Vinyl-terminated macromonomer oligomerization
AssigneeExxonMobil Chemical Patents Inc.
InventorsJohn R Hagadorn, Patrick Brant, Robbert Duchateau, Rafael Sablong
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Abstract
Vinyl-terminated macromonomer oligomerization, namely, a process to produce polymacromonomers comprising contacting a vinyl-terminated macromonomer with a catalyst system capable of oligomerizing vinyl-terminated macromonomer, in the presence of an aluminum containing compound, a zinc containing compound, or a combination thereof, under polymerization conditions to produce a polymacromonomer, and polymacromonomers produced thereby. Also, polymacromonomers having a degree of polymerization greater than 10, a glass transition temperature Tg of less than 60° C., and an Mn of greater than or equal to about 5000 Da.
Claims39
A process to produce polymacromonomers comprising contacting (1) a vinyl-terminated macromonomer having an Mn of 125 Da or more and at least 70% vinyl termination (as measured by 1H NMR) relative to total unsaturations, and (2) up to 40 wt % of C2 to C18 comonomer, with (3) a catalyst system capable of oligomerizing vinyl-terminated macromonomer, in the presence of a chain transfer agent, under polymerization conditions at a temperature from 20° C. to 180° C. and a reaction time of 1 min to 24 hours to produce a polymacromonomer having a degree of polymerization greater than 10, a branching index g′(vis) less than 0.9, a Tg from -10° C. to 40° C., and an Mn of greater than or equal to about 5000 Da.
A process to produce polymacromonomers comprising contacting (1) a vinyl-terminated macromonomer having an Mn of 160 Da or more and at least 30% vinyl termination (as measured by 1H NMR) relative to total unsaturations, and (2) up to 40 wt % of C2 to C18 comonomer, with (3), optionally, a catalyst system capable of oligomerizing vinyl-terminated macromonomer, in the presence of a reversible chain transfer agent selected from an aluminum containing compound, a zinc containing compound, or a combination thereof, under polymerization conditions at a temperature from 20° C. to 180° C. and a reaction time of 1 min to 24 hours to produce a polymacromonomer having a degree of polymerization greater than 10, a branching index g′(vis) less than 0.9, a Tg from -10° C. to 40° C. and an Mn of greater than or equal to about 1500 Da.
A process to produce polymacromonomers comprising contacting (1) a vinyl-terminated atactic propylene macromonomer comprising from 12 to 600 carbon atoms, an Mn of 220 Da or more, a melting point (Tm) of 60° C. or less and at least 70% vinyl termination (as measured by 1H NMR) relative to total unsaturations, and (2) up to 40 wt % of C2 to C18 comonomer, with (3), a hafnium catalyst system capable of oligomerizing vinyl-terminated macromonomer, in the presence of a reversible chain transfer agent selected from an aluminum containing compound, a zinc containing compound, or a combination thereof, under polymerization conditions at a temperature from 20° C. to 180° C., a ratio of equivalents of Al/Hf from about 10 to 10,000, a ratio of equivalents of macromonomer/catalyst Hf greater than 500 and a reaction time of 1 min to 24 hours, to produce a polymacromonomer having a degree of polymerization greater than 10, a branching index g′(vis) less than 0.3, a Tg from −10° C. to 40° C., an Mn of greater than or equal to about 5000 Da, an Mn (SEC-vis) greater than Mn (SEC-RI), an MWD (SEC-RI) greater than MWD (SEC-vis) and a flow activation energy greater than 10 kcal/mol.
A polymacromonomer comprising at least one vinyl-terminated macromonomer and from 0 wt % to 40 wt % of a C2 to C18 comonomer, wherein the polymacromonomer has a degree of polymerization greater than 10, an Mn greater than 5000 Da, a branching index g′(vis) less than 0.9, and a glass transition temperature less than 60° C., wherein the macromonomer prior to polymerization comprises:
- 1) from 12 to 600 carbon atoms,
- 2) an Mn of 170 or more,
- 3) a melting point (Tm) of 60° C. or less, and
- 4) less than 10 wt % aromatic containing monomer, based on the weight of the macromonomer.
Dependencies are inferred from the claim text.