Attenuated post-metallocene catalysts
A method of making an attenuated-light-off post-metallocene catalyst (“attenuated post-metallocene catalyst” or “attenuated P-M catalyst”), the method comprising combining a faster-light-off catalyst with an effective amount of a kinetics modifier compound of formula (A1), (B 1 ), or (C 1 ): R 5 —C≡C—R 6 (A 1 ), (R 5 ) 2 C═C═C(R 6 ) 2 (B 1 ), or (R 5 )(R 7 )C═C(R 6 )(R 7 ) (C 1 ) as defined herein under effective reaction conditions to give an attenuated post-metallocene catalyst that exhibits an attenuated light-off kinetics profile (relative to that of the faster-light-off catalyst); wherein the faster-light-off catalyst has been made by activating a post-metallocene precatalyst (i.e., an unactivated “coordination entity” or “ligand-metal complex”) of structural formula (I): (D) d M(T) t (Q) q (X) x (I) as defined herein; and related methods, compositions and uses.
1 . A method of making an attenuated post-metallocene catalyst, the method comprising combining a faster-light-off catalyst with an effective amount of a kinetics modifier compound of formula (A 1 ) or (B 1 ): R 5 -C≡C-R 6 (A 1 ) or; (R 5 ) 2 C═C═C(R 6 ) 2 (B 1 ) under effective reaction conditions to give an attenuated-light-off post-metallocene catalyst that exhibits an attenuated light-off kinetics profile; wherein the faster-light-off catalyst has been made by activating a post-metallocene precatalyst of structural formula (I): (D) d M(T) t (Q) q (X) x (I); wherein in formula (A 1 ) or (B 1 ) each of R 5 and R 6 independently is H or R 7 ; and each R 7 independently is a (C 1 -C 20 ) hydrocarbyl, -C(═O)-O-(unsubstituted C 1 -C 12 )hydrocarbyl), a (C 1 -C 17 ) heterohydrocarbyl, or a tri((C 1 -C 20 ) hydrocarbyl)silyl, or two R 7 are taken together to form a (C 3 -C 6 ) alkylene; with the proviso that each R 7 lacks a carbon-carbon double bond; wherein each (C 1 -C 20 )hydrocarbyl independently is unsubstituted or substituted with from 1 to 4 substituent groups R S ; wherein each substituent group R S is independently selected from halogen, unsubstituted (C 1 -C 5 )alkyl, -C≡CH, —OH, —NH 2 , —N(H)(unsubstituted (C 1 -C 5 )alkyl), —N(unsubstituted (C 1 -C 5 )alkyl) 2 , —COOH, and —COO(unsubstituted (C 1 -C 5 )alkyl); and wherein in formula (I): metal M is Ti, Hf, or Zr; subscript d is 0, 1, or 2; subscript t is 0 or 1; subscript q is 0 or 1; subscript x is 1, 2, or 3; each ligand D independently is a didentate organoheteryl or a didentate organoheterylene; ligand T is a tridentate organoheterylene; and ligand Q is a tetradentate organoheterylene; each X is a monodentate group independently selected from a halogen atom, ((C 1 -C 20 )alkyl) 3-g —(phenyl) g Si— wherein subscript g is 0, 1, 2, or 3; CH 3 , a(C 2 -C 20 )alkyl-CH 2 , a (C 6 -C 12 )aryl-((C 0 -C 10 )alkylene)-CH 2 , a (C 1 -C 6 ) alkyl-substituted (C 6 -C 12 )aryl, a (C 1 -C 6 )alkoxy-substituted (C 6 -C 12 )aryl, a (C 1 -C 6 ) alkoxy-substituted benzyl, and a (C 1 -C 6 )alkyl-substituted benzyl; or one X is a 4-(C 1 -C 20 ) alkyl-substituted 1,3-butadiene molecule and each of the remaining X, if any, independently is the monodentate group X.
2 . The method of claim 1 wherein the faster-light-off catalyst is of formula (II): (D) d [M + ](T) t (Q) q (X) x-1 A − (II); and wherein the attenuated post-metallocene catalyst is of formula (III): (D) d [M + ](T) t (Q) q (X) x-2 (R) A − (III); wherein subscripts d, t, q, and x; metal M; and ligands D, T, Q, and X are as defined for formula (I); wherein A − is an anion; and wherein R is a ligand of formula (A), (B), or (C): —C(R 5 )═C(X)R 6 (A), —C(R 5 ) 2 -C(X)═C(R 6 ) 2 (B), or —C(R 5 )(R 7 )—C(X)(R 6 )(R 7 ) (C), respectively; and wherein R 5 to R 7 are as defined previously for formula (A 1 ) or (B 1 ) respectively.
