Patent WO-2022238892-A1 (WO)
Inventor: BIAGINI PAOLO
IPC: C08G64/02
Filed: 2022-05-10
Abstract: Process for the preparation of a functionalized terpolymer having general formula (I): in which: - R 1  and R 2 , the same or different from each other, represent a hydrogen atom; or they are selected from C 1 -C 30  alkyl groups, preferably C 1 -C 20 , linear or branched, saturated, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups; - or R 1  and R 2 , can optionally be bonded together so as to form, together with the other atoms to which they are bonded, a cycle containing from 1 to 12 carbon atoms, saturated, optionally substituted with linear or branched C 1 -C 20  alkyl groups, saturated, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amino groups, dialkyl- or diaryl-phosphine groups C 1 -C 20  alkoxy groups, preferably C 1 -C 10 , linear or branched, saturated, optionally substituted aryloxy groups, optionally substituted thioalkoxyl or thioaryloxy groups, cyano groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulphur, nitrogen, silicon, phosphorus or selenium, preferably oxygen or nitrogen; - R 3  and R 4 , the same or different from each other, represent a hydrogen atom; or they are selected from C 1 -C 30 , alkyl groups, preferably C 1 -C 20 , linear or branched, saturated or unsaturated, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups; provided that at least one of R 3  and R 4  is different from hydrogen and that at least one of R 3  and R 4  contains at least a double or a triple bond between two adjacent carbon atoms, and in the event that two or more double or triple bonds are present; said bonds can be conjugated or unconjugated, preferably unconjugated; - or R 3  and R 4 , can optionally be bonded together so as to form, together with the other atoms to which they are bonded, a cycle containing from 1 to 12 carbon atoms, saturated or unsaturated, optionally substituted with C 1 -C 20  alkyl groups linear or branched, saturated or unsaturated, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amino groups or dialkyl- or diaryl-phosphine groups, C 1 -C 20 ,alkoxyl groups, preferably C 1 -C 10 , linear or branched, saturated or unsaturated, optionally substituted aryloxy groups, optionally substituted thioalkoxyl or thioaryloxy groups, cyano groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulphur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen; provided that within the cycle or in any of its substitutions there is at least one double or triple bond between two adjacent carbon atoms, and in the event that two or more double or triple bonds are present, said bonds can be conjugated or unconjugated, preferably unconjugated; - n and m, equal to or different from each other, are an integer between 1 and 5000, preferably between 1 and 3000, provided that n + m is greater than or equal to 5; comprising the following steps: i) reacting at least one first epoxy compound having general formula (II): in which R 1  and R 2  have the same meanings reported above; with at least a second epoxy compound having general formula (III): in which R 3  and R 4  have the same meanings reported above; and carbon dioxide (CO 2 ), in the presence of a catalytic system comprising at least one catalyst selected from complexes of a transition metal and, optionally, at least one co-catalyst selected from ionic compounds; in which said at least one first epoxy compound having general formula (II) and said at least one second epoxy compound having general formula (III) are used in a molar ratio between 1:99 and 99:1, thus obtaining a terpolymer; ii) reacting the terpolymer obtained in said step i) with at least one sulphur- containing compound having general formula (IV): in which R 5 , R 6  and R 7 , the same or different from each other, represent a hydrogen atom; or they are selected from C 1 -C 20  alkyl groups, preferably C 1 -C 12 , linear or branched, saturated or unsaturated, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups; provided that in said general formula (IV) at least one of between R 5 , R 6  and R 7  differs from hydrogen and at least one of between R 5 , R 6  and R 7 ,contains one of the following functional groups:-COOH, -COO - M + , -SO 3 H, -SO 3  M + , - SO 2 H, -SO 2 
 - M + , -OPO 3 H 2 , -OPO 3 
 2- M + 
 2 , -PO 3 H 2 , -PO 3 
 2-  M + 
 2 , -OH, in which M +  represents a monovalent inorganic cation such as, for example, cesium (Cs + ), rubidium (Rb + ), potassium (K + ), lithium (Li + ), sodium (Na + ), copper (Cu + ), silver (Ag + ), ammonium (NH 4 
 + ) or mixtures thereof; or M +  represents a monovalent organic cation such as, for example, methylammonium (CH 3 NH 3 
 + ),  n -butylammonium (C 4 H 12 N + ), ethanolammonium (C 2 H 5 ONH 3 
 + ), diethanolammonium (C 4 H 12 N + ), triethanolammonium (C 6 H 15 O 3 NH + ), pyridinium (C 5 H 5 NH + ), monohydroxypyridinium (C 5 H 5 ONH + ), dihydroxypyridinium (C 5 H 5 NO 2 H + ) or mixtures thereof; preferably M +  is selected from potassium (K + ), sodium (Na + ), ammonium (NH 4 
 + ) or, more preferably, is ammonium (NH 4 
 + ). The above process allows for terpolymers to be obtained which are soluble in polar solvents such as, for example, water, methanol, ethanol, butanol, acetone or dimethyl sulfoxide. Said terpolymers can be advantageously used, for example, as additives for cements.