Titanium biphenylphenol polymerization catalysts
Embodiments of the present disclosure directed towards titanium biphenylphenol polymerization precatalysts of Formula (I).
1. A titanium biphenylphenol polymerization precatalyst of Formula I:
wherein each of R 7 and R 8 is independently a C 1 to C 20 alkyl, aryl, aralkyl or a hydrogen; wherein each of R 5 and R 10 is a dialkyl or trialkyl substituted silyl;
wherein each of R 2 and R 13 is independently a C 1 to C 20 alkyl, aryl, aralkyl or a hydrogen; wherein each of R 15 and R 16 is a 2,7-disubstituted carbazolyl or a 3,6-disubstituted carbazolyl;
wherein L is a C 2 -C 4 alkylene that forms a 2-carbon bridge, 3-carbon bridge, or a 4-carbon bridge respectively, between the two oxygen atoms to which L is covalently bonded;
wherein each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is independently a halide or a hydrogen; and
wherein each X is independently a hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenoxy group, aryloxy group, or a hydrogen and at least one X is not a hydrocarbyl.
2. The precatalyst of claim 1 , wherein each of R 7 and R 8 is a C 1 alkyl or each of R 7 and R 8 is a hydrogen.
3. The precatalyst of claim 1 , wherein each of R 5 and R 10 is octyl dimethyl silyl.
4. The precatalyst of claim 1 , wherein each of R 2 and R 13 is a 1,1-dimethylethyl.
5. The precatalyst of claim 1 , wherein each of R 15 and R 16 is a 2,7-di-t-butylcarbaoyl or a 3,6-di-t-butylcarbazolyl.
6. The precatalyst of claim 1 , wherein L is a saturated C 3 alkylene.
7. The precatalyst of claim 1 , wherein each X is chlorine.
8. The precatalyst of claim 1 , further comprising a silica support that is free of activator, wherein the silica support that is free of activator supports the precatalyst.
9. A method of making a titanium biphenylphenol polymerization catalyst, the method comprising contacting, under activating conditions, a titanium biphenylphenol polymerization precatalyst of Formula I of claim 1 with an activator so as to activate the titanium biphenylphenol polymerization precatalyst of Formula I, thereby making the titanium biphenylphenol polymerization catalyst.
10. A titanium biphenylphenol polymerization catalyst made by the method of claim 9 .
11. A method of making a polyethylene composition, the method comprising:
polymerizing an olefin monomer in a single gas-phase polymerization reactor in presence of the titanium biphenylphenol polymerization catalyst of claim 10 to make a polyethylene composition.
12. The method of claim 11 , before the polymerizing step, further comprising:
making the titanium biphenylphenol polymerization catalyst; and
feeding the titanium biphenylphenol polymerization catalyst into the single gas-phase polymerization reactor.
13. A titanium biphenylphenol polymerization precatalyst of Formula I:
wherein each of R 7 and R 8 is independently a C 1 to C 20 alkyl, aryl, aralkyl or a hydrogen;
wherein each of R 5 and R 10 is fluorine;
wherein each of R 2 and R 13 is independently a C 1 to C 20 alkyl, aryl aralkyl or a hydrogen;
wherein each of R 15 and R 16 is a 2,7-disubstituted carbazolyl or a 3,6-disubstituted carbazolyl;
wherein L is a C 2 -C 4 alkylene that forms a 2-carbon bridge, 3-caron bridge, or a 4-carbon bridge respectively, between the two oxygen atoms to which L is covalently bonded;
wherein each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is independently a halide or a hydrogen; and
wherein each X is independently a hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenoxy group, aryloxy group, or a hydrogen and at least one X is not a hydrocarbyl.
14. A method making a titanium biphenylphenol polymerization catalyst, the method comprising contracting, under activating conditions, a titanium biphenylphenol polymerization precatalyst of Formula I with an activator so as to activate the titanium biphenylphenol polymerization precatalyst of formula I, thereby making the titanium biphenylphenol polymerization catalyst, wherein Formula I is:
wherein each of R 7 and R 8 is independently a C 1 to C 20 alkyl, aryl, aralkyl or a hydrogen;
wherein each of R 5 and R 10 is independently a C 1 to C 20 alkyl, aryl, aralkyl, halide, or a hydrogen;
wherein each of R 2 and R 13 is independently a C 1 to C 20 alkyl, aryl, aralkyl or a hydrogen;
wherein each of R 15 and R 16 is a 2,7-disubstituted carbazolyl or a 3,6-disubstituted carbazolyl;
wherein L is C 2 -C 4 alkylene that forms a 2-carbon bridge, 3-carbon bridge, or a 4-carbon bridge respectively, between the two oxygen atoms to which L is covalently bonded;
wherein each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is independently a halide or a hydrogen; and
wherein each X is independently a hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenyl group, aryloxy group, or a hydrogen and at least one X is not a hydrocarbyl and
contacting an activator-free solution of the titanium biphenylphenol polymerization precatalyst of Formula I dissolved in an alkane solvent with a silica support containing thereon a spray-dried activator to make the titanium biphenylphenol polymerization catalyst on a silica support.