Process for copolymerizing ethylene

Claim 2

A catalyst composition comprising a precursor composition cf the formula wherein R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I or mixtures thereof, ED is an electron donor compound, m is > 0.5 to < 56, n is 0, 1 or 2, p is > 2 to < 116, and q is > 2 to < 85, said precursor composition being impregnated in a porous support and being either unactivated, or partially activated with >0 to < 10 mols of activator compound per mol of Ti in said precursor composition or completely activated with >10 to < 400 mols of activator compound per mol of Ti in said precursor composition, said activator compound having the formula wherein X' is Cl or OR"', R" and R"' are the same or different, and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c + d + e = 3, said electron donor compound being a liquid organic compound in which said precursor composition is soluble and which is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones.

Claim 3

A catalyst composition as in claim 1 wherein said partially activated precursor composition is completely activated in a polymerization reactor with >10 to < 400 mols of said activator compound per mol of titanium compound in said precursor composition.

Claim 4

A catalyst composition as in claim 1 wherein said partially activated precursor composition is completely activated with >10 to < 400 mols of said activator compound per mole of Ti in said precursor composition, said complete activation being conducted so as to thereby prepare a solid dry catalyst composition prior to the feeding thereof to a polymerization reactor, without having to heat said catalyst composition above 50°C.

Claim 5

A process for preparing a catalyst composition which comprises A) forming a precursor composition of the formula wherein R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I or mixtures thereof, ED is an electron donor compound, m is s 0.5 to < 56, n is 0, 1 or 2, p is > 2 to < 116, and q is > 2 to ≤ 85 by dissolving at least one magnesium compound and at least one titanium compound in at least one electron donor compound so as to thereby form a solution of said precursor composition in said electron donor compound, and recovering said precursor composition from said solution, said magnesium compound having the structure MgX 2 , said titanium compound having the structure Ti(OR) a X b , wherein a is 0, 1 or 2, b is 1 to 4 inclusive and a + b = 3 or 4, said electron donor compound being a liquid organic compound in which said magnesium compound and said titanium compound are soluble and which is selected from the group consisting of alkyl esters. of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones, said magnesium compound, said titanium compound and said electron donor compound being employed in such amounts as to satisfy the values of m, n, p and q, B) impregnating said precursor composition onto a porous support either before or after recovering said precursor composition from the electron donor solution thereof, and C) partially activating said precursor composition with >0 to < 10 mols of activator compound per mol of Ti in said precursor composition, said activator compound having the formula wherein X' is Cl or OR"', R" and R"' are the same or different, and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c + d + e = 3, said activating being conducted after the recovery of said impregnated precursor composition from the electron donor solution thereof.

Claim 6

A process for preparing a catalyst composition which comprises A) forming a precursor composition of the formula wherein R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I or mixtures thereof, ED is an electron donor compound, m is s 0.5 to < 56, n is 0, 1 or 2, p is > 2 to < 116, and q is > 2 to ≤ 85 by dissolving at least one magnesium compound and at least one titanium compound in at least one electron donor compound so as to thereby form a solution of said precursor composition in said electron donor compound, and recovering said precursor composition from said solution, said magnesium compound having the structure MgX 2 , said titanium compound having the structure Ti(OR) a X b , wherein a is 0, 1 or 2, b is 1 to 4 inclusive and a + b = 3 or 4, said electron donor compound being a liquid organic compound in which said magnesium compound and said titanium compound are soluble and which is selected from the group consisting of alkyl esters. of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones, said magnesium compound, said titanium compound and said electron donor compound being employed in such amounts as to satisfy the values of m, n, p and q, B) impregnating said precursor composition onto a porous support either before or after recovering said precursor composition from the electron donor solution thereof, and C) partially activating said precursor composition with >0 to < 10 mols of activator compound per mol of Ti in said precursor composition, said activator compound having the formula wherein X' is Cl or OR"', R" and R"' are the same or different, and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c + d + e = 3, said activating being conducted after the recovery of said impregnated precursor composition from the electron donor solution thereof.

Claim 7

A process as in claim 4 in which said partially activated impregnated precursor composition is completely activated in a polymerization reactor with >10 to < 400 mols of said activator compound per mol of titanium compound in said precursor composition.

