Polymers of conjugated dienes which have terminal conjugated unsaturated alicyclic functional groups
AssigneePhillips Petroleum Company
InventorsCarl A. Uraneck, John E. Burleigh
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Abstract
Alicyclic organomonolithium compounds having delocalized conjugated unsaturation are effective initiators in the preparation of polymers of conjugated dienes. Polymers of conjugated dienes, prepared with or without the alicyclic organomonolithium compounds, are terminated with alicyclic compounds having conjugated unsaturation. Either or both approaches can be used to provide polymers containing alicyclic conjugated unsaturated functional groups. Alternatively, polymers prepared from the alicyclic organomonolithium compounds can be coupled to produce linear or branched polymers. Polymers prepared from multichelic lithium compounds also can be terminated with alicyclic conjugated unsaturated compounds.
Claims46
The process for the preparation of a conjugated diene polymer containing alicyclic conjugated unsaturated functional groups which comprises:
- (a) polymerizing at least one conjugated diene hydrocarbon monomer, optionally further employing a hydrocarbon monovinylarene comonomer, employing an organolithium initiator, under anionic solution polymerization conditions, thereby preparing a polymerization admixture containing a conjugated diene polymer containing active lithium termination,
- wherein said organolithium initiator is selected from the group consisting of (B) hydrocarbyl monolithium initiators, and (C) hydrocarbonic lithium multichelic initiators, and therefore (b) treating said polymerization admixture by treating mode (E),
- wherein said treating mode (E) employs at least a stoichiometric amount an alicyclic unsaturated triene or tetraene selected from the group consisting of ##STR9## wherein R' is hydrogen or alkyl such that the total number of carbon atoms in the molecule does not exceed 20, and R" is R', chlorine, bromine, or iodine, with the proviso that only one R" is halogen in each molecule of said (III) or (IV), thereby resulting in a conjugated diene polymer containing terminal conjugated unsaturation.
The process according to claim 10 wherein said monovinylarene comonomer is styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-n-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, or 4-(4-phenyl-n-butyl)styrene.
A conjugated diene polymer containing alicyclic conjugated unsaturated functional groups selected from the group consisting of conjugated diene homopolymers, conjugated diene copolymers, and copolymers of at least one conjugated diene with at least one monovinylarene, prepared by the process which comprises:
- (a) polymerizing at least one conjugated diene hydrocarbon monomer, optionally with a hydrocarbon monovinylarene comonomer, employing an organolithium initiator, under anionic solution polymerization conditions, thereby preparing a polymerization admixture containing conjugated diene polymer containing active lithium termination,
- wherein said organolithium initiator is selected from the group consisting of hydrocarbyl monolithium initiators, and (C) hydrocarbonic lithium multichelic initiators, and ##STR10## wherein R' is hydrogen or alkyl such that the total number of carbon atoms in the molecule does not exceed 20,
- and therefore (b) treating said polymerization admixture by treating mode (E), said treating mode (E) employs an alicyclic unsaturated triene or tetraene compound selected from the group consisting of ##STR11## wherein R' is hydrogen or alkyl such that the total number of carbon atoms in the molecule does not exceed 20, and R" is R', chlorine, bromine, or iodine, with the proviso that only one R" is halogen in each molecule of said (III) or (IV), thereby producing a conjugated diene polymer containing terminal conjugated unsaturation.
Dependencies are inferred from the claim text.