Functionalized high
A functionalized polymer prepared by a process comprising the steps of preparing a pseudo-living polymer by polymerizing conjugated monomer with a lanthanide-based catalyst, and reacting the pseudo-living polymer with a functionalizing agent defined by the formula (I) A-R 1 -Z (I) where R 1 is a divalent bond or divalent organic group comprising from 0 to about 20 carbon atoms, A is a substituent that will undergo an addition reaction with a pseudo-living polymer, and Z is a substituent that will react or interact with silica or carbon black reinforcing fillers, with the proviso that A, R 1 , and Z are substituents that will not protonate a pseudo-living polymer.
1. A method for preparing a functionalized polymer comprising the steps of:
preparing a pseudo-living polymer by polymerizing conjugated diene monomer with a lanthanide-based catalyst wherein the lanthanide-based catalyst comprises (a) a lanthanide compound, (b) an alkyl aluminoxane, and (c) a source of halogen; and
reacting the pseudo-living polymer with a functionalizing agent defined by the formula:
where R 1 is a divalent bond or divalent organic group comprising from 0 to about 20 carbon atoms, R 2 is a divalent organic group or trivalent organic group in the case where R 2 combines with R 3 to form a cyclic group, R 3 is a hydrogen atom, a monovalent organic group, or, in the case where R 3 combines with R 2 , R 3 may be a divalent organic group, and Z is selected from the group consisting of N,N-disubstituted aminophenyl groups, cyclic amino groups, imine groups, amide groups, isocyanate groups, isothiocyanate groups, and epoxy groups, with the proviso that R 1 , R 2 , R 3 , and Z are substituents that will not protonate a pseudo-living polymer.
2. The method of claim 1 , where Z is an N,N-disubstituted aminophenyl group.
3. The method of claim 2 , wherein (b) comprises an alkyl aluminoxane or a mixture of an alkyl aluminoxane and a trialkylaluminum, dialkylaluminum hydride, or alkylaluminum dihydride.
4. The method of claim 2 , wherein the pseudo-living polymer is prepared in the absence of phosphorus-containing compounds.
5. The method of claim 1 , where the functionalizing agent comprises 4,4′-bis(N,N-dimethylamino)benzophenone, 4,4′-bis(N,N-diethylamino)benzophenone, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-diethylamino)benzophenone, (4-N,N-dimethylaminophenyl)methyl ethyl ketone, 4,4′-bis(1-hexamethyleneiminomethyl) benzophenone, 4,4′-bis(1-pyrolidinomethyl) benzophenone, 4-(1-hexamethyleneiminomethyl) benzophenone, 4-(1-pyrolidinomethyl) benzophenone, or (4-(1-hexamethyleneimino)phenyl)methyl ethyl ketone.
6. The method of claim 1 , where the functionalizing agent comprises 4-(N,N-dimethylamino)benzaldehyde, 4-(N,N-diethylamino)benzaldehyde, 4-(1-hexamethyleneiminomethyl) benzaldehyde, or 4-(1-pyrolidinomethyl) benzaldehyde.
7. The method of claim 6 , prepared in the absence of aluminoxane compounds.
8. The method of claim 1 , wherein the lanthanide-based catalyst comprises (a) neodymium neodecanoate; (b) methylaluminoxane and diisobutylaluminum hydride; and (c) diethylaluminum chloride.
9. The method of claim 1 , wherein the conjugated diene monomer is 1,3-butadiene.
10. The method of claim 9 , wherein the functionalizing agent is 4,4′bis(N,N-diethylamino)benzophenone.
11. The method of claim 9 , wherein the functionalizing agent is 4,4′bis(N,N-dimethylamino)benzophenone.
12. A method for preparing a functionalized polymer comprising the steps of:
preparing a pseudo-living polymer by polymerizing conjugated diene monomer with a lanthanide-based catalyst, wherein the lanthanide-based catalyst comprises (a) a lanthanide compound, (b) an alkyl aluminoxane or a mixture of an alkyl aluminoxane and a trialkylaluminum, dialkylaluminum hydride, or alkylaluminum dihydride, and (c) a source of halogen; and
reacting the pseudo-living polymer with a functionalizing agent defined by the formula:
where R 1 is a divalent bond or divalent organic group comprising from 0 to about 20 carbon atoms, R 2 is a divalent organic group or trivalent organic group in the case where R 2 combines with R 3 to form a cyclic group, R 3 is a hydrogen atom, a monovalent organic group, or, in the case where R 3 combines with R 2 , R 3 may be a divalent organic group, and Z is a substituent that will react or interact with silica or carbon black reinforcing fillers.
13. The method of claim 12 , wherein the lanthanide-based catalyst comprises (a) neodymium neodecanoate; (b) methylaluminoxane and diisobutylaluminum hydride; and (c) diethylaluminum chloride.
14. The method of claim 12 , wherein the conjugated diene monomer is 1,3-butadiene.
15. The method of claim 14 , wherein the functionalizing agent is 4,4′bis(N,N-diethylamino)benzophenone.
16. The method of claim 14 , wherein the functionalizing agent is 4,4′bis(N,N-dimethylamino)benzophenone.