Polyalkoxylated terpenic compounds, their process of preparation and their use as defoaming agents

Abstract

The invention concerns polyalkoxylated terpenic compounds of formula Z—X—W—[CH(R 5 )—CH(R 6 )—O]q—A in which Z is a bicycloheptenyl or bicycloheptyl radical, preferably substituted by methy radicals; X is preferably a —CH 2 —CH 2 —O or O—CH 2 —CH 2 —O— radical; W is a polysequence, preferably polyoxypropylene and polyoxyethylene; [CH(R 5 )—CH(R 6 )—O]q is a sequence different from a polyoxyethylene sequence, preferably polyoxypropylene; A is H, a functional or hydrocarbon group. They can be prepared by successively polyalcoxylating the reagent Z—XH. They can be used as antifoaming agents in foaming aqueous media, in particular in degreasing aqueous media in alkaline medium of sheet metals, as well as detergent aqueous media in household washing or industrial and institutional washing.

1 . Polyalkoxylated terpenic compounds of formula (I)  
       Z—X—W—[CH(R 5 )—CH(R 6  )—O] q —A   (I)  
       in which formula: 
 the Z symbol represents a bicyclo[a.b.c]heptenyl or bicyclo[a.b.c]heptyl radical, optionally substituted by at least one C 1 -C 6  alkyl radical, preferably a methyl radical,  
 a, b and c being such that: 
 a+b+c=5,  
 a=2, 3 or 4,  
 b=1 or 2,  
 c=0 or 1,  
 
 the X symbol represents a group 
 —CH 2 —C (R 1 ) (R 2 ) —O—,  
 or —O—CH(R′ 1 )—CH(R′ 2 )—O—,  
 
 the R 1  and R 2  symbols being identical or different and representing a linear or branched C 1 -C 6  (cyclo)alkyl or (cyclo)alkenyl group, in particular a methyl group, or preferably a hydrogen atom,  
 the R′ 1  and R′ 2  symbols being identical or different and representing a linear or branched C 1 -C 22  (cyclo)alkyl or (cyclo)alkenyl group, in particular a methyl group, or preferably a hydrogen atom,  
 the R 5  and R 6  symbols are different, one representing a hydrogen atom and the other a linear or branched C 1 -C 22  (cyclo)alkyl or (cyclo)alkenyl group, preferably a methyl group,  
 q is a mean value which can range from 1 to 30, preferably from 5 to 20,  
 W represents a polyblock group composed of different  
 [B] n — and —[C] p — blocks, 
 B representing a —CH(R 3 )—CH(R 4 )—O— group, in which R 3  and R 4  are identical or different and represent a hydrogen atom or a linear or branched C 1 -C 22  (cyclo)alkyl or (cyclo)alkenyl group, preferably a methyl group, R 3  and R 4  being different when one of them represents hydrogen,  
 C representing an oxyethylene group —CH 2 —CH 2 —O— (EO),  
 n being a mean value which can range from 1 to 10, preferably from 2 to 4,  
 p being a mean value which can range from 1 to 100, preferably from 3 to 20, the said polyblock group W being bonded to the X unit by one of its —[B] n — blocks,  
 
 A represents a hydrogen atom, a C 1 -C 6  alkyl radical, an aryl or alkylaryl radical, a halogen atom, a —CH 2 —CH(OH)R 7  group, where the R 7  symbol represents a linear or branched or cyclic C 1 -C 22  alkyl radical or an aryl radical, or a group chosen from —SO 3 M, —OPO 3 (M) 2 , —(CH 2 ) a —COOM or —(CH 2 ) b —SO 3 M, with a and b ranging from 1 to 6 and M representing H, Na, K, Li or N(RR′R″R″′) + , where the R, R′, R″ and R″′ symbols are identical or different and represent a hydrogen atom or an optionally hydroxylated linear or branched or cyclic C 1 -C 22  alkyl radical.  
 
