Attenuated post-metallocene catalysts

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 (A1), (B1), or (C1);

• R5-C≡C-R6 (A1), (R5)2C═C═C(R6)2 (B1), or (R5)(R7)C═C(R6)(R7) (C1) 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)dM(T)t(Q)q(X)x (I):
• wherein in formula (A1), (B1) , or (C1) each of R5 and R6 independently is H or R7;
• and each R7 independently is a (C1-C20)hydrocarbyl, —C(═O)—O—(unsubstituted C1-C12)hydrocarbyl), a (C1-C17)heterohydrocarbyl, or a tri((C1-C20)hydrocarbyl)silyl, or two R7 are taken together to form a (C3-C6)alkylene;
• with the proviso that each R7 lacks a carbon-carbon double bond;
• wherein each (C1-C20)hydrocarbyl independently is unsubstituted or substituted with from 1 to 4 substituent groups RS;
• wherein each substituent group RS is independently selected from halogen, unsubstituted (C1-C5)alkyl, —C≡CH, —OH, —NH2, —N(H)(unsubstituted (C1-C5)alkyl), —N(unsubstituted C1-C5)alkyl)2, —COOH, and —COO(unsubstituted) (C1-C5)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 Ar1 and Ar2 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 Ra1 and Ra2 independently is H or a (C1-C20) 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 Ra3 and Ra7 independently is (C1-C20)alkyl or (C6-C12) aryl and each of Ra4 to Ra6 independently is (C1-C20)alkyl or Ra4 to Ra6 are taken together to form a trivalent group of formula ═C(H)—CH2CH2CH2—.

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 (A1), (B1), or (C1);

• R5-C≡C-R6(A1), (R5)2C═C═C(R6)2 (B1), or (R5)(R7)C═C(R6)(R7) (C1) 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)dM(T)t(Q)q(X)x (I):
• wherein in formula (A1), (B1), or (C1) each of R5 and R6 independently is H or R7;
• and each R7 independently is a (C1-C20)hydrocarbyl, —C(═O)—O—(unsubstituted C1-C12)hydrocarbyl), a(C1-C17)heterohydrocarbyl, or a tri((C1-C20)hydrocarbyl)silyl or two R7 are taken together to form a (C3-C6)alkylene;
• with the proviso that each R7 lacks a carbon-carbon double bond;
• wherein each C1-C20)hydrocarbyl independently is unsubstituted or substituted with from 1 to 4 substituent groups RS;
• wherein each substituent group RS is independently selected from halogen, unsubstituted(C1-C5) alkyl, —C≡CH, —OH, —NH2, —N(H)(unsubstituted (C1-C5)alkyl), —N(unsubstituted C1-C5)alkyl)2, —COOH, and —COO(unsubstituted (C1-C5)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 Rb1 to Rb6 independently is H or a (C1-C20)alkyl;
• and X is as defined for formula (I).