Polymerization catalyst and method

Claim 2

A catalyst prepared by dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia, and mixtures and composites thereof a reaction product of (1) a chromium carboxylate essentially of the formula ##STR6## wherein R is selected from hydrogen, alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, and cycloalkenyl radicals and combinations of these radicals with R containing 0-30 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, m is a whole number of 1 to 3, n is a whole number of 0 to 2, m plus n is 2 or 3 and X is a halide, alkyl or alkoxy and (2) an organic nitrogen compound capable of forming a complex with trivalent chromium and essentially of the formula of the class consisting of ##STR7## wherein each R' is individually selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, and arylalkyl radicals with each R' containing 0-10 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, j is a whole number of 1 to 5, k is a whole number of 1 to 3, and Y is >CO, >NH, or >CH 2 , and activating the resulting mixture by heating to and at an elevated temperature of from about 600°-2000° F. in a non-oxidizing atmosphere.

Claim 3

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR8##

Claim 4

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR9##

Claim 5

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR10##

Claim 6

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR11##

Claim 7

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR12##

Claim 8

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR13##

Claim 9

The catalyst of claim 1 wherein said nitrogen compound is essentially of the formula ##STR14##

Claim 10

The catalyst of claim 1 wherein said support prior to the addition of said reaction product is pretreated by heating at a temperature of from about 300°-2000° F. until volatile matter is at least partially driven off.

Claim 11

The catalyst of claim 1 wherein said reaction product is dissolved in a solvent and the resulting solution used to impregnate said support.

Claim 12

The catalyst of claim 1 wherein said dispersing of said reaction product is accomplished by dry blending with said finely divided support followed by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through said support during said heating.

Claim 13

The catalyst of claim 1 wherein said activating is accomplished in a fluid bed maintained in suspension with the flow of a non-oxidizing gas.

Claim 14

The catalyst of claim 1 wherein said catalyst on a dry basis contains an amount of said reaction product to provide about 0.05-10 wt.% of chromium.

Claim 15

The catalyst of claim 1 wherein said chromium carboxylate is a member of the class consisting of chromium (III) formate, chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) benzoate, chromium naphthenate and chromium oleate.

Claim 16

The catalyst of claim 1 wherein said organic nitrogen compound is a member of the class consisting of ethylenediamine, propylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, 3,4-diaminotoluene, 2,2'-bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, aniline and diphenylamine.

Claim 17

The process of preparing an active polymerization catalyst comprising the steps of dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia, and mixtures and composites thereof a reaction product of (1) a chromium carboxylate essentially of the formula ##STR15## wherein R is selected from hydrogen, alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, and cycloalkenyl radicals and combinations of these radicals with R containing 0-30 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, m is a whole number of 1 to 3, n is a whole number of 0 to 2, m plus n is 2 or 3 and X is a halide, alkyl or alkoxy and (2) an organic nitrogen compound capable of forming a complex with trivalent chromium and essentially of the formula of the class consisting of ##STR16## wherein each R' is individually selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and arylalkyl radicals with each R' containing 0-10 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, j is a whole number of 1 to 5, k is a whole number of 1 to 3, and Y is >CO, >NH, or >CH 2 , and activating the resulting mixture by heating to and at an elevated temperature of from about 600°-2000° F. in a non-oxidizing atmosphere.

Claim 18

The process of preparing an active polymerization catalyst comprising the steps of dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia, and mixtures and composites thereof a reaction product of (1) a chromium carboxylate essentially of the formula ##STR15## wherein R is selected from hydrogen, alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, and cycloalkenyl radicals and combinations of these radicals with R containing 0-30 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, m is a whole number of 1 to 3, n is a whole number of 0 to 2, m plus n is 2 or 3 and X is a halide, alkyl or alkoxy and (2) an organic nitrogen compound capable of forming a complex with trivalent chromium and essentially of the formula of the class consisting of ##STR16## wherein each R' is individually selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and arylalkyl radicals with each R' containing 0-10 carbon atoms and a corresponding number of valence-satisfying hydrogen atoms, j is a whole number of 1 to 5, k is a whole number of 1 to 3, and Y is >CO, >NH, or >CH 2 , and activating the resulting mixture by heating to and at an elevated temperature of from about 600°-2000° F. in a non-oxidizing atmosphere.

Claim 19

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR17##

Claim 20

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR18##

Claim 21

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR19##

Claim 22

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR20##

Claim 23

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR21##

Claim 24

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR22##

Claim 25

The process of claim 16 wherein said nitrogen compound is essentially of the formula ##STR23##

Claim 26

The process of claim 16 wherein said support prior to the addition of said reaction product is pretreated by heating at a temperature of from about 300°-2000° F. until volatile matter is at least partially driven off.

Claim 27

The process of claim 16 wherein said reaction product is dissolved in a solvent and the resulting solution used to impregnate said support.

Claim 28

The process of claim 16 wherein said dispersing of said reaction product is accomplished by dry blending with said finely divided support followed by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through said support during said heating.

Claim 29

The process of claim 16 wherein said catalyst on a dry basis contains an amount of said reaction product to provide about 0.05-10 wt.% of chromium.

Claim 30

The process of claim 16 wherein said chromium carboxylate is a member of the class consisting of chromium (III) formate, chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) benzoate, chromium naphthenate and chromium oleate.

Claim 31

The process of claim 16 wherein said organic nitrogen compound is a member of the class consisting of ethylenediamine, propylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, 3,4-diaminotoluene, 2,2'-bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, aniline and diphenylamine,.

Claim 32

The process of claim 16 wherein said activating is in a fluid bed maintained by the flow of a non-oxidizing gas.

Claim 33

The process of claim 16 wherein said activating is in a stationary bed in a non-oxidizing atmosphere provided by evacuation of gas from said bed.

Claim 34

The process of claim 16 wherein said activating is in a stationary bed in a non-oxidizing atmosphere provided by a non-oxidizing gas.

Claim 35

The process of claim 30 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.

Claim 36

The process of claim 10 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of support and said chromium-containing reaction product in suspension while heating to a final activation temperature of from 850°-2000° F.

Claim 37

The process of claim 32 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.

Claim 38

The process of claim 16 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of support and said chromium-containing reaction product in a fluid condition while heating at activating temperatures of from about 300°-350° F. for from about 1 to 3 hours and then at about 550°-600° F. for about 1 to 3 hours to produce an interaction between the chromium compound and the support, followed by final activation at a temperature of about 850°-2000° F., for a period of about 0.5-12 hours.

Claim 39

The process of claim 36 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.