     
     
         2 . Polyalkoxylated terpenic compounds according to  claim 1 , characterized in that the Z symbol represents a Z 1  or Z 2  radical, Z 1  being 
 a bicyclo[3.1.1]heptenyl radical, preferably substituted on its carbon atom at the 6-position by at least one C 1 -C 6  alkyl radical, very particularly by two methyl radicals,    the said bicyclo[3.1.1]heptenyl radical being bonded to the X unit of formula —CH 2 —C(R 1 ) (R 2 )—O— via its carbon atom at the 2-position;    or a bicyclo[2.2.1]heptenyl radical, preferably substituted on its carbon atom at the 7-position by at least one C 1 -C 6  alkyl radical, very particularly by two methyl radicals,    the said bicyclo[2.2.1]heptenyl radical being bonded to the X unit of formula —CH 2 —C(R 1 ) (R 2 )—O— via its carbon atom at the 2-position or at the 3-position; and Z 2  being a bicyclo[2.2.1]heptyl radical, preferably substituted on its carbon atom at the 7-position by at least one C 1 -C 6  alkyl radical, very particularly by two methyl radicals,    the said bicyclo[2.2.1]heptyl radical being bonded to the X unit of formula —O—CH(R′ 1 )—CH(R′ 2 )—O— via its carbon atom at the 2-position or at the 3-position.    
     
     
         3 . Polyalkoxylated terpenic compounds according to  claim 1  or  2 , characterized in that the said [B] n  and [CH(R 5 )—CH(R 6 )] q  blocks are [PO] n  and [PO] q  polyoxypropylene blocks.  
     
     
         4 . Polyalkoxylated terpenic compounds according to any one of  claims 1  to  3 , characterized in that the W symbol represents a —[B] n —[C] p — diblock group, the [B] n  block being a [PO] n  polyoxypropylene block and the [C] p  block being an [EO] p  polyoxyethylene block.  
     
     
         5 . Polyalkoxylated terpenic compounds according to  claim 2 , characterized in that they have the formula  
       Z 1 —CH 2 —CH 2 —O—[PO] n —[PO] q —A  
       or  
       z 2 —O—CH 2 —CH 2 —O—[PO] n —[EO] p —[PO] q —A  
     
     
         6 . Polyalkoxylated terpenic compounds according to any one of  claims 1  to  5 , characterized in that they have the formula  
       
         
           
           
               
               
           
         
       
     
     
         7 . Polyalkoxylated terpenic compounds according to any one of  claims 1  to  6 , characterized in that the mean values of n, p and q are chosen so that a 1% by weight solution in distilled water of the said compound exhibits a cloud point of less than 40° C.  
     
     
         8 . Process for the preparation of the polyalkoxylated terpenic compounds forming the subject-matter of  claim 1  by successive polyalkoxylation reactions of a reactant of formula Z—XH, where Z and X have the definition given in  claim 1 , with alkylene oxide (AO1) of formula  
       
         
           
           
               
               
           
         
       
       ethylene oxide (EO) of formula  
       
         
           
           
               
               
           
         
       
       and alkylene oxide (AO2) of formula  
       
         
           
           
               
               
           
         
       
       R 3 , R 4 , R 5  and R 6  having the definition given in  claim 1 , with successive introduction of the alkylene oxides (AO1) and (EO) and final introduction of alkylene oxide (AO2), 
 in order to obtain a product of formula  
 Z—X—W—[CH(R 5 )—CH(R 6 )—O] q H  
 in which W and q have the definition given in  claim 1 , and then optionally functionalization in order to convert the terminal hydrogen atom into one of the A substituents, other than hydrogen, as defined in  claim 1 .  
 
     
     
         9 . Process according to  claim 8 , characterized in that the Z—XH reactant has the formula  
       
         
           
           
               
               
           
         
       
     
     
         10 . Process according to  claim 8  or  9 , characterized in that the alkylene oxides (AO1) and (AO2) are propylene oxide.  
     
     
         11 . Use as defoaming agent in aqueous media which can form foams of at least one polyalkoxylated terpenic compound forming the subject-matter of any one of  claims 1  to  7  or obtained according to the process forming the subject-matter of any one of  claims 8  to  10 .  
     
     
         12 . Use according to  claim 11 , characterized in that the said aqueous media, for which it is necessary to limit the volume of foam which can be formed, are aqueous media for degreasing metal sheets in alkaline medium, aqueous media for degreasing drilling platforms, aqueous media employed for cleaning oil drilling wells drilled by means of oil-based fluids, and aqueous detergent media used in household detergency or in industrial and institutional detergency.  
     
     
         13 . Aqueous compositions for degreasing metal surfaces in alkaline medium or oil drilling wells or detergents comprising at least one polyalkoxylated terpenic compound forming the subject-matter of any one of  claims 1  to  7  or obtained according to the process forming the subject-matter of any one of  claims 8  to  10 .