Catalyst composition for polymerizing olefins of narrow molecular weight distribution and polymerization therewith

Claim 2

In a process of preparing a supported olefin polymerization catalyst composition comprising a transition metal or a compound thereof and a catalyst activator, an improvement comprising using such a support that the catalyst composition has an average pore diameter of about 20 to about 300 Angstroms at a substantially constant particle size, so that the span of the particle size distribution of the catalyst is less than about 0.5.

Claim 3

A process of claim 1 wherein the catalyst composition also comprises magnesium or a compound thereof.

Claim 4

A process of claim 2 wherein the supported catalyst composition has an average pore diameter of about 50 to about 200 Angstroms.

Claim 5

A process of claim 3 wherein the supported catalyst composition has an average pore diameter of about 90 to about 150 Angstroms.

Claim 6

A process of claim 4 wherein the catalyst composition is prepared by: (a) contacting a solid, porous carrier with a magnesium compound; and (b) contacting the product of said step (a) with a transition metal compound.

Claim 7

A process of claim 5 wherein the magnesium compound is a halide-containing magnesium compound or an organomagnesium compound.

Claim 8

A process of claim 6 wherein the supported catalyst composition is prepared by a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different C 1 -C 12 hydrocarbyl groups, provided that R', but not R, may also be a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier; (ii) evaporating said liquid from step (i) to produce a supported magnesium composition in the form of a dry, free-flowing powder; and (iii) reacting said powder of step (ii) with at least one transition metal compound in a liquid medium, the number of moles of said transition metal compound being in excess of the number of the OH groups on said carrier prior to the reaction of the carrier with said organomagnesium composition in step (i), said transition metal compound being soluble in said liquid medium, and said supported magnesium composition being substantially insoluble in said liquid medium, whereby a reacted form of transition metal which is insoluble in said liquid medium becomes supported on said carrier.

Claim 9

A process of claim 7 wherein the catalyst composition produces such polymers in which the R 2 value of the regression plot of MFR as a function of the catalyst average pore diameter is greater than 60%.

Claim 10

A process of claim 8 wherein the R 2 value is greater than 70%.

Claim 11

A process of claim 9 wherein the R 2 value is greater than 80%.

Claim 12

A process of claim 10 wherein the R 2 value is about 85 to about 100%.

Claim 13

A process of claim 11 wherein the R 2 value is 88%.

Claim 14

A process of claim 12 wherein the supported catalyst composition has a constant particle size of about 90 microns.

Claim 15

A process of claim 13 wherein said step (i) comprises: (a) slurrying the carrier in a non-Lewis base liquid; and (b) adding to the slurry resulting from said step (a) the organomagnesium composition in the form of an ether solution thereof.

Claim 16

A process of claim 14 wherein the ether is tetrahydrofuran.

Claim 17

A process of claim 15 wherein the catalyst is supported on a porous, solid carrier which is silica, alumina or combinations thereof.

Claim 18

A process of claim 16 wherein the porous, solid carrier is silica.

Claim 19

A process of claim 17 wherein the transition metal compound is a tetravalent titanium compound.

Claim 20

A process of claim 18 wherein the tetravalent titanium compound is TiCl 4 .

Claim 21

A process of claim 19 wherein, in said step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.1 to about 3.5.

Claim 22

A process of claim 20 wherein, in said step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is about 2.0 to about 3.5.

Claim 23

A process of claim 21 wherein said liquid medium is an alkane, cycloalkane, aromatics or halogenated aromatics.

Claim 24

A process of claim 22 wherein said liquid medium is hexane.

Claim 25

A process of claim 23 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. for at least four hours.

Claim 26

A process of claim 24 wherein the organomagnesium composition is ethylmagnesium chloride.

Claim 27

In an olefin polymerization catalyst composition supported on a solid, porous carrier, comprising a transition metal or a compound thereof, and a catalyst activator, an improvement comprising using such a solid, porous carrier that the catalyst composition has an average pore diameter of about 20 to about 300 Angstroms at a substantially constant particle size such that the span of the particle size distribution of the catalyst is less than about 0.5.

Claim 28

In an olefin polymerization catalyst composition supported on a solid, porous carrier, comprising a transition metal or a compound thereof, and a catalyst activator, an improvement comprising using such a solid, porous carrier that the catalyst composition has an average pore diameter of about 20 to about 300 Angstroms at a substantially constant particle size such that the span of the particle size distribution of the catalyst is less than about 0.5.

Claim 29

A catalyst composition of claim 26 which has an average pore diameter of about 50 to about 200 Angstroms.

Claim 30

A catalyst composition of claim 27 which has an average pore diameter of about 90 to about 150 Angstroms.

Claim 31

A catalyst composition of claim 28 which also comprises magnesium or a compound thereof.

Claim 32

A catalyst composition of claim 29 wherein it is prepared by: (a) contacting a solid, porous carrier with a magnesium compound; and (b) contacting the product of said step (i) with a transition metal compound.

Claim 33

A catalyst composition of claim 30 wherein it is prepared by a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different C 1 -C 12 hydrocarbyl groups, provided that R', but not R, may also be a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier; (ii) evaporating said liquid from step (i) to produce a supported magnesium composition in the form of a dry, free-flowing powder; and (iii) reacting said powder of step (ii) with at least one transition metal compound in a liquid medium, the number of moles of said transition metal compound being in excess of the number of the OH groups on said carrier prior to the reaction of the carrier with said organomagnesium composition in step (i), said transition metal compound being soluble in said liquid medium, and said supported magnesium composition being substantially insoluble in said liquid medium, whereby a reacted form of transition metal which is insoluble in said liquid medium becomes supported on said carrier.

