Supramolecular polymers from low-melting, easily processable building blocks

Abstract

PCT The present invention relates to a supramolecular polymer comprising 1-50 4H-units, said supramolecular polymer being obtainable by reacting at least one monomeric building block with a prepolymer. The present invention further relates to articles or compositions comprising the supramolecular polymer, in particular articles or compositions selected from the group consisting of decorative, thermo-reversible, or self-healing coatings, adhesive compositions, sealing compositions, thickeners, gelators and binders.

1 . A supramolecular polymer comprising 1-50 4H-units, said supramolecular polymer being obtainable by reacting at least one monomeric building block selected from the group consisting of monomeric building blocks (I)-(VI) with a prepolymer P—(F i ) n , 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is selected from the group consisting of hydrogen, cyclic, linear or branched C 2 -C 20  alkyl groups, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; 
         R 2  and R 3  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 20  alkyl groups, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; with the proviso that R 1  and R 2  are not both hydrogen; 
         A is a linking moiety that is selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         B 1  is a linking moiety that is independently selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         D is —OH, —SH, —NH 2  or —NHR 4 , wherein R 4  is selected from the group consisting of cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups; 
         X is independently selected from the group consisting of —NCO, —OH, —SH, —NHR 5 , oxiranyl, —C(Z)ZR 6  and —C(Z)NHR 6 , wherein R 5  and R 6  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups and wherein Z is independently O or S; and 
         P represents a polymeric or oligomeric chain, 
         F i  represents a group that is complementary reactive with X, and 
         n represents the average number of the groups F i  in P and is in the range of 1 to 10,000. 
       
     
     
         2 . The supramolecular polymer according to  claim 1 , wherein the monomeric building block is selected from the group consisting of monomeric building blocks (I), (III), (IV) and (VI). 
     
     
         3 . The supramolecular polymer according to  claim 1 , wherein the monomeric building block is monomeric building block (I). 
     
     
         4 . The supramolecular polymer according to  claim 1 , wherein n is 2 to 50. 
     
     
         5 . The supramolecular polymer according to  claim 1 , wherein the prepolymer P—(F i ) n  has an average molecular weight of 100-10,000. 
     
     
         6 . A process for the preparation of a supramolecular polymer, said process comprising reacting at least one monomeric building block selected from the group consisting of monomeric building blocks (I)-(VI) with a prepolymer P—(F i ) n , 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is selected from the group consisting of hydrogen, cyclic, linear or branched C 2 -C 20  alkyl groups, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; 
         R 2  and R 3  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 20  alkyl groups, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; with the proviso that R 1  and R 2  are not both hydrogen; 
         A is a linking moiety that is selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         B 1  is a linking moiety that is independently selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         D is —OH, —SH, —NH 2  or —NHR 4 , wherein R 4  is selected from the group consisting of cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups; 
         X is independently selected from the group consisting of —NCO, —OH, —SH, —NHR 5 , oxiranyl, —C(Z)ZR 6  and —C(Z)NHR 6 , wherein R 5  and R 6  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, and wherein Z is independently O or S; and 
         P represents a polymeric or oligomeric chain, 
         F i  represents a group that is complementary reactive with X, and 
         n represents the average number of the groups F i  in P and is in the range of 1 to 10,000. 
       
     
     
         7 . The process according to  claim 6 , wherein the reacting is performed in the melt. 
     
     
         8 . The process according to  claim 6 , wherein the reacting is performed at a temperature below 150° C. 
     
     
         9 . The process according to  claim 6 , wherein the monomeric building block is selected from the group consisting of monomeric building blocks (I), (III), (IV) and (VI). 
     
     
         10 . The process according to  claim 6 , wherein the monomeric building block is monomeric building block (I). 
     
     
         11 . The process according to  claim 6 , wherein n is 2 to 50. 
     
     
         12 . The process according to  claim 6 , wherein the prepolymer P—(F i ) n  has an average molecular weight of 100-10,000. 
     
     
         13 . A composition comprising the supramolecular polymer according to  claim 1 . 
     
     
         14 . A composition according to  claim 13 , wherein the composition is selected from the group consisting of coatings, adhesive compositions, sealing compositions, thickeners, gelators and binders. 
     
     
         15 . A composition according to  claim 14 , wherein the coating is a decorative coating, thermo-reversible coating, or self-healing coating. 
     
     
         16 . (canceled) 
     
     
         17 . A monomeric building block according to formulae (I)-(VI), enantiomers, diastereomers and tautomers thereof: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is selected from the group consisting of hydrogen, cyclic, linear or branched C 7 -C 20  alkyl groups, C 6 -C 70  aryl groups, C 7 -C 70  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, R 2  and R 3  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 20  alkyl groups, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl groups and arylalkyl groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; with the proviso that R 1  and R 2  are not both hydrogen; 
         A is a linking moiety that is selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         B 1  is a linking moiety that is independently selected from the group consisting of linear, cyclic or branched C 1 -C 20  alkylene and C 6 -C 20  arylene groups, wherein the alkylene and arylene groups optionally comprise 1-5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the arylene groups are optionally substituted with one or more linear or branched C 1 -C 20  alkyl, alkylene groups, or both; 
         D is —OH, —SH, —NH, or —NHR 4 , wherein R 4  is selected from the group consisting of cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 10  alkaryl groups and C 7 -C 10  arylalkyl groups; and 
         X is independently selected from the group consisting of —NCO, —OH, —SH, oxiranyl, —C(Z)ZR 6  and —C(Z)NHR 6 , wherein R 5  and R 6  are independently selected from the group consisting of hydrogen, cyclic, linear or branched C 1 -C 6  alkyl, C 6 -C 20  aryl groups, C 7 -C 20  alkaryl groups and C 7 -C 20  arylalkyl groups, and wherein Z is independently O or S.