Polymacromonomer and process for production thereof

A polymacromonomer comprising at least one macromonomer and from 0 to 20 wt % of a C2 to C18 comonomer, wherein the polymacromonomer has:

• a) a g value of less than 0.6,
• b) an Mw of greater than 30,000 g/mol,
• c) an Mn of greater than 20,000 g/mol,
• d) a branching index (g′)vis of less than 0.5,
• e) less than 25% vinyl terminations (as measured by 1H NMR) relative to total unsaturations,
• f) at least 70 wt % macromonomer, based upon the weight of the polymacromonomer, and
• g) from 0 to 20 wt % aromatic containing monomer, based upon the weight of the polymacromonomer;
• and the macromonomer comprises one or more of:
• i) propylene co-oligomer having an Mn of 300 to 30,000 g/mol comprising 10 to 90 mol % propylene and 10 to 90 mol % of ethylene, wherein the oligomer has at least X % allyl chain ends (relative to total unsaturations), where:
• 1) X=(−0.94 (mol % ethylene incorporated)+100), when 10 to 60 mol % ethylene is present in the co-oligomer, and 2) X=45, when greater than 60 and less than 70 mol % ethylene is present in the co-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83), when 70 to 90 mol % ethylene is present in the co-oligomer;
• and/or
• ii) propylene oligomer, comprising more than 90 mol % propylene and less than 10 mol % ethylene, wherein the oligomer has:
• at least 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum;
• and/or
• iii) propylene oligomer, comprising at least 50 mol % propylene and from 10 to 50 mol % ethylene, wherein the oligomer has:
• at least 90% allyl chain ends, Mn of about 150 to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomers having four or more carbon atoms are present at from 0 to 3 mol %;
• and/or
• iv) propylene oligomer, comprising at least 50 mol % propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % C4 to C12 olefin, wherein the oligomer has:
• at least 87% allyl chain ends (alternately at least 90%), an Mn of about 150 to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;
• and/or
• v) propylene oligomer, comprising at least 50 mol % propylene, from 0.1 to 45 wt % ethylene, and from 0.1 to 5 mol % diene, wherein the oligomer has:
• at least 90% allyl chain ends, an Mn of about 150 to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0;
• and/or
• vi) a homooligomer, comprising propylene, wherein the oligomer has:
• at least 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum.

A polymacromonomer comprising at least one macromonomer and from 0 to 20 wt % of a C2 to C18 comonomer, wherein the macromonomer, prior to polymerization, has:

• 1) from 20 to 600 carbon atoms,
• 2) an Mn of 280 g/mol or more,
• 3) an Mw of 400 g/mol or more,
• 4) an Mz of 600 g/mol or more,
• 5) an Mw/Mn of 1.5 or more,
• 6) vinyl termination of at least 70% (as determined by 1H NMR) relative to total unsaturations,
• 7) a melting point (Tm) of 60° C. or more or an Hm of 20 J/g or less, and
• 8) less than 10 wt % aromatic containing monomer, based upon the weight of the macromonomer;
• and
• wherein the polymacromonomer has:
• a) a g value of less than 0.6,
• b) an Mw of greater than 30,000 g/mol,
• c) a branching index (g′)vis of less than 0.5,
• d) a melting point of 50° C. or more or an Hm of 20 J/g or less,
• e) less than 25% vinyl terminations (as measured by 1H NMR) relative to total unsaturations,
• f) at least 70 wt % macromonomer, based upon the weight of the polymacromonomer, and
• g) from 0 to 20 wt % aromatic containing monomer, based upon the weight of the polymacromonomer.

A process to produce polymacromonomers comprising contacting macromonomer and up to 40 wt % of C2 to C18 comonomer with a catalyst system capable of polymerizing vinyl terminated macromonomer, wherein the macromonomer, prior to polymerization, has:

• 1) from 20 to 600 carbon atoms,
• 2) an Mn of 280 g/mol or more,
• 3) an Mw of 400 g/mol or more,
• 4) an Mz of 600 g/mol or more,
• 5) an Mw/Mn of 1.5 or more,
• 6) at least 70% vinyl termination (as measured by 1H NMR) relative to total unsaturations,
• 7) a melting point Tm of 60° C. or more or an Hm of 20 J/g or less, and
• 8) less than 20 wt % aromatic containing monomer;
• under polymerization conditions of a temperature of 60 to 130° C. and a reaction time of 1 to 90 minutes, wherein the molar ratio of all comonomer present in the reactor to all macromonomer present in the reactor is 3:1 or less and where conversion of macromonomer to polymacromonomer is 70 wt % or more;
• and
• obtaining a polymacromonomer having:
• a) a g value of less than 0.6,
• b) an Mw of greater than 30,000 g/mol,
• c) an Mn of greater than 20,000 g/mol,
• d) a branching index (g′)vis of less than 0.5, and
• e) a melting point of 50° C. or more or an Hm of 20 J/g or less,
• f) less that 25% vinyl termination (as measured by 1H NMR) relative to total unsaturations,
• g) at least 70 wt % macromonomer, based upon the weight of the polymacromonomer, and
• h) from 0 to 20 wt % aromatic containing monomer, based upon the weight of the polymacromonomer.