the invention as interface-active substances. 
     In a further preferred embodiment of the invention, the ethanolamine glyceryl ether condensation products according to the invention are used as interface-active substances in dispersions. 
    
    
     EXAMPLES 
     Preparation examples of glyceryl ethers according to the invention are described below without limiting the invention to these. 
     General Preparation Method 
     a) Polymerization of Glycerol to Oligoglycerols or Polyglycerols 
     The polymerization of glycerol to oligoglycerols or polyglycerols takes place in a known manner. 
     For this, glycerol is heated at 200 to 280° C., preferably 240 to 270° C., in the presence of acidic catalysts, for example HCl, H 2 SO 4 , sulfonic acids or H 3 PO 4  or in the presence of alkaline catalysts, such as sodium hydroxide, potassium hydroxide, alkali metal alkoxides, alkali metal carbonates, alkali metal bicarbonates, in a concentration range from 0.1 to 0.4% by weight of catalyst in a stirred apparatus with water separator and while nitrogen is passed through. While discharging water of condensation, the formation of the oligoglycerol or polyglycerol with an average degree of condensation of from 2 to 100, preferably 3 to 35 glycerol units takes place over the course of 3 to 14 hours. From the OH number it is possible to calculate the average molar mass of the oligo- or polyglycerols. 
     The ratio of the degree of condensation n to the condensation time during the polymerization of glycerol to oligoglycerols or polyglycerols is shown in table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Ratio of degree of condensation n to condensation time 
               
            
           
           
               
               
               
               
            
               
                 Degree of 
                 OH number 
                 Molar mass 
                 Condensation time 
               
               
                 condensation n 
                 [mg KOH/g] 
                 [g/mol] 
                 [hours] 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 2.0 
                 1352 
                 166 
                 3-4 
               
               
                 3.0 
                 1169 
                 240 
                 3-4 
               
               
                 4.0 
                 1072 
                 314 
                 4-5 
               
               
                 5.0 
                 1012 
                 388 
                 5-7 
               
               
                 6.0 
                 971 
                 462 
                 6-7 
               
               
                 7.0 
                 942 
                 536 
                 7-9 
               
               
                 8.0 
                 920 
                 610 
                 8-9 
               
               
                 9.0 
                 902 
                 684 
                  9-11 
               
               
                 10 
                 888 
                 758 
                 10-11 
               
               
                 11 
                 877 
                 832 
                 11-12 
               
               
                 12 
                 867 
                 906 
                 11-12 
               
               
                 13 
                 859 
                 980 
                 12-13 
               
               
                 14 
                 850 
                 1056 
                 12-13 
               
               
                 15 
                 844 
                 1130 
                 13-14 
               
               
                   
               
            
           
         
       
     
     b) Preparation of Ethanolamine Glyceryl Ethers 
     To prepare the ethanolamine glyceryl ether condensation products according to the invention, the abovementioned mono-, oligo- or polyglycerols or the corresponding oxalkylated glycerols are combined with nitrogen-containing mono- or polyols and, if appropriate, further comonomers in the desired mixing ratio. Following the addition of 0.1-1.0 mol % (preferably 0.28 mol %) of a basic catalyst (e.g. NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , CaCO 3 , Li 2 CO 3 , preferably NaOH, particularly preferably 50% strength by weight aqueous NaOH), the reaction mixture is heated to 220-290° C., preferably 250-270° C., with vigorous stirring and, at this temperature, while azeotropically removing the water which forms, is condensed until the desired degree of condensation is reached. The reaction progress is monitored by regularly determining the OH number. 
     The compounds according to the invention are characterized by an excellent dispersing power and a high electrolyte stability. Additionally, the glyceryl ethers according to the invention bring about an improvement in the compatibility of hydrophilic and hydrophobic components and in particular an increase in the wetting power and absorption capacity of formulations which comprise these glyceryl ethers. 
     Example 1 
     Cocondensation of Glycerol/Alkyldiethanolamine 
     Glycerol and alkyldiethanolamine are initially introduced in the stated molar ratio together with 0.1 to 1.0 mol % of NaOH (based on the amount of glycerol used) in the form of a 50% strength by weight aqueous NaOH solution and, with stirring at 220° C. and light nitrogen blanketing, are subsequently condensed until the calculated target OH number is approximately reached (see table 2). The resulting products are dark brown and solid. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Ethanolamine glyceryl ether condensation products with 
               
               
                 alkyldiethanolamine 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Average 
               
               
                   
                   
                   
                   
                   
                 molar mass 
               
               
                   
                 Glycerol:alkyldiethanolamine 
                 Reaction 
                 OH number 
                 Degree of 
                 from OH 
               
               
                 Alkyl chain 
                 molar ratio 
                 time 
                 of product 
                 condensation* 
                 number 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 2-Ethylhexyl 
                 10:1 
                 19 h 
                 701 mg 
                 5.0 
                  960 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                 2-Ethylhexyl 
                 30:1 
                 17 h 
                 732 mg 
                 13 
                 2130 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                 Coconut 
                 10:1 
                 11 h 
                 655 mg 
                 4.4 
                  925 g/mol 
               
               
                 (C 8 -C 18 ) 
                   
                   
                 KOH/g 
               
               
                 Coconut 
                 30:1 
                 12 h 
                 729 mg 
                 20 
                 3230 g/mol 
               
               
                 (C 8 -C 18 ) 
                   
                   
                 KOH/g 
               
               
                   
               
               
                 *Degree of condensation of the glycerol per CH 2 OH group of the alkydiethanolamine calculated from OH number 
               
            
           
         
       
     
     Example 2 
     Cocondensation of Glycerol/Triethanolamine 
     Glycerol and triethanolamine are initially introduced in the stated molar ratio together with 0.1-1.0 mol % of NaOH (based on the amount of glycerol used) in the form of a 50% strength by weight aqueous NaOH solution and, with stirring at 270° C. and light nitrogen blanketing, are condensed until the calculated target OH number is approximately reached (see table 3). The resulting products are dark brown and viscous-flowing to solid. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Ethanolamine glyceryl ether condensation products with 
               
               
                 triethanolamine 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Average 
               
               
                 Glycerol:tri- 
                   
                   
                   
                   
                 molar mass 
               
               
                 ethanolamine 
                 Reaction 
                 Reaction 
                 OH number 
                 Degree of 
                 from OH 
               
               
                 molar ratio 
                 time 
                 temperature 
                 of product 
                 condensation* 
                 number 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                  9:1 
                  6 h 
                 270° C. 
                 820 mg 
                 3.3 
                  883 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                 15:1 
                  9 h 
                 270° C. 
                 795 mg 
                 6.1 
                 1500 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                 30:1 
                 14 h 
                 270° C. 
                 781 mg 
                 10.2 
                 2410 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                 45:1 
                 18 h 
                 270° C. 
                 770 mg 
                 20.3 
                 4660 g/mol 
               
               
                   
                   
                   
                 KOH/g 
               
               
                   
               
               
                 *Degree of condensation of the glycerol per CH 2 OH group of the triethanolamine calculated from OH number