ZIEGLER-NATTA CATALYST COMPOSITIONS FOR PRODUCING POLYETHYLENES WITH A HIGH MOLECULAR WEIGHT TAIL AND METHODS OF MAKING THE SAME

1 . A method of preparing a catalyst component, the method comprising:

a) contacting in a slurrying agent:

i) at least one magnesium dihydrocarbyl oxide;

ii) at least one Lewis acidic solubilizing agent; and

iii) at least one titanium compound;

and

b) spray drying the slurry of step a) to evaporate the slurrying agent and to produce solid particles;

where the magnesium dihydrocarbyl oxide and the titanium compound are present in the slurry in any molar ratio.

2 . The method according to claim 1 , where step a) of contacting in a slurrying agent components i), ii), and iii) further comprises contacting with:

iv) at least one transition metal compound different from the titanium compound, where the transition metal is selected from the Groups 4-6 metals.

3 . The method according to claim 2 , where the transition metal compound different from the titanium compound is selected from:

a) Zr(OR 4 ) b Cl 4-b , Hf(OR 4 ) b Cl 4-b , VOCl 3 , or any combination thereof, where b is an integer from 0 to 4, and R 4 in each occurrence is an alkyl group having from 1 to 12 carbon atoms;

b) Ti(OR 5 ) c X 1 4-c , or any combination of compounds of this formula, where X 1 is Cl, Br, or I; c is an integer from 0 to 3; and R 5 in each occurrence is an alkyl group having from 1 to 12 carbon atoms;

c) TiX 2 d where X 2 is Cl, Br, or I and d is a number from greater than 0 to less than 4; or

d) any combination thereof.

4 . The method according to claim 1 , where step a) of contacting in a slurrying agent components i), ii), and iii) further comprises contacting with:

v) a non-porous filler.

5 . The method according to claim 1 , where the slurrying agent is selected from an alcohol having up to 4 carbon atoms or any combination of alcohols having up to 4 carbon atoms.

6 . The method according to claim 1 , where the Lewis acid solubilizing agent is carbon dioxide and the slurrying agent is an alcohol having from 1 to 4 carbon atoms.

7 . The method according to claim 1 , where:

the magnesium dihydrocarbyl oxide has the formula Mg(OR 1 ) 2 where R 1 in each occurrence, is selected independently from an alkyl having up to 6 carbon atoms inclusive; and

the Lewis acidic solubilizing agent is selected from carbon dioxide, sulfur dioxide, formaldehyde, Al(OR 2 ) 3 , B(OR 2 ) 3 , or any combination thereof, where R 2 in each occurrence is selected independently from an alkyl having up to 6 carbon atoms inclusive.

8 . The method according to claim 1 , further comprising step c), as follows:

c) contacting the solid particles of step b) with at least one halogenating agent under conditions that partially halogenate the catalyst precursor.

9 . The method according to claim 1 , further comprising step c), as follows:

c) contacting the solid particles of step b) with:

i) at least one mild first halogenating agent and at least one strong second halogenating agent in succession, under conditions which partially halogenate the catalyst precursor; or

ii) at least one strong halogenating agent under conditions which partially halogenate the catalyst precursor.

10 . A catalyst system comprising:

a) a catalyst component prepared according to claim 1 ;

b) a halogenating agent; and

c) an activating co-catalyst.

11 . The catalyst system according to claim 10 , where the activating co-catalyst is selected from at least one compounds of the formula AlR 10 3 , where R 10 in each occurrence is independently a saturated hydrocarbon groups having from 1 to 14 carbon atoms, optionally substituted with one or more substituents which are inert under the polymerization reaction conditions employed.

12 . A method of preparing a catalyst component, the method comprising:

a) contacting in a slurrying agent:

i) at least one magnesium dihydrocarbyl oxide;

ii) at least one Lewis acidic solubilizing agent;

iii) at least one titanium compound; and

iv) at least one non-porous filler;

b) spray drying the slurry of step a) to evaporate the slurrying agent and to produce solid particles;

and

c) treating the solid particles of step b) with at least one halogenating agent;

where the magnesium dihydrocarbyl oxide, the titanium compound, and the optional transition metal compound different from the titanium compound are present in the slurry in any molar ratio.

13 . The method according to claim 12 , where step a) of contacting in a slurrying agent components i), ii), iii), and iv) further comprises contacting with:

v) at least one transition metal compound different from the titanium compound, where the transition metal is selected from the Groups 4-6 metals.

14 . A catalyst system comprising:

a) catalyst component prepared according to claim 12 ; and

b) an activating co-catalyst selected from at least one compounds of the formula AlR 10 3 , where R 10 in each occurrence is independently a saturated hydrocarbon groups having from 1 to 14 carbon atoms, optionally substituted with one or more substituents which are inert under the polymerization reaction conditions employed.

15 . A catalyst component comprising the contact product of:

a) a spray-dried mixture or reaction product of:

i) at least one magnesium dihydrocarbyl oxide;

ii) at least one Lewis acidic solubilizing agent;

iii) at least one titanium compound;

iv) at least one transition metal compound different from the titanium compound, where the transition metal is selected from the Groups 4-6 metals; and

v) at least one non-porous filler;

b) at least one strong second halogenating agent;

where contacting occurs under conditions that partially or exhaustively halogenate the spray-dried mixture or reaction product.

16 . The catalyst component according to claim 15 , where the contact product further comprises the contact product of components a) and b) with:

c) at least one mild first halogenating agent.

17 . The catalyst component according to claim 14 , where contacting occurs under conditions that partially halogenate the spray-dried mixture or reaction product.