Silane-terminated polydiorganosiloxane urethane copolymer
View Patent ↗Curable, silane-terminated polydiorganosiloxane-urethane copolymers exhibit the beneficial properties of isocyanate-terminated polysiloxane-urethane copolymers without the detriments associated with free isocyanate groups.
1. A silane-terminated polydiorganosiloxane-urethane copolymer of the formula 1,
wherein R is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
X is an alkylene radical having 1 to 20 carbon atoms in which non-adjacent methylene units are optionally replaced by —O—,
A is an oxygen atom or an amino group —NR′—,
R′ is hydrogen or an alkyl radical having 1 to 10 carbon atoms,
Y is a hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
D is an alkylene radical optionally substituted by fluorine, chlorine, C 1 –C 6 -alkyl or C 1 –C 6 -alkyl ester and having 1 to 700 carbon atoms, in which non-adjacent methylene units are optionally replaced by —O—, —COO—, —OCO—, or —OCOO—,
B is a radical of the formula 2
-Z-Si(R 1 ) m (R″) 3-m , (2),
wherein
Z is an alkylene radical having 1 to 10 carbon atoms,
R 1 is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 12 carbon atoms,
R″ is a moisture-reactive radical selected from the group consisting of C 1 –C 4 -alkoxy, C 1 –C 20 -acyl, C 1 –C 6 -alkylaminooxy, and C 1 –C 6 -alkyloximo radicals,
W is a radical B or hydrogen,
m is 0, 1 or 2,
n is an integer from 1 to 2000,
a is an integer of at least 1,
b is 0 or an integer from 1 to 2000,
c is an integer from 1 to 30, and
d is 0 or 1,
with the proviso that, based on the sum of urethane groups and urea groups, at least 30 mol % of urethane groups are present.
2. The copolymer of claim 1 , wherein n is an integer from 3 to 400.
3. The copolymer of claim 1 , wherein a is an integer of not more than 10.
4. A silane-terminated polydiorganosiloxane-urethane copolymer of the formula 1,
wherein R is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
X is an alkylene radical having 1 to 20 carbon atoms in which non-adjacent methylene units are optionally replaced by —O—,
A is an oxygen atom or an amino group —NR′—,
R′ is hydrogen or an alkyl radical having 1 to 10 carbon atoms,
Y is a hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
D is an alkylene radical optionally substituted by fluorine, chlorine, C 1 –C 6 -alkyl or C 1 –C 6 -alkyl ester and having 1 to 700 carbon atoms, in which non-adjacent methylene units are optionally replaced by —O—, —COO—, —OCO—, or —OCOO—,
B is a radical of the formula 2
-Z-Si(R 1 ) m (R″) 3-m , (2),
wherein
Z is an alkylene radical having 1 to 10 carbon atoms,
R 1 is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 12 carbon atoms,
R″ is a moisture-reactive radical selected from the group consisting of C 1 –C 4 -alkoxy, C 1 –C 20 -acyl, C 1 –C 6 -alkylaminooxy, and C 1 –C 6 -alkyloximo radicals,
W is a radical B or hydrogen,
m is 0, 1 or 2,
n is an integer from 1 to 2000,
a is an integer of at least 1,
b is 0 or an integer from 1 to 2000,
c is an integer from 1 to 30, and
d is 0 or 1,
with the proviso that, based on the sum of urethane groups and urea groups, at least 30 mol % of urethane groups are present wherein b is 0.
5. The copolymer of claim 1 , wherein Y is an alkylene radical.
6. The copolymer of claim 1 , containing, based on the sum of the urethane groups and urea groups, at least 50 mol % of urethane groups.
7. The copolymer of claim 1 , wherein A is an oxygen atom.
8. A process for preparing the copolymer of claim 1 , wherein aminoalkyl- or hydroxyalkyl-terminated polydiorganosiloxanes of the general formula 3
are reacted with diisocyanates of the general formula 4
OCN—Y—NCO (4),
and silanes of the general formula 5
E[-Z-Si(R 1 ) m (R″) 3-m ] p (5),
and, if b is at least 1, additionally with α,ω-OH-terminated alkylenes of the general formula 6
HO-D-OH (6),
where
p is 1, and
E is an isocyanate group or an amino group —NHR′″, in which R′″ is hydrogen or a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 12 carbon atoms, or
p is 2 and
E is an —NH radical.
9. A process for preparing a copolymer of the formula 1
wherein R is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
wherein R is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
X is an alkylene radical having 1 to 20 carbon atoms in which non-adjacent methylene units are optionally replaced by —O—,
A is an oxygen atom or an amino group —NR′—,
R′ is hydrogen or an alkyl radical having 1 to 10 carbon atoms,
Y is a hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 20 carbon atoms,
D is an alkylene radical optionally substituted by fluorine, chlorine, C 1 –C 6 -alkyl or C 1 –C 6 -alkyl ester and having 1 to 700 carbon atoms, in which non-adjacent methylene units are optionally replaced by —O—, —COO—, —OCO—, or —OCOO—,
B is a radical of the formula 2
-Z-Si(R 1 ) m (R″) 3-m , (2),
wherein
Z is an alkylene radical having 1 to 10 carbon atoms,
R 1 is a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine and having 1 to 12 carbon atoms,
R″ is a moisture-reactive radical selected from the group consisting of C 1 –C 4 -alkoxy, C 1 –C 20 -acyl, C 1 –C 6 -alkylaminooxy, and C 1 –C 6 -alkyloximo radicals,
W is a radical B or hydrogen,
m is 0, 1 or 2,
n is an integer from 1 to 2000,
a is an integer of at least 1,
b is 0 or an integer from 1 to 2000,
c is an integer from 1 to 30, and
d is 0 or 1,
with the proviso that, based on the sum of urethane groups and urea groups, at least 30 mol % of urethane groups are present,
wherein aminoalkyl- or hydroxyalkyl-terminated polydiorganosiloxanes of the general formula 3
are reacted with diisocyanates of the general formula 4
OCN—Y—NCO (4),
and silanes of the general formula 5
E[-Z-Si(R 1 ) m (R″) 3-m ] p (5),
and, if b is at least 1, additionally with α,ω-OH-terminated alkylenes of the general formula 6
HO-D-OH (6),
where
p is 1, and
E is an isocyanate group.
10. A moisture-curing composition, comprising at least one copolymer of claim 1 .
11. An adhesive, comprising at least one copolymer of claim 1 .
12. A thermoplastic elastomer, comprising as at least one component thereof, a copolymer of claim 1 .
13. A vulcanizable elastomer composition, comprising as at least one component thereof, a copolymer of claim 1 .
14. In a polymer blend containing a curable additive, the improvement comprising selecting as at least one curable additive, a copolymer of claim 1 .
15. A coating, comprising a copolymer of claim 1 or a cured reaction product thereof.
16. A biocompatible material comprising a copolymer of claim 1 or a cured reaction product thereof.
17. The process of claim 8 , which is conducted in the absence of water.
18. The process of claim 8 , which is conducted in the absence of solvent.
19. The process of claim 8 , which is conducted both in the absence of solvent and of water.
20. The process of claim 8 , wherein the copolymer is a liquid.
21. The copolymer of claim 1 , which is a liquid.