Claim 34

A catalyst composition of claim 31 which produces such polymers in which the R 2 value of the regression plot of MFR as a function of the catalyst average pore diameter is greater than 60%.

Claim 35

A catalyst composition of claim 32 wherein the R 2 value is greater than 70%.

Claim 36

A catalyst composition of claim 33 wherein the R 2 value is greater than 80%.

Claim 37

A catalyst composition of claim 34 wherein the R 2 value is about 85 to about 100%.

Claim 38

A catalyst composition of claim 35 wherein the R 2 value is 88%.

Claim 39

A catalyst composition of claim 36 wherein the supported catalyst composition has a constant particle size of about 90 microns.

Claim 40

A catalyst composition of claim 37 wherein the porous, solid carrier is silica.

Claim 41

A catalyst composition of claim 33 wherein the transition metal compound is a tetravalent titanium compound.

Claim 42

A catalyst composition of claim 39 wherein the tetravalent titanium compound is TiCl 4 .

Claim 43

A catalyst composition of claim 40 wherein, in said step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is about 2.0 to about 3.5.

Claim 44

A catalyst composition of claim 41 wherein the organomagnesium composition is ethylmagnesium chloride.

Claim 45

A process of claim 4 wherein the supported catalyst composition is prepared by forming a precursor composition from a magnesium compound, a titanium compound, and an electron donor compound, diluting the precursor composition with an inert carrier, and activating the diluted precursor composition with the catalyst activator.

Claim 46

A process of claim 43 wherein the titanium compound has the structure: Ti(OR).sub.a X.sub.b wherein R is an aliphatic or aromatic hydrocarbon radical containing 1 to 14 carbon atoms or COR', where R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I, and mixtures thereof, a is 0, 1 or 2, b is 1 to 4, inclusive, and a+b=3 or 4.

Claim 47

A process of claim 44 wherein the titanium compound is TiCl 3 , TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OC 6 H 5 )Cl 3 , Ti(OCOCH 3 )Cl 3 or Ti(OCOC 6 H 5 )Cl 3 .

Claim 48

A process of claim 45 wherein the titanium compound is TiCl 3 .

Claim 49

A process of claim 46 wherein the magnesium compound has the structure: MgX.sub.2 wherein X is Cl, Br, I or mixtures thereof.

Claim 50

A process of claim 47 wherein the magnesium compound is MgCl 2 , MgBr 2 or MgI 2 .

Claim 51

A process of claim 48 wherein the magnesium compound is anhydrous MgCl 2 .

Claim 52

A process of claim 49 wherein the electron donor compound is an alkyl ester of an aliphatic carboxylic acid, an alkyl ester of an aromatic carboxylic acid, an aliphatic ether, a cyclic ether or an aliphatic ketone.

Claim 53

A process of claim 50 wherein the electron donor compound is methyl formate, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, dioxane, acetone or methyl ethyl ketone.

Claim 54

A process of claim 51 wherein the supported catalyst composition has the formula: Mg.sub.m Ti(OR).sub.n X.sub.p [ED].sub.q wherein R is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I, and mixtures thereof, ED is an electron donor compound, m is 0.5 to 56, preferably 1.5 to 5, n is 0, 1 or 2, p is 2 to 116, preferably 6 to 14, and q is 2 to 85, preferably 3 to 10.

Claim 55

A catalyst composition of claim 27 prepared by forming a precursor composition from a magnesium compound, a titanium compound, and an electron donor compound, diluting the precursor composition with an inert carrier, and activating the diluted precursor composition with the catalyst activator.

Claim 56

A catalyst composition of claim 53 wherein the titanium compound has the structure: Ti(OR).sub.a X.sub.b wherein R is an aliphatic or aromatic hydrocarbon radical containing 1 to 14 carbon atoms or COR',where R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I, and mixtures thereof, a is 0, 1 or 2, b is 1 to 4, inclusive, and a+b=3 or 4.

Claim 57

A catalyst composition of claim 54 wherein the titanium compound is TiCl 3 , TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OC 6 H 5 )Cl 3 , Ti(OCOCH 3 )Cl 3 or Ti(OCOC 6 H 5 )Cl 3 .

Claim 58

A catalyst composition of claim 55 wherein the titanium compound is TiCl 3 .

Claim 59

A catalyst composition of claim 56 wherein the magnesium compound has the structure: MgX.sub.2 wherein X is Cl, Br, I or mixtures thereof.

Claim 60

A catalyst composition of claim 57 wherein the magnesium compound is MgCl 2 , MgBr 2 or MgI 2 .

Claim 61

A catalyst composition of claim 58 wherein the magnesium compound is anhydrous MgCl 2 .

Claim 62

A catalyst composition of claim 59 wherein the electron donor compound is an alkyl ester of an aliphatic carboxylic acid, an alkyl ester of an aromatic carboxylic acid, an aliphatic ether, a cyclic ether or an aliphatic ketone.

Claim 63

A catalyst composition of claim 60 wherein the electron donor compound is methyl formate, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, dioxane, acetone or methyl ethyl ketone.

Claim 64

A catalyst composition of claim 61 having the formula: Mg.sub.m Ti(OR).sub.n X.sub.p [ED].sub.q wherein R is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I, and mixtures thereof, ED is an electron donor compound, m is 0.5 to 56, preferably 1.5 to 5, n is 0, 1 or 2, p is 2 to 116, preferably 6 to 14, and q is 2 to 85, preferably 3 to 10.