Preparation of linear alpha olefin polymers having broad molecular weight distributions

Claim 2

The improvement according to claim 1 wherein hydrogen is present in concentration in the range of from about 0.001 to about 0.5 mole per mole of the alpha olefin.

Claim 3

The improvement according to claim 1 wherein MRnXm of the transition metal catalyst composition is an aluminum trialkyl.

Claim 4

The improvement according to claim 1 wherein the reducible compound is a reducible titanium halide.

Claim 5

The improvement according to claim 1 wherein the reducible compound is a reducible vanadium oxyhalide.

Claim 6

The improvement according to claim 1 wherein MRnXm of the zirconium catalyst composition is an aluminum trialkyl.

Claim 7

The improvement according to claim 1 wherein the temperature is within a range from about 130* to about 300* C.

Claim 8

The improvement according to claim 1 wherein the pressure is within a range from about 100 to about 1,000 psig.

Claim 9

The improvement according to claim 1 wherein the reducible compound/zirconium molar ratio is within a range from about 0.5:1 to about 7:1.

Claim 10

The improvement according to claim 1 wherein the molar ratio of titanium or vanadium to M of the transition metal catalyst composition ranges from about 0.5:1 to about 5:1 and the molar ratio of zirconium to M of the zirconium catalyst composition is about 0.5:1 to about 5:1.

Claim 11

In a process for polymerizing in a polymerization zone an alpha olefin selected from the group consisting of ethylene, propylene and butene-1 in the presence of a catalytic amount of a transition metal catalyst composition formed by reacting an organometallic reducing compound selected from the group consisting of aluminum trialkyls, aluminum alkyl hydrides, and aluminum alkyl halides wherein alkyl has from one to eight carbon atoms and halide is chloride or bromide with a reducible compound of a transition metal selected from the group consisting of titanium and vanadium; the improvement according to claim 11 which comprises (1) introducing into the polymerization zone, in addition to said transition metal catalyst composition, a sufficient amount of a zirconium catalyst composition which is a reaction product of (a) an organo-metallic reducing compound selected from the group consisting of aluminum trialkyls, aluminum alkyl hydrides and aluminum alkyl halides wherein alkyl has from one to eight carbon atoms and halide is chloride or bromide with (b) a reducible zirconium compound to yield a transition metal/zirconium molar ratio ranging from about 0.5:1 to about 10:1 and (2) polymerizing the alpha olefin in the presence of from about 0.001 to about 0.5 mole of hydrogen per mole of alpha olefin at temperatures and pressures sufficient to maintain the resulting polymer in solution thereby providing an alpha olefin polymer having broad molecular weight distribution.

Claim 12

In a process for polymerizing ethylene in the presence of a catalytic amount of a transition metal catalyst composition formed by reacting aluminum triethyl with a reducible transition metal compound selected from the group consisting of titanium tetrachloride and vanadium oxychloride; the improvement according to claim 11 which comprises (1) introducing into the polymerization zone, in addition to said transition metal catalyst composition, a sufficient amount of a zirconium catalyst composition which is a reaction product of (a) aluminum triethyl with zirconium tetrachloride to yield a transition metal/zirconium molar ratio ranging from about 0.5:1 to about 10: 1 and (2) polymerizing the alpha olefin in the presence of from about 0.001 to about 0.5 mole of hydrogen per mole of alpha olefin at temperatures and pressures sufficient to maintain the resuLting polymer in solution thereby providing an alpha olefin polymer having broad molecular weight distribution.

Claim 13

In a process for polymerizing in a polymerization zone an alpha olefin selected from the group consisting of ethylene, propylene and butene-1 in the presence of a catalytic amount of a transition metal catalyst composition formed by reacting an organometallic reducing compound selected from the group consisting of aluminum trialkyls and diethyl aluminum chloride one to eight carbon atoms with a reducible compound of a transition metal selected from the group consisting of titanium and vanadium wherein the aluminum/transition metal molar ratio is in the range from about 0.5:1 to about 5:1; the improvement according to claim 11 which comprises (1) introducing into the polymerization zone, in addition to said transition metal catalyst composition, a sufficient amount of a zirconium catalyst composition which is a reaction product of (a) an organometallic reducing compound selected from the group consisting of aluminum trialkyls, and diethyl aluminum chloride wherein alkyl has from 1 to 8 carbon atoms with (b) a reducible zirconium compound wherein the aluminum/zirconium molar ratio is in the range from about 0.5:1 to about 5:1 to yield a transition metal/zirconium molar ratio ranging from about 0.5:1 to about 10:1 and (2) polymerizing the alpha olefin in the presence of from about 0.001 to about 0.5 mole of hydrogen per mole of alpha olefin at temperatures and pressures sufficient to maintain the resulting polymer in solution thereby providing an alpha olefin polymer having broad molecular weight distribution.