Modified polymers prepared with lanthanide-based catalysts
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, and reacting the pseudo-living polymer with at least one functionalizing agent defined by the formula (I) where A is a substituent that will undergo an addition reaction with a pseudo-living polymer, R 1 is a divalent organic group, R 2 is a monovalent organic group, and each R 4 , which may be the same or different, is a monovalent organic group or a substituent defined by —OR 5 where R 5 is a monovalent organic group, with the proviso that A, R 1 , R 2 , R 4 , and R 5 are substituents that will not protonate a pseudo-living polymer. Also, the functionalized polymer and a vulcanizable composition containing the polymer.
1. 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, where said pseudo-living polymer is characterized by having greater than about 85 percent of the polymer in the 1,4-cis microstructure and less than about 3 percent of the polymer is in the 1,2- or 3,4-microstructure; and
reacting the pseudo-living polymer with a functionalizing agent defined by the formula (I)
where A is a substituent that will undergo an addition reaction with a pseudo-living polymer, R 1 is a divalent organic group, R 2 is a monovalent organic group, and each R 4 , which may be the same or different, is a monovalent organic group or a substituent defined by —OR 5 where R 5 is a monovalent organic group, with the proviso that A, R 1 , R 2 , R 4 , and R 5 are substituents that will not protonate a pseudo-living polymer.
2. The polymer of claim 1 , where the functionalizing agent is defined by the formula (II)
where R 1 , R 2 , and R 4 are as defined above, R 6 is a divalent organic group, and R 8 and R 9 , which may be the same or different, are hydrogen atoms or monovalent organic groups, or, in the case where R 6 combines with R 8 , R 9 , or R 10 to form a cyclic group, or R 8 combines with R 9 or R 10 to form a cyclic group, R 6 may be a trivalent organic group and R 8 , R 9 , and R 10 may be divalent organic groups, with the proviso that these substituents will not protonate a pseudo-living polymer.
3. The polymer of claim 1 , where the functionalizing agent is defined by the formulas (III) & (IV)
where R 1 , R 2 , R 4 and R 6 are as defined above, and R 11 is a monovalent organic group, or, in the case where R 6 combines with R 11 to form a cyclic group, R 6 may be a trivalent organic group and R 11 may be a divalent organic group, with the proviso that these substituents will not protonate a pseudo-living polymer.
4. The polymer of claim 1 , where the functionalizing agent is defined by the formulas (V) or (VI)
where R 1 , R 2 , R 4 , R 6 , and R 11 are as defined above, and R 12 is a hydrogen atom or a monovalent organic group, with the proviso that at least one of R 12 or R 6 in formula (V) is attached to the imine carbon via a carbon atom, R 11 or R 12 in formula (VI) is attached to the imine carbon via a carbon atom, R 11 in formula (V) is attached to the imine nitrogen via a carbon atom, and R 6 in formula (VI) is attached to the imine nitrogen via a carbon atom, or, in the case where R 6 combines with R 11 or R 12 to form a cyclic group, or R 11 combines with R 12 to form a cyclic group, R 6 may be a trivalent organic group, and R 11 and R 12 may be divalent organic groups, with the proviso that these substituents will not protonate a pseudo-living polymer.
5. The polymer of claim 1 , where the functionalizing agent is defined by the formula (VII)
where R 1 , R 2 , R 4 , R 6 , and R 12 are as defined above, or, in the case where R 6 combines with R 12 to form a cyclic group, R 6 may be a trivalent organic group and R 12 may be a divalent organic group, with the proviso that these substituents will not protonate a pseudo-living polymer.
6. The polymer of claim 1 , where the functionalizing agent is defined by the formula (VIII)
where R 1 , R 2 , R 4 , and R 6 are as defined above, and where E is an oxygen atom or a sulfur atom, with the proviso that these substituents will not protonate a pseudo-living polymer.
7. The polymer of claim 1 , where the functionalizing agent is defined by the formulas (IX) or (X)
where R 1 , R 2 , R 4 , R 6 , and R 11 are as defined above, and R 13 is a monovalent organic group, or, in the case where R 6 combines with R 11 or R 13 to form a cyclic group, or R 11 and R 13 combine to form a cyclic group, R 6 may be a trivalent organic group and R 11 and R 13 may be divalent organic groups, with the proviso that these substituents will not protonate a pseudo-living polymer.
8. The polymer of claim 1 , further comprising the step of quenching the polymer.
9. The polymer of claim 2 , where the functionalizing agent comprises 3-glycidoxypropyltrimethoxysilane (GPMOS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EGMOS), 3-(trimethoxysilyl)propyl methacrylate, 3-glycidoxypropyl methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriisopropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)methyldimethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)methyldiethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)ethyldiethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)methyldiphenoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltriphenoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)ethyldiethoxysilane, (3-glycidoxypropyl)methyldiphenoxysilane, partial condensation products of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, partial condensation products of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, partial condensation products of 2-(3,4-epoxycyclohexyl)ethyltriisopropoxysilane, partial condensation products of 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, partial condensation products of 3-glycidoxypropyltrimethoxysilane, partial condensation products of 3-glycidoxypropyltriethoxysilane, partial condensation products of 3-glycidoxypropyltriisopropoxysilane, or partial condensation products of 3-glycidoxypropyltriphenoxysilane.
