Catalyst for the preparation of polyurethanes
Novel thermolatent bases and their use as catalysts for the preparation of polyurethanes or epoxy resins are disclosed herein. A process for the preparation of polyurethanes or epoxy resins in the presence of the catalyst is also disclosed.
1. A process for preparing a polyurethane comprising reacting at least one polyisocyanate with a polyol composition, wherein the polyol composition comprises at least one polyol and a catalyst composition;
wherein the catalyst composition comprises at least one compound (C) selected from the group consisting of compounds of the general formula (Ia) and compounds of the general formula (Ib)
wherein
n is 0 or 1 when X is a carbon atom,
n is 2 when X is a sulfur atom,
n′ is 0 or 1,
m is an integer from 1 to 6,
R is H, OH, substituted or unsubstituted, linear or branched C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl which can be substituted by OH, OR 1 or NR 2 R 3 , and which may be interrupted by one or more —O—, —S— or —NR 4 —;
R′ is linear or branched C 1 -C 5 alkyl substituted by NHR 2 ,
B is a nitrogen containing organic base,
L is C 1 -C 8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted C 6 cycloalkylene chain, or substituted or unsubstituted C 9 -C 11 polycyclic chain, or a substituted or unsubstituted double bond, which can be interrupted by O, S, NR 4 , or a substituted or unsubstituted C 3 to C 4 alkenylene chain, or a substituted or unsubstituted benzene ring, or substituted or unsubstituted naphthalene ring,
R 1 is H, C 1 -C 18 alkyl,
R 2 and R 3 , independently are hydrogen, unsubstituted or substituted C 1 -C 18 alkyl or phenyl; or R 2 and R 3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom,
R 4 is H, unsubstituted or substituted C 1 -C 18 alkyl,
the ratio between A a and B a or between A b and B b ranges from 0.5:1 to 10:1.
2. The process according to claim 1 , wherein the compound (C) is selected from the group consisting of compounds of the general formula (Ia) and compounds of the general formula (Ib)
wherein
n is 1 when X is a carbon atom,
n is 2 when X is a sulfur atom,
n′ is 0 or 1,
m is 1 or 2,
R is H, OH, linear or branched C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl which may be interrupted by one or more —O—, —S— or —NR 4 —;
R′ is linear or branched C 1 -C 5 alkyl substituted by NHR 2 ,
B is substituted or unsubstituted 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN), Triazabycyclodecene (TBD), 1,4-Diazabicyclo[2.2.2]octan (DABCO), 1,1,3,3-tetramethylguanidine (TMG), or substituted or unsubstituted tertiary aliphatic amines,
L is C 1 -C 8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted double bond, or a substituted or unsubstituted C 3 to C 4 alkenylene chain, or has the formula:
when m is 1 or has the formula:
when m is 2
R 5 , R 6 , R 7 , R 8 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 5 -C 16 heteroaralkyl, phenyl or naphthyl, OR 1 , NR 2 R 3 , or halogen,
or
R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more —O—, —S— or —NR 4 —;
R 1 is H, C 1 -C 18 alkyl,
R 2 , R 3 , independently are hydrogen, unsubstituted or substituted C 1 -C 18 alkyl or phenyl; or R 2 and R 3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom,
R 4 is H, unsubstituted or substituted C 1 -C 18 alkyl,
the ratio between A a and B a or between A b and B b ranges from 1:1 to 4:1.
3. The process according to claim 1 , wherein the compound (C) is selected from the group consisting of compounds of the general formula (I′a) and compounds of the general formula (I′b)
wherein
n is 1 when X is a carbon atom,
n is 2 when X is a sulfur atom,
n′ is 0 or 1,
R is H, linear or branched C 1 -C 18 alkyl or C 5 -C 7 cycloalkyl,
R′ is linear or branched C 1 -C 5 alkyl substituted by NH 2 or NH(C 1 -C 18 alkyl),
B is 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN), Triazabycyclodecene (TBD), 1,4-Diazabicyclo[2.2.2]octan (DABCO), 1,1,3,3-tetramethylguanidine (TMG), or tertiary aliphatic amines,
L is C 1 -C 8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted double bond, or a substituted or unsubstituted C 3 to C 4 alkenylene chain, or has the formula:
R 5 , R 6 , R 7 , R 8 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 5 -C 16 heteroaralkyl, phenyl or naphthyl, OR 1 , NR 2 R 3 , or halogen,
or
R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more —O—, —S— or —NR 4 —;
R 1 is H, C 1 -C 18 alkyl,
R 2 , R 3 , independently are hydrogen, unsubstituted or substituted C 1 -C 18 alkyl or phenyl; or R 2 and R 3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom,
R 4 is H, unsubstituted or substituted C 1 -C 18 alkyl,
the ratio between A a and B a or between A b and B b ranges from 1:1 to 4:1.
4. The process according to claim 1 , wherein the compound (C) is selected from the group consisting of compounds of the general formula (I″a) and compounds of the general formula (I″b)
wherein
R is H, linear or branched C 1 -C 18 alkyl or C 5 -C 7 cycloalkyl,
R′ is linear or branched C 1 -C 5 alkyl substituted by NH 2 or NH(C 1 -C 18 alkyl),
B is 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN), Triazabycyclodecene (TBD), 1,4-Diazabicyclo[2.2.2]octan (DABCO), 1,1,3,3-tetramethylguanidine (TMG), or tertiary aliphatic amines,
L is a C 1 to C 8 substituted or unsubstituted alkylene chain, or has the formula:
R 5 , R 6 , R 7 , R 8 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 5 -C 16 heteroaralkyl, phenyl or naphthyl, OR 1 , NR 2 R 3 , or halogen,
or
R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more —O—, —S— or —NR 4 —;
R 1 is H, C 1 -C 18 alkyl,
R 2 , R 3 , independently are hydrogen, unsubstituted or substituted C 1 -C 18 alkyl or phenyl; or R 2 and R 3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom,
R 4 is H, unsubstituted or substituted C 1 -C 18 alkyl,
the ratio between A a and B a or between A b and B b ranges from 1:1 to 4:1.
5. The process according to claim 1 , wherein the compound (C) is selected from the group consisting of compounds of the general formula (I″a) and compounds of the general formula (I″b)
wherein
R is H, linear or branched C 1 -C 18 alkyl or C 5 -C 7 cycloalkyl,
R′ is linear or branched C 1 -C 5 alkyl substituted by NH 2 or NH(C 1 -C 18 alkyl),
B is 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU),
L is a C 1 to C 8 substituted or unsubstituted alkylene chain, or has the formula:
R 5 , R 6 , R 7 , R 8 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 5 -C 16 heteroaralkyl, phenyl or naphthyl, OR 1 , NR 2 R 3 , or halogen,
or
R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more —O—, —S— or —NR 4 —;
R 1 is H, C 1 -C 16 alkyl,
R 2 , R 3 , independently are hydrogen, unsubstituted or substituted C 1 -C 18 alkyl or phenyl; or R 2 and R 3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom,
R 4 is H, unsubstituted or substituted C 1 -C 18 alkyl,
the ratio between A a and B a or between A b and B b ranges from 1:1 to 4:1.
6. The process according to claim 1 , wherein the catalyst composition comprises at least one further catalyst.
7. The process according to claim 1 , wherein the at least one polyisocyanate is selected from MDI, polymeric MDI, and TDI, and also derivatives thereof or prepolymers of these polyisocyanates.