Coupled hydrocarbon polymers and process for their preparation

Claim 2

A process to couple a living polymer having the formula wherein Q is a hydrocarbon polymer having one alkali metal atom M terminally attached thereto with a coupling agent in order to chemically connect such living polymer molecules to form larger polymer molecules, characterized in that said coupling comprises two coupling steps of (a) in a first coupling step reacting said living polymer Q - M with a non-terminating first coupling agent such as to form an initial living coppled polymer having the formula wherein Q represents one of m' polymer chains Q coupled via the coupling unit X which is derived from said non-terminating first coupling agent, and m' and m are integers essentially equal to each other, (b) in a second coupling step further coupling said coupled living polymer Q m , - X - M m with a second coupling agent to form a further coupled polymer.

Claim 3

A process according to claim 1) characterized in that said living polymer has the formula wherein E represents a block selected from the group of poly- a monovinylarene blocks from monovinylarenes having from 8 to 20 carbon atoms per molecule, and hydrogenated low vinyl polybutadiene blocks and D consists of one or more homopolymer or copolymer blocks of alkadienes having 4 - 12 carbon atoms per molecule, said section D contributing to rubbery properties of the coupled polymer.

Claim 4

A process in accordance with claim 1) or 2) characterized in that a polyvinyl aromatic compound selected from the group defined by the following general formulae is used as said non-terminating first coupling agent, wherein Y is a vinyl group, R' is selected from the group consisting of hydrogen, and alkyl groups containing from 1 to 4 carbon atoms with the total of actual substituents having not more than 12 carbon atoms, n is an integer of 2 or 3 and the vinyl substituents in the formula (b) and (c) being attached to one or both of the aromatic rings and in that said second coupling agent is selected from the group consisting of carbon monoxide, carbon dioxide, α,α-dichloro-p-xylene, methyl methacrylate and dimethyl dichlorosilane.

Claim 5

'4. A process in accordance with one of claims 1) to 3) characterized by at least partially hydrogenating the olefinic unsaturations of the coupled polymer while leaving the aromatic unsaturations essentially unchanged by contacting the final coupled polymer with hydrogen and a hydrogenation catalyst under hydrogenation conditions, and recovering a hydrogenated coupled polymer as the product of the process.

Claim 6

A process in accordance with one of claims 1) to 4) characterized in that said living polymer Q - M is produced by polymerizing the monomers in at least one polymerization step under polymerization conditions in a hydrocarbon diluent and utilizing a monoalkali initiator having the formula wherein R is a hydrocarbyl radical having 1 to about 20 carbon atoms per molecule and M is an alkali metal selected from the group consisting of sodium, potassium and lithium.

Claim 7

A coupled polymer made by a process defined in one of claims 1) to 5).

Claim 8

A coupled polymer having a molecular weight distribution as characterized by the GPC curves of the two-step coupled polymer shown in the drawing.

Claim 9

A coupled polymer having a molecular weight distribution as characterized by the GPC curves of the two-step coupled polymer shown in the drawing.

Claim 10

A polymer having the formula wherein m' polymerchains Q - and e units - Y - Q' are attached to a central hydrocarbyl unit X' and wherein Q is a polymer or copolymer of at least one alkadiene of 4 to about 12 carbon atoms, Y is a radical or bond resulting from a coupling process with a difunctional coupling agent capable of coupling alkali metal terminated Q polymers, the radicals Q' which can be the same or different are -Q or 4X" - Q m" ), X' and X" is a central, hydrocarbyl unit derived from coupling agents of 10 to about 30 carbon atoms having two or three vinyl radicals directly attached to otherwise unsubstituted or alkyl substituted benzene, bi-phenyl, or naphthalene, the central units X' and X" being the same or different, and e, m' and m" being integers and the average number of polymer chains Q being present in the molecules is in the range of 8 to 15.

Claim 11

A polymer having the formula wherein m' polymerchains Q - and e units - Y - Q' are attached to a central hydrocarbyl unit X' and wherein Q is a polymer or copolymer of at least one alkadiene of 4 to about 12 carbon atoms, Y is a radical or bond resulting from a coupling process with a difunctional coupling agent capable of coupling alkali metal terminated Q polymers, the radicals Q' which can be the same or different are -Q or 4X" - Q m" ), X' and X" is a central, hydrocarbyl unit derived from coupling agents of 10 to about 30 carbon atoms having two or three vinyl radicals directly attached to otherwise unsubstituted or alkyl substituted benzene, bi-phenyl, or naphthalene, the central units X' and X" being the same or different, and e, m' and m" being integers and the average number of polymer chains Q being present in the molecules is in the range of 8 to 15.

Claim 12

A polymer in accordance with claim 8) characterized in that said central units X' are derived from divinylbenzene and said radical Y is derived from a coupling agent selected from the group consisting of carbon monoxide, carbon dioxide, α,α'-dichloro-p-xylene, methyl methacrylate and dimethyl dichlorosilane.

Claim 13

A polymer in accordance with claim 8) or 9) characterized in that Q is a polymer chain of the structure wherein E represents a block selected from the group of hydrogenated low vinyl polybutadiene and poly- vinylarene from monovinylarene monomers having 8 to 20 carbon atoms per molecules and D comprises one or more homopolymer or copolymer blocks of alkadiene monomers of 4 - 12 carbon atoms contributing rubbery properties to the polymer.