10. The polymer of claim 3 , where the functionalizing agent comprises 3-(trimethoxysilyl)propyl methacrylate, 3-(meth) acryloyloxypropyltrimethoxysilane (MPMOS), 3-(meth) acryloyloxypropyltriethoxysilane, 3-(meth) acryloyloxypropyltriisopropoxysilane, 3-(meth) acryloyloxypropyltriphenoxysilane, (3-(meth) acryloyloxypropyl)methyldimethoxysilane, (3-(meth) acryloyloxypropyl)methyldiethoxysilane, (3-(meth) acryloyloxypropyl)ethyldiethoxysilane, (3-(meth)acryloyloxypropyl)methyldiphenoxysilane, partial condensation products of 3-(meth)acryloyloxypropyltrimethoxysilane, partial condensation products of 3-(meth) acryloyloxypropyltriethoxysilane, partial condensation products of 3-(meth) acryloyloxypropyltriisopropoxysilane, or partial condensation products of 3-(meth) acryloyloxypropyltriphenoxysilane.
11. The polymer of claim 4 , where the functionalizing agent comprises N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (TEOSI) or N-(1,3-dimethylbutylidene)-(3-triethoxysilyl)-1-propaneamine (HAPEOS).
12. The method of claim 5 , where the functionalizing agent comprises 4-(3-(triethoxysilyl)propoxy)benzophenone, 4-(3-(triethoxysilyl)ethyl)benzophenone, 4,4′-bis ((3-triethoxysilyl)propoxy)benzophenone, trimethoxysilyl)propoxybenzophenone, or 4,4′-bis((3-trimethoxysilyl)propoxy)benzophenone.
13. A vulcanizable composition of matter comprising:
a rubber component comprising 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 where said pseudo-living polymer is characterized by having greater than about 85 percent of the polymer in the 1,4-cis microstructure and less than about 3 percent of the polymer is in the 1,2- or 3,4-microstructure; and
reacting the pseudo-living polymer with a functionalizing agent defined by the formula (I)
where A is a substituent that will undergo an addition reaction with a pseudo-living polymer, R 1 is a divalent organic group, R 2 is a monovalent organic group, and each R 4 , which may be the same or different, is a monovalent organic group or a substituent defined by —OR 5 where R 5 is a monovalent organic group, with the proviso that A, R 1 , R 2 , R 4 , and R 5 are substituents that will not protonate a pseudo-living polymer; and
a reinforcing filler including an inorganic filler.
14. The composition of claim 13 , where the functionalizing agent is defined by the formula (II)
where R 1 , R 2 , and R 4 are as defined above, R 6 is a divalent organic group, and R 8 and R 9 , which may be the same or different, are hydrogen atoms or monovalent organic groups, or, in the case where R 6 combines with R 8 , R 9 , or R 10 to form a cyclic group, or R 8 combines with R 9 or R 10 to form a cyclic group, R 6 may be a trivalent organic group and R 8 , R 9 , and R 10 may be divalent organic groups, with the proviso that these substituents will not protonate a pseudo-living polymer.
15. The composition of claim 13 , where the functionalizing agent is defined by the formulas (III) & (IV)
where R 1 , R 2 , R 3 , and R 6 are as defined above, and R 11 is a monovalent organic group, or, in the case where R 6 combines with R 11 to form a cyclic group, R 6 may be a trivalent organic group and R 11 may be a divalent organic group, with the proviso that these substituents will not protonate a pseudo-living polymer.
16. The composition of claim 13 , where the functionalizing agent comprises 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane (IPMOS), 3-isocyanatopropyltriisopropoxysilane, 3-isocyanatopropyltriphenoxysilane, (3-isocyanatopropyl)methyldimethoxysilane, (3-isocyanatopropyl)methyldiethoxysilane, (3-isocyanatopropyl)ethyldiethoxysilane, (3-isocyanatopropyl)methyldiphenoxysilane, partial condensation products of 3-isocyanatopropyltrimethoxysilane, partial condensation products of 3-isocyanatopropyltriethoxysilane, partial condensation products of 3-isocyanatopropyltriisopropoxysilane, or partial condensation products of 3-isocyanatopropyltriphenoxysilane.
17. The composition of claim 13 , where the functionalizing agent comprises tris(3-trimethoxysilylpropyl)isocyanulate, N-(3-trimethoxysilylpropyl)caprolactam, N(3-trimethoxysilylpropyl)pyrrolidone, tris (3-triethoxysilylpropyl)isocyanulate (TMOSPI), N(3-triethoxysilylpropyl)caprolactam, or N-(3-triethoxysilylpropyl)pyrrolidone.
18. The composition of claim 13 , where the functionalizing agent is defined by the formulas CV) or (VI)
where R 1 , R 2 , R 4 , R 6 , and R 11 are as defined above, and R 12 is a hydrogen atom or a monovalent organic group, with the proviso that at least one of R 12 or R 6 in formula (V) is attached to the imine carbon via a carbon atom, R 11 or R 12 in formula (VI) is attached to the imine carbon via a carbon atom, R 11 in formula (V) is attached to the imine nitrogen via a carbon atom, and R 6 in formula (VI) is attached to the imine nitrogen via a carbon atom, or, in the case where R 6 combines with R 11 or R 12 to form a cyclic group, or R 11 combines with R 12 to form a cyclic group, R 6 may be a trivalent organic group, and R 11 and R 12 may be divalent organic groups, with the proviso that these substituents will not protonate a pseudo-living polymer.
19. The composition of claim 13 , where the functionalizing agent is defined by the formula (VII)
where R 1 , R 2 , R 4 , R 6 , and R 12 are as defined above, or, in the case where R 6 combines with R 12 to form a cyclic group, R 6 may be a trivalent organic group and R 12 may be a divalent organic group, with the proviso that these substituents will not protonate a pseudo-living polymer.
20. The composition of claim 13 , where the functionalizing agent is defined by the formula (VIII)
where R 1 , R 2 , R 4 , and R 6 are as defined above, and where E is an oxygen atom or a sulfur atom, with the proviso that these substituents will not protonate a pseudo-living polymer.