3 . The method of claim 1 wherein the post-metallocene precatalyst is of formula (Ia): (D) d M(X) x (Ia), wherein metal M is Ti, Hf, or Zr; subscript d is 1 or 2; subscript x is 2 or 3; each ligand D independently is the didentate organoheteryl or the didentate organoheterylene; each X is as defined for formula (I).
4 . The method of claim 1 wherein the post-metallocene precatalyst of formula (I) is of formula (Ib): MT(X) 2 (Ib), wherein metal M is Ti, Hf, or Zr; ligand T is the tridentate organoheterylene; each X is as defined for formula (I).
5 . The method of claim 1 wherein the post-metallocene precatalyst of formula (I) is of formula (Ic): MQ(X) 2 (Ic), wherein metal M is Ti, Hf, or Zr; ligand Q is the tetradentate organoheterylene; each X is as defined for formula (I).
6 . The method of claim 1 wherein the kinetics modifier compound is of formula (A 1 ):R 5 -C≡C-R 6 (A 1 ) that is selected from phenylacetylene; a (substituted-phenyl)acetylene; diphenylacetylene; a substituted diphenylacetylene; a cycloalkylacetylene; an acetylene of formula HC≡CSi(phenyl) h ((C 1 -C 20 )alkyl) 3-h , wherein subscript h is an integer from 0 to 3; and an acetylene of formula HC≡C-(CH 2 ) m CH 3, wherein subscript m is an integer from 1 to 15.
7 . The method of claim 1 wherein the kinetics modifier compound is of formula (B 1 ) (R 5 ) 2 C═C═C(R 6 ) 2 (B 1 ) and is selected from a cycloalkylallene; an alkylallene; a dialkylallene; a trialkylallene; a trialkylsilylallene; a vinylidenecycloalkane; and an alkyl ester of an allenecarboxylic acid.
8 . The method of claim 1 wherein the method further comprises making a mixture of the attenuated post-metallocene catalyst, a support material, and an inert hydrocarbon solvent and removing the inert hydrocarbon solvent from the mixture so as to give the attenuated post-metallocene catalyst disposed on the support material.
9 . A method of making an attenuated post-metallocene catalyst the method comprising combining a faster-light-off catalyst with an effective amount of a kinetics modifier compound of formula (A 1 ), (B 1 ), or (C 1 ); R 5 -C≡C-R 6 (A 1 ), (R 5 ) 2 C═C═C(R 6 ) 2 (B 1 ), or (R 5 )(R 7 )C═C(R 6 )(R 7 ) (C 1 ) under effective reaction conditions to give an attenuated-light-off post-metallocene catalyst that exhibits an attenuated light-off kinetics profile; wherein the faster-light-off catalyst has been made by activating a post-metallocene precatalyst of structural formula (I): (D) d M(T) t (Q) q (X) x (I): wherein in formula (A 1 ), (B 1 ) , or (C 1 ) each of R 5 and R 6 independently is H or R 7 ; and each R 7 independently is a (C 1 -C 20 )hydrocarbyl, —C(═O)—O—(unsubstituted C 1 -C 12 )hydrocarbyl), a (C 1 -C 17 )heterohydrocarbyl, or a tri((C 1 -C 20 )hydrocarbyl)silyl, or two R 7 are taken together to form a (C 3 -C 6 )alkylene; with the proviso that each R 7 lacks a carbon-carbon double bond; wherein each (C 1 -C 20 )hydrocarbyl independently is unsubstituted or substituted with from 1 to 4 substituent groups R S ; wherein each substituent group R S is independently selected from halogen, unsubstituted (C 1 -C 5 )alkyl, —C≡CH, —OH, —NH 2 , —N(H)(unsubstituted (C 1 -C 5 )alkyl), —N(unsubstituted C 1 -C 5 )alkyl) 2 , —COOH, and —COO(unsubstituted) (C 1 -C 5 )alkyl; wherein the post-metallocene precatalyst of formula (I) is selected from the group consisting of: a post-metallocene precatalyst of formula (Ia)-1
wherein each Ar 1 and Ar 2 independently is an unsubstituted or substituted aromatic group selected from phenyl, substituted phenyl, biphenyl, substituted biphenyl, anthracene, substituted anthracene, carbazolyl, and substituted carbazolyl, wherein each substituent of the substituted aromatic group independently is alkyl; each group R a1 and R a2 independently is H or a (C 1 -C 20 ) alkyl; each subscript 0-3 independently is 0, 1, 2, or 3; and M and X are as defined for formula (I); and a post-metallocene precatalyst of formula (Ia)-2:
wherein M and X are as defined for formula (I); each subscript 1-5 independently is 1, 2, 3, 4, or 5; and each of R a3 and R a7 independently is (C 1 -C 20 )alkyl or (C 6 -C 12 ) aryl and each of R a4 to R a6 independently is (C 1 -C 20 )alkyl or R a4 to R a6 are taken together to form a trivalent group of formula ═C(H)—CH 2 CH 2 CH 2 —.
