Attenuated post-metallocene catalysts

Patent metadata

Field	Value
Publication number	US-12545751-B2
Application number	US-202117995864-A
Country	US
Kind code	B2
Filing date	May 26, 2021
Priority date	May 29, 2020
Publication date	Feb 10, 2026
Grant date	Feb 10, 2026

Abstract

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.

First claim

The invention claimed is:

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

Assignees

• Dow Global Technologies Llc

Inventors

• Neilson Bethany M
• Kuhlman Roger L
• Baillie Rhett A
• Szul John F

Classifications

• C08F4/611

  Pretreating with non-metals or metal-free compounds · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F4/659 Primary

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64193

  OOOO · CPC title