Claim 8

A process as in claim 4 in which said partially activated impregnated precursor composition is completely activated with >10 to < 400 mols of said activator compound per mol of Ti in said precursor composition, said complete activation being conducted so as to thereeby prepare a solid dry catalyst composition, prior to the feeding thereof to a polymerization reactor, without having to heat said catalyst composition above 50°C.

Claim 9

A catalyst process for producing ethylene copolymer with a Ti containing catalyst at a productivity of ≥ 50,000 pounds of polymer per pound of Ti in a reactor under a pressure of<1000 psi in the gas phase, said polymer being produced in granular form and having a density of > 0.91 to < 0.94 and a melt flow ratio of > 22 to < 32, which comprises polymerizing ethylene with at least one C 3 to C 8 alpha olefin at a temperature of about 30 to-105°C by contacting the monomer charge with, in the presence of about 0 to 2.0 mols of hydrogen per mol of ethylene in the gas phase reaction zone, particles of a catalyst composition comprising a precursor composition of the formula ; wherein R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I or mixtures thereof, ED is an electron donor compound, m is > 0.5 to ≤ 56, n is 0, 1 or 2, p is > 2 to < 116, and q is > 2 to ≤ 85, ; said precursor composition being impregnated in a porous support and being first partially activated outside of said reactor with >0 to < 10 mols of activator compound per mol of Ti in said precursor composition, and then completely acti- vated either outside of said reactor with >10 to < 400 mols of activator compound per mol of Ti in said precursor composition so as to thereby prepare a solid dry catalyst composition, prior to the feeding thereof to said reactor, without heating said catalyst composition above 50°C during activation stages conducted with >10 mols of said activator compound, or completely activated in said reactor with >10 to < 400 mols of activator compound permol of Ti in said precursor composition, said activator compound having the formula wherein X 1 is.Cl or OR"', R" and R"' are the same or different, and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c + d + e = 3, said electron donor compound being a liquid organic compound in which said precursor composition is soluble and which is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, ali- phatic ethers, cyclic ethers and aliphatic ketones.

Claim 10

A catalyst process for producing ethylene copolymer with a Ti containing catalyst at a productivity of ≥ 50,000 pounds of polymer per pound of Ti in a reactor under a pressure of<1000 psi in the gas phase, said polymer being produced in granular form and having a density of > 0.91 to < 0.94 and a melt flow ratio of > 22 to < 32, which comprises polymerizing ethylene with at least one C 3 to C 8 alpha olefin at a temperature of about 30 to-105°C by contacting the monomer charge with, in the presence of about 0 to 2.0 mols of hydrogen per mol of ethylene in the gas phase reaction zone, particles of a catalyst composition comprising a precursor composition of the formula ; wherein R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I or mixtures thereof, ED is an electron donor compound, m is > 0.5 to ≤ 56, n is 0, 1 or 2, p is > 2 to < 116, and q is > 2 to ≤ 85, ; said precursor composition being impregnated in a porous support and being first partially activated outside of said reactor with >0 to < 10 mols of activator compound per mol of Ti in said precursor composition, and then completely acti- vated either outside of said reactor with >10 to < 400 mols of activator compound per mol of Ti in said precursor composition so as to thereby prepare a solid dry catalyst composition, prior to the feeding thereof to said reactor, without heating said catalyst composition above 50°C during activation stages conducted with >10 mols of said activator compound, or completely activated in said reactor with >10 to < 400 mols of activator compound permol of Ti in said precursor composition, said activator compound having the formula wherein X 1 is.Cl or OR"', R" and R"' are the same or different, and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c + d + e = 3, said electron donor compound being a liquid organic compound in which said precursor composition is soluble and which is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, ali- phatic ethers, cyclic ethers and aliphatic ketones.

Claim 11

A process as in claim 7 which is conducted in a fluid bed process.

Claim 12

A process as in claim 7 in which said precursor composition is partially activated with about >0 to ≤ 10 mols of said activator compound outside of said reactor and is completely activated in said reactor with sufficient activator compound to provide an Al/Ti ratio of about 15 to 60 in said reactor.