Silane-containing carboxy-terminated polymers
View Patent ↗Polymers are functionalized at chain ends thereof with silane-containing carboxyl groups of the formula (I) where R 1 and R 2 are the same or different and are each an H, alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, alkaryl, alkaryloxy, aralkyl or aralkoxy radical; R 3 and R 4 are the same or different and are each an H, alkyl, cycloalkyl, aryl, alkaryl or aralkyl radical; and A is a divalent organic radical.
1. End group-functionalized polymers comprising a polymer chain terminated by a silane-containing carboxyl group of the formula (I)
wherein the silane containing carboxyl group is bonded with the polymer chain via one or more divalent structural elements of the formula (V)
where
R is H,
R 1 , R 2 are the same or different and are each an H, alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, alkaryl, alkaryloxy, aralkyl, or aralkoxy radical
R 3 , R 4 are the same or different and are each an H, alkyl, cycloalkyl, aryl, alkaryl or aralkyl radical,
A is a divalent organic radical,
n=3-6, and
R 5 , R 6 are the same or different and are each an H, alkyl, cycloalkyl, aryl, alkaryl or aralkyl radical wherein the polymers are diene polymers or diene copolymers.
2. The end group-functionalized polymers according to claim 1 , wherein the polymer is obtained by reaction of reactive ends of the polymer chain with one or more silalactone functionalizing reagents, wherein the silalactones are compounds of the formula (III)
3. The end group-functionalized polymers according to claim 2 , wherein:
any alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, alkaryl, alkaryloxy, aralkyl, aralkoxy, or divalent organic radical may contain one or more heteroatoms;
the silalactones are compounds of the formula (III)
and
the one or more divalent structural elements of the formula (V) are derived from cyclosiloxanes of the formula (IV)
4. The end group-functionalized polymers according to claim 3 , wherein:
the heteroatoms are O, N, S and Si;
the cyclosiloxanes are a member of the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, or dodecamethylcyclcohexasiloxane;
the silalactones comprise one or more of 2,2-diethyl-1-oxa-2-silacyclohexan-6-one, 2,2,4-trimethyl-1-oxa-2-silacyclohexan-6-one, 2,2,5-trimethyl-1-oxa-2-silacyclohexan-6-one, 2,2,4,5-tetramethyl-1-oxa-2-silacyclohexan-6-one, 2,2-diethyl-1-oxa-2-silacyclohexan-6-one, 2,2-diethoxy-1-oxa-2-silacyclohexan-8-one, 2,2-dimethyl-1,4-dioxa-2-silacyclohexan-6-one, 2,2,5-trimethyl-1,4-dioxa-2-silacyclohexan-6-one, 2,2,3,3-tetramethyl-1,4-dioxa-2-silacyclohexan-6-one, 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one, 2,2-diethyl-1-oxa-4-thia-2-silacyclohexan-6-one, 2,2-diphenyl-1-oxa-4-thia-2-silacyclohexan-6-one, 2-methyl-2-ethenyl-1-oxa-4-thia-2-silacyclohexan-6-one, 2,2,5-trimethyl-1-oxa-4-thia-2-silacyclohexan-8-one, 2,2-dimethyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,4-dimethyl-2-phenyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2-dimethyl-4 trimethylsilyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2-diethoxy-4-methyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2,4,4-tetramethyl-1-oxa-2,4-disilacyclohexane-6-one, 3,4-dihydro-3,3-dimethyl-1H-2,3-benzoxasilin-1-one, 2,2-dimethyl-1-oxa-2-silacyclopentan-5-one, 2,2,3-trimethyl-1-oxa-2-silacyclopentan-5-one, 2,2-dimethyl-4-phenyl-1-oxa-2-silacyclopentan-5-one, 2,2-di(tert-butyl)-1-oxa-2-silacyclopentan-5-one, 2-methyl-2-(2-propen-1-yl)-1-oxa-2-silacyclopentan-5-one, 1,1-dimethyl-2,1-benzoxasilol-3(1H)-one, and 2,2-dimethyl-1-oxa-2-silacycloheptan-7-one;
the polymers comprise at least one of polybutadiene, polyisoprene, butadiene-isoprene copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, and butadiene-isoprene-styrene terpolymer; and
the polymers have mean molar masses of 100,000 to 1,000,000 g/mol, and glass transition temperatures of −110° C. to 0° C.
5. The end group-functionalized polymers according to claim 1 , wherein the polymers have mean molar masses of 10,000 to 2,000,000 g/mol.
6. The end group-functionalized polymers according to claim 1 , wherein the polymers have glass transition temperatures of −110° C. to +20° C.
7. A process for preparing the end group-functionalized polymers according to claim 1 , the process comprising adding one or more silalactones to polymers having reactive ends on the polymer chain.
8. The process according to claim 7 , further comprising adding the silalactones to the polymers after completion of polymerization.
9. The process according to claim 7 , further comprising using an excess or a stoichiometric amount or a deficiency of silalactones, based on the amount of polymer.
10. The process according to claim 9 , wherein the amount of silalactones is from 0.005 to 2% by weight, based on the amount of polymer.
11. The process according to claim 7 , wherein prior to addition of the silalactones, the process further comprises:
polymerizing monomers to form polymer chains having reactive chain ends, and
reacting reactive chain ends with cyclosiloxanes of the formula (IV)
where n=3-6, and
where R 5 , R 6 in formula (IV) are the same or different and are each an H, alkyl, cycloalkyl, aryl, alkaryl or aralkyl radical.
12. The process according to claim 11 , further comprising reacting the reactive chain ends with 0.002 to 4% by weight of the cyclosiloxanes of the formula (IV) based on the amount of polymer.
13. The process according to claim 11 , wherein a ratio of silalactone to cyclosiloxane is from 20:1 to 1:1.
14. Vulcanizable rubber compositions comprising:
a) end group-functionalized polymers according to claim 1 , and
b) ageing stabilizers, oils, fillers, rubbers and/or further rubber auxiliaries.
15. Mouldings produced from vulcanizable rubber compositions comprising the end group-functionalized polymers according to claim 1 .