Method for preparing polyhydroxy-urethanes

Abstract

The invention relates to a method for preparing polyhydroxy-urethanes without using a compound having an isocyanate function, and from amino compounds and compounds carrying carbonate functions, in particular cyclic carbonate functions. The invention also relates to a method for preparing aqueous or hydro-organic formulations containing polyhydroxy-urethanes, and to the use of said polyhydroxy-urethanes and of said aqueous or hydro-organic formulations.

1 . A method for preparing a compound, an oligomer or a polymer (U) having at least one urethane group and at least one hydroxyl functional group, said method comprising reacting simultaneously, or in succession:
 a) at least one compound (1) having a cyclic carbonate functional group and at least one hydroxyl functional group, wherein the oxygen atom of the hydroxyl group is separated from the carbon atom of the carbonyl group of said cyclic carbonate by from 3 to 5 atoms, or its precursor (1′) having at least three functional groups;   b) at least one compound (2) carrying at least one linear carbonate functional group;   c) at least one compound (3) carrying at least one primary or secondary amine functional group; and   d) at least one catalyst (4) comprising a non-ionic phosphazene type-base;   optionally in the presence of a solvent, and optionally followed by removal of said solvent and/or co-products of the reaction.   
     
     
         2 . The method according to  claim 1 , in which said at least one hydroxyl functional group of said compound, oligomer or polymer (U) is located in the β- or γ-position of said at least one urethane functional group. 
     
     
         3 . The method according to  claim 1 , in which said compound, oligomer or polymer (U) having at least one urethane group and at least one hydroxyl functional group is a polyhydroxy-urethane. 
     
     
         4 . The method according to  claim 1 , in which compound (1) is a polyol carbonate. 
     
     
         5 . The method according to  claim 1 , in which compound (1) is present in the form of its precursor (1′) having at least three hydroxyl functional groups, of which two are capable of forming the cyclic carbonate functional group of compound (1) and a third is located in the β- or γ-position of said carbonyl functional group capable of being formed. 
     
     
         6 . The method according to  claim 5 , in which precursor (1′) is selected from the group consisting of ethane-1,1,2-triol (glycerol), 2,2-(dihydroxymethyl)butan-1-ol (trimethylolpropane), propane-1,2,3-triol, 2,2-(dihydroxymethyl)propane-1,3-diol, derivatives of trishydroxymethylaminomethane, wherein the amine functional group is optionally protected and is present as an amide, urethane or salt, a sugars (carbon hydrates), polyethers functionalized by hydroxyl functional groups and polyesters functionalized by hydroxyl functional groups. 
     
     
         7 . The method according to  claim 1 , in which the boiling point of compound (2) is from 80° C. to 280° C. at atmospheric pressure (1013.25 hPa). 
     
     
         8 . The method according to  claim 1 , in which compound (2) has the general formula (a) below: 
       
         
           
           
               
               
           
         
         in which R and R′, which are identical or different, each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms, wherein each alkyl radical is optionally substituted by at least one cyclic carbonate. 
       
     
     
         9 . The method according to  claim 1 , in which compound (2) has the general formula (a): 
       
         
           
           
               
               
           
         
       
       in which R and R′, which are identical or different, each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms or a linear or branched alkyl radical having from 1 to 6 carbon atoms substituted by at least one cyclic carbonate group, with the proviso that R and/or R′ has (have) at least one cyclic carbonate group. 
     
     
         10 . The method according to  claim 1 , in which compound (2) is selected from the group consisting of dimethyl carbonate, diethyl carbonate, and mixtures thereof. 
     
     
         11 . The method according to  claim 1 , in which compound (3) comprises one or more other functional groups selected from the group consisting of ether, urethane, amide, hydroxyl, thiol, carboxyl and an ionic functional group, and a mixture thereof. 
     
     
         12 . The method according to  claim 1 , in which compound (3) is selected from the group consisting of:
 primary or secondary monoamines, having a linear, branched or cyclic chain, optionally containing one or more unsaturated bonds, and having from 1 to 20 carbon atoms;   primary or secondary monoamines, having a linear, branched or cyclic chain, optionally containing one or more unsaturated bonds, and having from 1 to 20 carbon atoms, and having one or more ionic functional groups, and/or having one or more functional groups selected from —OH, —SH and ether;   polyether monoamines, which can also have one or more ionic functional groups, and/or one or more functional groups selected from —OH, —SH;   aliphatic or cycloaliphatic diamines,   aromatic diamines;   diamines having ionic functional group(s); and   oligomers and polymers having at least two amine functional groups.   
     
     
         13 . The method according to  claim 1 , in which compound (3) is selected from the group consisting of di-, tri- or tetra-functional polyether amines and polyoxyalkyleneamines, in which the alkylene structural unit is linear or branched, and mixtures thereof. 
     
     
         14 . The method according to  claim 1 , in which the reaction solvent is methoxypropyl acetate, N-methylpyrrolidone, dimethyl sulfoxide, an alcohol or an acetal. 
     