10 . A method of making an attenuated post-metallocene catalyst, the method comprising combining a faster-light-off catalyst with an effective amount of a kinetics modifier compound of formula (A 1 ), (B 1 ), or (C 1 ); R 5 -C≡C-R 6 (A 1 ), (R 5 ) 2 C═C═C(R 6 ) 2 (B 1 ), or (R 5 )(R 7 )C═C(R 6 )(R 7 ) (C 1 ) under effective reaction conditions to give an attenuated-light-off post-metallocene catalyst that exhibits an attenuated light-off kinetics profile; wherein the faster-light-off catalyst has been made by activating a post-metallocene precatalyst of structural formula (I): (D) d M(T) t (Q) q (X) x (I): wherein in formula (A 1 ), (B 1 ), or (C 1 ) each of R 5 and R 6 independently is H or R 7 ; and each R 7 independently is a (C 1 -C 20 )hydrocarbyl, —C(═O)—O—(unsubstituted C 1 -C 12 )hydrocarbyl), a(C 1 -C 17 )heterohydrocarbyl, or a tri((C 1 -C 20 )hydrocarbyl)silyl or two R 7 are taken together to form a (C 3 -C 6 )alkylene; with the proviso that each R 7 lacks a carbon-carbon double bond; wherein each C 1 -C 20 )hydrocarbyl independently is unsubstituted or substituted with from 1 to 4 substituent groups R S ; wherein each substituent group R S is independently selected from halogen, unsubstituted(C 1 -C 5 ) alkyl, —C≡CH, —OH, —NH 2 , —N(H)(unsubstituted (C 1 -C 5 )alkyl), —N(unsubstituted C 1 -C 5 )alkyl) 2 , —COOH, and —COO(unsubstituted (C 1 -C 5 )alkyl); wherein the post-metallocene precatalyst of formula (I) is a post-metallocene precatalyst of formula (Ib)-1
wherein M is Ti, Hf, or Zr; each subscript 0-3 independently is 0, 1, 2, or 3; each of groups R b1 to R b6 independently is H or a (C 1 -C 20 )alkyl; and X is as defined for formula (I).
11 . An attenuated post-metallocene catalyst made by the method of claim 1 .
12 . A method of feeding a post-metallocene catalyst to a slurry-phase or gas-phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, the method comprising making the attenuated post-metallocene catalyst outside of the reactor and according to the method of claim 1 , and feeding the attenuated post-metallocene catalyst in neat form or as a solution or slurry thereof in an inert hydrocarbon liquid through a feed line free of olefin monomer into the slurry-phase or gas-phase polymerization reactor.
13 . A multimodal catalyst system comprising the attenuated post-metallocene catalyst of claim 12 and at least one second catalyst selected from the group consisting of an unattenuated a post-metallocene catalyst described herein, a different attenuated post-metallocene catalyst, and a metallocene catalyst.
14 . A method of making a polyolefin polymer, the method comprising contacting at least one 1-alkene monomer with the attenuated post-metallocene catalyst made by the method of claim 1 under slurry-phase or gas-phase polymerization conditions in a slurry-phase or gas-phase polymerization reactor containing a moving bed of polyolefin resin, thereby making the polyolefin polymer.