     
         15 . The method according to  claim 12 , wherein the polymer having at least two amine functional groups is a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof. 
     
     
         16 . A method for preparing a compound (U) having at least one urethane group and at least one hydroxyl functional group, said method comprising reacting:
 a) at least one compound of formula (a)   
       
         
           
           
               
               
           
         
       
       in which R and R′, which are identical or different, each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms, and R and/or R′ has (have) at least one cyclic carbonate group;
 b) at least one compound (3) carrying at least one primary or secondary amine functional group; and 
 c) at least one catalyst (4) comprising a non-ionic phosphazene type-base; 
 optionally in the presence of a solvent, and optionally followed by removal of said solvent and/or co-products of the reaction. 
 
     
     
         17 . The method of  claim 1 , wherein compound (U) is an oligomer or a polymer. 
     
     
         18 . The method of  claim 16 , wherein compound (U) is an oligomer or a polymer. 
     
     
         19 . A method for preparing a compound, an oligomer or a polymer (U) having at least one urethane group and at least one hydroxyl functional group, said method employing:
 a) at least one compound of formula (a)   
       
         
           
           
               
               
           
         
         
           in which R and R′, which are identical or different, each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms, and R and/or R′ has (have) at least one cyclic carbonate group 
         
         b) at least one compound (3) carrying at least one primary or secondary amine functional group; and 
         d) optionally at least one catalyst (4); 
         the compounds (a), (3) and optionally the catalyst (4) taking part, simultaneously or in succession, in a reaction, optionally in the presence of a solvent, to yield, optionally after removal of said solvent and/or of the co-products of the reaction, said compound, oligomer or polymer (U). 
       
     
     
         20 . A composition comprising at least one compound obtained according to  claim 1 . 
     
     
         21 . The composition according to  claim 20  which is an organic, aqueous or hydro-organic formulation. 
     
     
         22 . A coating or an adhesive composition, comprising the composition according to  claim 20 , in association with one or more conventional polyurethane(s) or conventional polyol(s), and optionally with one or more curing agents, especially polyisocyanate-based curing agents. 
     
     
         23 . A method for preparing an aqueous-phase formulation of polyhydroxy-urethane, comprising the following steps:
 a) reacting at least one compound carrying at least one cyclic carbonate functional group, with   b) at least one compound having at least two primary and/or secondary amine functional groups; and   c) optionally at least one compound carrying at least one primary and/or secondary amine functional group;   d) mixing the reagents, or the reaction product(s), in an aqueous phase, optionally containing an organic phase; and   e) obtaining an aqueous polyhydroxy-urethane formulation.   
     
     
         24 . The method according to  claim 23 , in which the compound carrying at least one cyclic carbonate functional groups, also has at least one carbamate (urethane) functional group. 
     
     
         25 . The method according to  claim 23 , in which the compound carrying at least one, carbonate functional groups has at least two cyclic carbonate functional groups and is selected from the group consisting of:
 diglycerol dicarbonate;   pentaerythritol dicarbonate;   the diester of adipic acid and glycerol carbonate;   the addition products of a diisocyanate with glycerol carbonate;   the diurethane of isophoronediamine and glycerol carbonate;   the diurethane of hexamethylenediamine and glycerol carbonate;   the diurethane of tricyclodecanediamine and glycerol carbonate;   the diurethane of a polyether amine and glycerol carbonate; and   the diurethane of bis-(4,4′-aminocyclohexyl)methane) and glycerol carbonate.   
     
     
         26 . The method according to  claim 23 , in which the compound carrying at least one cyclic carbonate functional groups is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         27 . The method according to  claim 23 , in which the compound having at least two primary and/or secondary amine functional groups has a molar mass of from 60 to 5000. 
     
     
         28 . The method according to  claim 23 , in which the compound having at least two amine functional groups is selected from the group consisting of
 aliphatic or cycloaliphatic diamines;   aliphatic or cycloaliphatic diamines;   aromatic diamines;   diamines having (an) ionic functional group(s); and   oligomers and polymers having at least two amine functional groups, it being possible for the polymer skeleton to be a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof.   
     
     
         29 . The method according to  claim 23 , in which the compound carrying at least one primary and/or secondary amine functional group is a monoamine selected from the group consisting of monoamines of polymers or oligomers, polyamides, polyethers, polyesters, polyurethanes and copolymers thereof. 
     
     
         30 . A coating comprising an aqueous-phase formulation of polyhydroxy-urethane. 
     
     
         31 . A coating comprising an aqueous-phase formulation of polyhydroxy-urethane which is obtained by the method according to  claim 23 . 
     
     
         32 . An adhesive comprising an aqueous-phase formulation of polyhydroxy-urethane. 
     
     
         33 . An adhesive comprising an aqueous-phase formulation of polyhydroxy-urethane, which is obtained by the method according to  claim 23 .